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Tartaric acid has two asymmetric carbons which permit In processes where 50% stock solutions are mandatory
the formation of a dextro ( + ) rotatory form, a Ievo (-) such as carbonated beverages and jams and jellies, fumaric
rotatory form, and a meso form which is inactive due to acid cannot be used.
internal compensation. A racemic mixture of dextro- and Fumaric acid is extensively used in noncarbonated fruit
levo-rotatory forms is also a possibility. juice drinks. Its greater acid strength allows lower use lev-
Apart from very limited synthetic production in South els than citric acid and its solubility and rate of solution
Africa, tartaric acid is extracted from the residues of the are sufficient for this process. Fumaric is also used in con-
wine industry. Therefore the natural form, L-( + )tartaric sumer packed gelatin desserts because of its low hygro-
acid, is the article of commerce. The structure in Table 1 scopicity. The only salt of fumaric acid that has had any
is L-( + )tartaric acid. application in the food industry is ferrous fumarate for iron
Potassium acid tartrate, also known as cream of tartar, fortification.
is the major salt used in the food industry. It is occasionally
used as the acid portion of a chemical leavening system for
baked goods. It is also used as a doctor in candy making to FUNCTIONS OF FOOD ACIDS
prevent sugar crystallization by inverting a portion of the
sucrose. Food acidulants and their salts perform a variety of func-
Tartaric acid can be used in most food categories and tions. These functions are as antioxidants, curing and pick-
functions that require acidification but in practice it is lim- ling agents, flavor enhancers, flavoring agents and adju-
ited to grape flavored products, particularly beverages and vants, leavening agents, pH control agents, sequestrants,
candies. It is also used where high tartness is desired in a and synergists. The definitions for these functions are con-
highly soluble acid. tained in the U.S. Code of Federal Regulations (5). Some
of the functions overlap and in any given application an
acidulant will often perform two or more functions.
FUMARIC ACID
Flavor Enhancer and Flavor Adjuvant
Fumaric acid is also a naturally occurring, organic, general
purpose food acid. Although not found ubiquitously or in These functions are performed by a majority of the acidu-
the concentrations of citric acid, fumaric nevertheless is lants consumed by the food and beverage industries. Acids
found in all mammals as well as rice, sugar cane, wine, provide a tang or tartness that compliments and enhances
plant leaves, bean spouts, and edible mushrooms. many flavors but do not impart a characteristic flavor of
Fumaric acid is made synthetically by the isomerization their own. The acid itself should have a clean taste and be
of maleic acid. It is also produced by fermentation of glu- free of off notes that are foreign to foods. Some acids, such
cose or molasses with Rhizopus spp. (4). It is a white crys- as succinic acid, have a distinctive taste which is incom-
talline powder that has the clean tartness necessary for a patible with most food products; and hence, these acids
food acidulant. Table 1 shows that fumaric acid is the have achieved very little use.
strongest of the food acids and is also the least soluble. The The need for tartness is obvious. Citrus and berry fla-
low solubility of fumaric acid limits its usefulness in foods. vors would be flat and lifeless without at least a touch of
acidity. However, not all fruit flavors require the same de- cure color in processed meats, and aids the peelability of
gree of tartness. Lemon candies and beverages are tradi- frankfurters.
tionally very sour, while orange and cherry are a little less Gelatin desserts are generally adjusted to an average
tart. Flavors like strawberry, watermelon, and tropical pH of 3.5 for proper flavor and good gel strength. However,
fruits require only a trace of acidity for flavor enhance- the pH can range from 3.0-4.0. Adipic and fumaric acids
ment. are used in gelatin desserts that are packaged for retail
In noncola carbonated beverages, beverage mixes, can- sales. Their low hygroscopicity allows use of packaging ma-
dies and confections, syrups and toppings, and any appli- terials that are less moisture resistance and less expen-
cation where high solubility is required, citric and malic sive.
acids are used extensively. Fumaric acid is used in all In jams and jellies, the firmness of pectin gel is depen-
ready constituted still beverages for economic reasons. dent on rigid pH control. Slow set pectin attains maximum
Several acids are suitable for some flavors but not for firmness at pH 3.05-3.15 while rapid set pectin reaches
others. For example, phosphoric acid is used in cola bev- maximum firmness at pH 3.35-3.45 (8). The addition of
erages but not in fruit flavored ones. Tartaric acid presents buffer salts such as sodium citrate and sodium phosphate
still another category. It has traditionally been used in assist in maintaining the pH within the critical pH range
grape flavored products even though it is suitable for other for the pectin type. These salts also delay the onset of gel-
flavors. ation by lowering the gelation temperature. The acid
The general purpose acids impart different degrees of should be added as late as possible in the process. Pre-
tartness that are in part a result of their different acid mature acid addition will result in some pectin hydrolysis
strengths. Table 2 summarizes the tartness equivalence of and weakening of the gel in the finished product. The acid
the general purpose acids. The relationship shown is based is added as a 50% stock solution and thus soluble acids are
only on tartness intensity and not character of flavor. This required. Citric is generally used in this application but
relationship can change depending on the formulation in- malic and tartaric are also satisfactory.
gredients and the particular flavor system being studied. The United States Federal Standards of Identity (9)
Malic acid, for example, has been claimed to be 10-15% provide for the direct acidification of cottage cheese by the
more tart than citric acid in juice based, fruit flavored still addition of phosphoric, lactic, citric, or hydrochloric acid as
beverages. In fruit and berry carbonated beverages, both an alternate procedure to production with lactic acid pro-
acids have been perceived as being of equal tartness. Tart- ducing bacteria. Milk is acidified to a pH of 4.5-4.7 without
ness is a difficult property to measure precisely and it must coagulation, and then after mixing, is heated to a maxi-
be determined by a trained and experienced taste panel. mum of 12O0F without agitation to form a curd. Glucono-
Acids have also been used for their effects on masking delta-lactone is also permitted for this application. It is
undesired flavors in foods and food ingredients. Both citric added in such amounts as to reach a final pH value of 4.5-
and malic acids and citrate salts are known for their ability 4.8 and is held until it becomes coagulated. GDL is pre-
to mitigate the unpleasant aftertaste of saccharin. Gluco- ferred for this application because it must undergo hydro-
nate salts and glucono-delta-lactone (GDL) have been pat- lysis to gluconic acid before it can lower pH. Thus the rate
ented for this function (6,7). Claims of enhanced benefits at which the pH is lowered is slowed, avoiding local de-
for malic acid over citric acid when used with the new in- naturation.
tense sweeteners have been made but definitive advan- The activity of antimicrobial agents (benzoic acid, sorbic
tages have not yet been demonstrated. acid, propionic acid) is due primarily to the undissociated
acid molecule (10). On the basis of undissociated acid con-
pH Control centration, Giannuzzi et al. (11) have shown that citric acid
is more effective than ascorbic or lactic acids in inhibiting
Control of acidity in many food products is important for a Listeria monocytogenes in a trypticase soya broth contain-
variety of reasons. Precise pH control is important in the ing yeast extract. Under refrigerated temperatures, higher
manufacture of jams, jellies, gelatin desserts, and pectin inhibition indices were obtained in the presence of lower
jellied candies in order to achieve optimum development concentrations of citric acid. Activity is therefore pH de-
of gel character and strength. Precise pH control is also pendent and theoretical activity at any pH can be calcu-
important in the direct acidification of dairy products to lated. Table 3 shows the effect of pH on dissociation. It can
achieve a smooth texture and proper curd formation. In- be seen why acidification improves preservative perfor-
creasing acidity enhances the activity of antimicrobial food
preservatives, decreases the heat energy required for ster-
ilization, inactivates enzymes, aids the development of
Table 3. Effect of pH on Dissociation0
pH Sorbic Benzoic Propionic
Table 2. Tartness Equivalence 3 98 94 99
4 86 60 88
General-purpose acids Weight equivalence
5 37 13 42
Citric 1.0 6 6 1.5 6.7
Fumaric 0.6-0.7 7 0.6 0.15 0.7
Tartaric 0.8-0.9 (pKJ 4.67 4.19 4.87
Malic 0.85-1.0
"Percentage of undissociated acid.
mance and why benzoates are not generally recommended ically leavened baked goods is the reaction of an acidulant
above pH 4.5. with a carbonate or bicarbonate resulting in the generation
The use of acid to make heat preservation more effec- of carbon dioxide. The physical state of some food acids as
tive, especially against spore-forming food spoilage organ- dry solids is a property appropriate for beverage mixes and
isms, is an established part of food technology. Under U.S. chemical leavening systems. In the absence of water, there
Federal Standards of Identity (12), the addition of a suit- is essentially no interaction between such acids and so-
able organic acid or vinegar is required in the canning of dium bicarbonate. Thus these dry mixes can be stored for
artichokes (to reduce the pH to 4.5 or below) and is optional long periods.
in the canning of the vegetables listed in Table 4. Vinegar A desired property for an acidulant in a chemical leav-
is not permitted in mushrooms. Citric acid is specifically ening system is that it react smoothly with the sodium
permitted as an optional ingredient in canned corn and bicarbonate to assure desirable volume, texture, and taste.
canned field corn. Leavening acids and acid salts vary quantitatively in their
The advantage of acidification is especially well illus- neutralizing capacity. This relationship is shown in Table
trated in the canning of whole tomatoes. When the pH of 5. A new heat-activated leavening agent, dimagnesium
these is greater than 4.5, there is increased incidence of phosphate, was recently reported for use in finished baked
spoilage in the cans. When tomatoes of pH 3.9 are pro- products (14).
cessed at 2120F, only 34 min are required to kill a normal The various acids differ in their rate of reaction in re-
or high spore load without decreases in color and flavor and sponse to elevation of temperature. This must be taken
deterioration of structure. In contrast, at pH 4.8 the cook- into consideration in selecting an acidulant for a particular
ing must be 110 min (13). condition. Under some conditions, a mixture of acidulants
In the processing of fruits and vegetables, whether for may be most suitable to achieve desired reaction times.
canning, freezing, or dehydration, the prevention of dis- Table 6 compares the reaction times of GDL and cream of
coloration in the fresh cut tissue is a major concern. Re- tartar.
actions in which polyphenolic compounds are changed by Glucono-delta-lactone is an inner ester of gluconic acid
oxidation into colored materials play an important part in that is produced commercially by fermentation involving
this discoloration which may be accompanied by undesir- Aspergillus niger or A. suboxydans. When it hydrolyzes,
able flavors. The ascorbic acid naturally present in many gluconic acid forms and this reacts with sodium bicar-
fruits and vegetables offers some protection, but this is of bonate. Although GDL is relatively expensive, there are
relatively short duration because of destruction of ascorbic certain specialized types of products such as pizza dough
acid by natural enzymes and air. Heating, as applied in and cake doughnuts for which it is eminently suited as an
blanching, destroys the oxidative enzymes which cause acid component of the leavening system. Cream of tartar
discoloration but may alter flavor and texture if continued (potassium acid tartrate) has limited solubility at lower
sufficiently to completely inactivate oxidative enzymes. temperatures. There is a limited evolution of gas during
Lowering pH by addition of acid substantially decreases the initial stages of mixing in reduced temperature bat-
the activity of natural color producing enzymes in fruits.
Citric acid also sequesters traces of metals which may ac-
celerate oxidation. Even greater protection is obtained by Table 5. Neutralizing Value of Various Acidulants Used in
using citric acid in conjunction with a reducing agent such Chemical Leavening
as ascorbic or erythorbic acid. Some processors have found
that a combination of sodium erythorbate and citric acid Parts acid to neutralize
best serves their needs. one part sodium
Acid bicarbonate
Leavening Agent Fumaric 0.69
Glucono-delta-lactone 2.12
The basis for the formulation of effervescent beverage pow- Cream of tartar 2.24
ders, effervescent compressed tablet products, and chem- Sodium acid pyrophosphate 1.39
Anhydrous monocalcium phosphate 1.20
Monocalcium phosphate monohydrate 1.25
Table 4. Canned Vegetables in which Use of Acids is Sodium aluminum sulfate 1.00
Optional Sodium aluminum phosphate 1.00
Asparagus Celery Potatoes
Bean sprouts Greens, collard Rutabagas
Beans, butter Greens, dandelion Salsify
Beans, lima Greens, mustard Spinach Table 6. Comparison of Carbon Dioxide Evaluation in
Beans, shelled Kale Sweet peppers, green GDL and Cream of Tartar at Room Temperature
Beet greens Mushrooms Sweet peppers, red
Time (min) GDL (%) Cream of tartar (%)
Beets Okra Sweet potatoes
Broccoli Onions Swiss chard 0.5 12.7 53.7
Brussels sprouts Parsnips Tomatoes 2 19.5 80.0
Cabbage Peas, black-eyed Truffles 5 32.3 92.0
Carrots Peas, field Turnip greens 20 69.0 99.4
Cauliflower Pimientos Turnips 60 92.4 100.0
ters. At room temperature and above, the rate of reaction 2. GDL to be used at 8 oz to each 100 Ib of meat in
increases. Because of these characteristics, and its pleas- cured, comminuted meat products and at 16 oz per
ant taste, cream of tartar is used in some baking powders 100 Ib of meat in Genoa salami.
and in the leavening systems of a number of baked goods 3. Sodium acid pyrophosphate not to exceed, alone or
and dry mixes. in combination with other curing accelerators, 8 oz
per 100 Ib of meat nor 0.5% in the finished product.
Antioxidants, Sequestrants, and Synergists 4. Citric acid or sodium citrate to replace up to 50% of
Oxidation is promoted by the catalytic action of certain me- the ascorbate or erythorbates used or in 10% solution
tallic ions present in many foods in trace quantities. If not to spray surfaces of cured cuts.
naturally present in a food, minute quantities of these met-
als, particularly iron and copper, can be picked up from In conjunction with sodium erythorbate or related re-
processing equipment. Oxidation is the cause of rancidity, ducing compounds, GDL accelerates the rate of develop-
an off flavor development in fat. It is also responsible for ment of cure color in frankfurters during smoking. This
off color development that renders a food unappetizing in permits shortening smokehouse time by one half or more
appearance. Hydroxy-polycarboxylic acids such as citric and products have less shrinkage and better shelf life.
acid sequester these trace metals and render them un- The special property of GDL upon which these advan-
available for reaction. In this regard the acids function as tages depend is its lactone structure at room temperature.
antioxidants. In this form there is no free acid group and the GDL can
Hydroxy-polycarboxylic acids are often used in combi- thus be safely added during the emulsifying stage of sau-
nation with antioxidants such as ascorbates or erythor- sage making without fear of shorting out the emulsion. Un-
bates to inhibit color and flavor deterioration caused by der the influence of heat in the smoking process, the ester
trace metal catalyzed oxidation. The ascorbates and ery- hydrolyzes rapidly and is converted in part to gluconic
thorbates as well as BHA, BHT, and other approved anti- acid. This lowers the pH of the emulsion during smoking,
oxidants and reducing agents are oxygen scavengers and providing conditions under which sodium erythorbate or
are effective when used alone. The effect of the combina- other reducing compounds (erythorbic acid, ascorbic acid,
tion of a sequestrant, such as a hydroxy-polycarboxylic and sodium ascorbate) react with greater speed to convert
acid, and an antioxidant is synergistically greater than the the nitrite of the cure mixture into nitric oxide. The nitric
additive effect of either component used alone. oxide, in turn, acts upon the meat pigment to form the
Citric acid is the most prominent antioxidant synergist desired red nitrosomyoglobin.
although malic and tartaric acid have been used. In meat
products, U.S. Department of Agriculture regulations per- CONCLUSION
mit citric acid in dry sausage (0.003%), fresh pork sausage
(0.01%), and dried meats (0.01%). A short dip in a bath
containing 0.25% citric and 0.25% erythorbic acid improves The many functions and broad range of applications of food
quality retention in frozen fish. This treatment is also ap- acidulants makes the selection of the most suitable acid
plicable to shellfish to sequester iron and copper that cat- for a food product a matter of serious concern. The physical
alyze complex blueing and darkening reactions. and chemical properties of food approved acidulants must
Untreated fats and oils, both animal and vegetable, are be an essential part of the knowledge of those food tech-
likely to become rancid in storage. Oxidation is promoted nologists who make the decision.
by the catalytic action of certain metallic ions such as iron,
nickel, manganese, cobalt, chromium, copper, and tin. Min- BIBLIOGRAPHY
ute quantities of these metals are picked up from process-
ing equipment. Adding citric acid to the oil sequesters
1. J. D. Dziezak, "Acidulants: Ingredients That Do More Than
these trace ions, thereby assisting antioxidants to prevent Meet the Acid Test," Food Technol. 44, 75-83 (1990).
development of off flavors. Although the oil solubility of
2. E. F. Bouchard and E. G. Merritt in M. Grayson, ed., Kirk-
citric acid is limited, this can be overcome by first dissolv- Othmer, Encyclopedia of Chemical Technology, Vol. 6, 3rd ed.,
ing it in propylene glycol. The antioxidant can be dissolved John Wiley & Sons, Inc., New York, 1979, pp. 150-179.
in the same solvent so that the two can be added in com- 3. Code of Federal Regulations, Title 21 184.1069.
bination.
4. D. E. Blenford, "Food Acids," Food Flavor Ingredients Pro-
cessing and Packaging 8, 11 (1986).
Curing Accelerator 5. Code of Federal Regulations, Title 21 170.3(o).
The acids approved by the U.S. Department of Agriculture 6. U.S. Pat. 3,285,751 (Nov. 15, 1966) Artificial Sweetner Com-
for this function in meat products (1) must be used only in position, P. Kracauer (to Cumberland Packing Company).
combination with curing agents. In addition to ascorbates 7. U.S. Pat. 3,684,529 (Aug. 15,1972) Sweetening Compositions,
and erythorbates, the approved acids are: J. J. Liggett (to William E. Hoerres).
8. M. Glicksman, Gum Technology in the Food Industry, Aca-
demic Press, Inc., Orlando, FIa., 1969, p. 179.
1. Fumaric acid to be used at a maximum of 0.065% (1
oz-100 Ib) of the weight of the meat before process- 9. Code of Federal Regulations, Title 21 133.129.
ing. 10. Davidson and Juneja, 1990.
11. L. Giannuzzi and N. E. Zaritsky, "Effect of Ascorbic Acid in shown in Table 1. Direct assessment of body fat can be used
Comparison to Citric Acid and Lactic Acid on Listeria mono- to evaluate obesity but the procedure is mainly limited to
cytogenes Inhibition at Refrigerated Temperatures," Lebens-
mittel Wissenschaft and Technologic 29, 278-285 (1996).
research. For public health studies and clinical practice,
simple measures such as height and weight tables, body
12. Code of Federal Regulations, Title 21 155.200.
mass index (BMI), or skinfold measurements are used. The
13. C. T. Townsend, cited in S. Leonard, R. M. Pangborn, and B. BMI (weight in kilograms divided by the square of height
S. Luh, Food Technology 13, 418 (1959). in meters) is an indicator that shows the best correlation
14. D. R. Gard et al., "Evaluation of a New Leavening Acid, Di- with independent measures of body fat (2,5). The use of
magnesium Phosphate, With a Traditional Chemical Leav- BMI was first proposed in 1871 and was long known as the
ening System," Proc. IFTAnn. Meet., 1996, p. 114.
Quetelet index. It is now widely used for assessing the de-
15. Code of Federal Regulations, Title 9 318.7(c)(4). gree of obesity or overweight (Table 2).
Obesity is more than a problem in its own right since it
is closely linked to other diseases such as hypertension,
diabetes, and cardiovascular disease. Many long-term
AFFLUENCE, FOOD EXCESS,
studies have shown a greater risk of these diseases with
AND NUTRITIONAL DISORDERS
increasing levels of obesity, even when other risk factors
are present (5). Later studies have refined these conclu-
Nutrition research in the first half of the present century sions and have demonstrated that the distribution of fat,
focused mainly on identifying and assessing nutrients in especially in the abdominal area, is an additional factor
foods and recognizing deficiency diseases. Since essential (5). A waist circumference of over 40 in. (102 cm) in men
nutrients were unevenly distributed in individual foods, and over 35 in. (89 cm) in women signifies increased risk
consumption of a variety of foods was recommended to in those who have a BMI of 25.0 to 34.9.
provide a more nutritionally balanced diet (1). With un- With increasing BMI, average blood pressure and total
dernutrition still a problem even in the richer countries, cholesterol levels rise while average high-density lipopro-
greater consumption of meat and dairy products was rec- tein (HDLa protective indicator) levels fall (6). Men in
ommended. Increasing wealth in society allowed these the highest obesity category have more than twice the risk
recommendations to match producer and consumer of hypertension and elevated cholesterol when compared
wishes and acknowledged, at the same time, the perceived with men of normal weight. Women in the highest obesity
high nutritional values of these foods of animal origin. By category have four times the risk of either or both of these
the 1950s, however, evidence was accumulating that the risk factors (6). Obese individuals are also at increased risk
high rates of premature deaths from some of the major for several other problems, including lipid disorders, type
chronic diseases could be related to diet. Originally this II diabetes, coronary heart disease, stroke, gallbladder dis-
was thought to be a problem only in the industrialized ease, osteoarthritis, sleep apnea, respiratory problems,
countries but, as medicine conquered infectious diseases, and certain cancers.
the phenomenon became recognized as existing world- A number of efforts have been initiated to educate the
wide. public on altering behavioral risk factors such as improper
The major nutrition-related degenerative diseases in- dietary habits and lack of exercise. Examples include the
clude obesity, diabetes mellitus, cardiovascular diseases, Dietary Guidelines for Americans (Table 3), revised edi-
and certain cancers. The still continuing Framingham tions of which are periodically issued by the U.S. Depart-
Heart Study, which began in 1948, has been responsible ment of Agriculture (USDA) (7). Recently the first federal
for demonstrating many associations between these dis- guidelines on the identification, evaluation, and treatment
eases and diet, notably excess intake of food energy and of overweight and obesity in adults were released (6).
fat, especially saturated fat and cholesterol, as well as life- These clinical practice guidelines are designed to help phy-
style factors such as smoking, emotional stress, and lack sicians in their care of overweight and obesity and include
of physical exercise. Consequently, current diet/health rec- the scientific background for assessment as well as the
ommendations differ dramatically from those made ear- principles of safe and effective weight loss. Three key in-
lier. dicators are recommended BMI, waist circumference, and
the patient's risk factors for diseases and conditions asso-
ciated with obesity. Overweight is defined as a BMI of 25.0
OBESITY to 29.9 while obesity is a BMI greater than 30.0. These
values are consistent with the definitions used in many
Obesity affects many millions of Americans and is a major other countries and support the Dietary Guidelines for
public health problem. It is characterized by excess body Americans. A BMI of 30.0, for example, a weight of 221 Ib
fat caused by an imbalance between energy intake and for a 6-ft person (100 kg: 1.83 m) or 186 Ib for a person of
energy expenditure (2). The specific reasons behind such 5 ft, 6 in. (84 kg: 1.68 m) indicates about 30 Ib (13.6 kg)
an imbalance, however, remain the subject of much de- overweight for both men and women. Highly muscular peo-
bate. ple may have a high BMI without increased health risks.
Genetic, environmental and behavioral variables all in- For the majority, however, BMI is an excellent indicator of
fluence the risk of becoming overweight (2,4), but the rela- overall risk.
tive importance of each remains unclear. The prevalence The most successful strategies for weight loss include
of obesity for different age groups in the United States is reduction of food energy intake, increased physical activity,
Table 1. Prevalence of Overweight, Severe Overweight, and Morbid Obesity (NHANES II)
Males Females Total
Millions Prevalence % Millions Prevalence % Millions
Overweight 15.4 24.2 18.6 27.1 34.0
Severe overweight 5.1 8.0 7.4 10.6 12.5
Morbid obesity 0.327 0.6 1.7 2.5 2.0
Source: Ref. 3.
Table 2. Classification of Overweight and Obesity Based Table 4. Selected Recommendations from the First
on Body Mass Index Federal Obesity Guidelines Panel
Degree of Obesity BMP Engage in moderate physical activity (30 min or more) on
most/all days of the week.
Grade III (morbid obesity) >40
Reduce dietary fat and calories. Cutting back on dietary fat
Grade II (obese) 30-39.9
can help reduce calories and is heart-healthy.
Grade I (overweight) 25-29.9
The initial goal of treatment should be to reduce body weight
Grade O (normal) 20-24.9
by about 10% from baseline, an amount that reduces obesity-
0
BMI = weight in kilograms divided by the square of the height in meters. related risk factors. With success, and if warranted, further
Source: Ref. 2. weight loss can be attempted.
A reasonable time line for a 10% reduction in body weight is
six months of treatment (weight loss of 1 to 2 Ib per week).
Weight maintenance should be a priority after the first 6
Table 3. Dietary Guidelines for Americans months of weight-loss therapy.
Overweight and obese patients who do not wish to lose
Eat a variety of foods. weight, or are otherwise not candidates for weight-loss
Balance the food you eat with physical activity; maintain or treatment, should be counseled on strategies to avoid further
improve your weight. weight gain.
Choose a diet with plenty of grain products, vegetables, and Age alone should not preclude weight-loss treatment in older
fruits adults. A careful evaluation of potential risks and benefits in
Choose a diet low in fat, saturated fat, and cholesterol. the individual patient should guide management.
Choose a diet moderate in sugars.
Choose a diet moderate in salt and sodium. Source: Ref. 6.
If you drink alcoholic beverages, do so in moderation.
Source: Ref. 7.
Americans and the obese. Heavy drinkers and women who
are taking oral contraceptives (11) are also at increased
risk. Individuals with diabetes mellitus, gout, or kidney
and behavior therapy designed to improve eating and
disease also have a higher frequency of hypertension. Salt
physical activity habits. Other recommendations are listed
consumption can increase blood pressure for some. High
in Table 4.
blood pressure is related to obesity and to increases in body
One in five children in the United States is now over-
weight over time (9,12). Factors increasing the risk of de-
weight. Care and treatment differ from adults, and there-
veloping high blood pressure are listed in Table 5.
fore pediatric guidelines have been proposed by an expert
Weight loss, an active lifestyle, reduction in sodium in-
committee (8). Clinicians who care for these children and
take, and moderation of alcohol consumption are recom-
their families are urged not to express blame but to show
mended for prevention and management (9). For many,
"sensitivity, compassion and a conviction that obesity is an
however, medical intervention with antihypertensive
important chronic medical condition that can be treated."
drugs is required to maintain acceptable blood pressure.
Balanced nutritional intakes with avoidance of excess to-
gether with adequate physical activity are important goals
for all family members.
Table 5. Risk Factors for Hypertension (High Blood
Pressure)
HYPERTENSION
Heredity
Male gender
In the adult, hypertension (high blood pressure) is defined Sodium or salt sensitivity
as a pressure greater than, or equal to, 140 mmHg systolic, Heavy alcohol consumption
or greater than or equal to, 90 mmHg diastolic pressure Sedentary and inactive lifestyle
(9). In 90 to 95% of the cases of high blood pressure, the Race (African Americans are at greater risk)
specific cause may be unknown (10). Hypertension is a risk Age
factor for both coronary heart disease and stroke. Although Obesity and overweight
it can occur in children and adolescents, it is more preva- Use of oral contraceptives and some other medications
lent in the middle-aged and elderly, especially African Source: Ref. 11.
DIABETES MELLITUS der, and genetic background cannot be changed, treated,
or modified (16). Others, for example, smoking, high serum
What can now be recognized as diabetes was described in cholesterol, high blood pressure, physical inactivity, obe-
the ancient civilizations of Egypt, Greece, and India. The sity, and overweight, are under some control by the indi-
sweet taste of urine in those with the condition was noted vidual. Smokers have twice the risk of heart disease com-
in the 160Os and the term "mellitus" meaning honeylike pared with nonsmokers. Nearly one-fifth of all deaths from
was introduced (13). Diabetes mellitus is a major public cardiovascular diseases (180,000 deaths per year) are at-
health problem worldwide. It ranks sixth as a primary tributable to smoking (14). Surveillance data indicate that
cause of death in the United States, but when its compli- an estimated 1 million young people become regular smok-
cations are included, it ranks third. These complications ers each year (14).
can be very serious and involve, in the United States, 50% The risk of heart disease increases with a rise in cho-
of the amputations of all lower extremities in adults and lesterol levels especially when other risk factors are pres-
25% of all kidney failure and are also a leading cause of ent (17-19). Plasma total cholesterol was accepted as a
blindness. causal factor (among multiple factors) by the World Health
Non-insulin-dependent diabetes (NIDDM, or type II) is Organization (WHO) expert committee in 1982 and by the
the form of diabetes characterized as a chronic nutrition- U.S. National Institute of Health Consensus Development
ally related condition (Table 6) and is a disorder showing Conference in 1985 (17). Diet and its effects on plasma cho-
abnormalities in glucose, fat, and protein metabolism. The lesterol levels are discussed in the next section. Plasma
onset of type II diabetes can be triggered by dietary and triglyceride levels have also been correlated with increased
lifestyle factors similar to those associated with cardiovas- risk of heart disease (17) and are associated with increased
cular diseases. Diabetes and heart disease in later life ap- low-density lipoprotein (LDL) cholesterol levels. High
pear to be linked to weight at birth (13). blood pressure increases the risk of a stroke, heart attack,
kidney failure, and congestive heart failure. When obesity,
smoking, high blood cholesterol levels, or diabetes are also
CARDIOVASCULAR DISEASE present, high blood pressure increases the risk of a heart
attack or stroke severalfold.
Cardiovascular disease (CVD) has been for many years the Regular moderate-to-vigorous exercise plays a signifi-
leading single cause of death in the United States (14): it cant role in preventing heart and blood vessel disease (16).
includes both coronary heart disease (CHD) and stroke. Exercise helps control blood cholesterol, diabetes, and obe-
CHD is the most common form of cardiovascular disease. sity as well as maintaining blood pressure. However, sur-
In 1987 nearly 1 million deaths in the United States, veys have shown that more than half of American adults
half of the total number, occurred due to some form of CVD do not practice the recommended level of physical activity.
(15). In 1998, CVD remains the leading cause of death in Obese people are at a greater risk of heart disease, high
the United States (14), although there have been some re- blood pressure, high cholesterol, and other chronic dis-
ductions in the rate. Cardiovascular disease is often eases and diabetes (14,16). Diabetes is also a serious risk
thought to affect mainly men and the elderly, but it is also factor for heart disease with more than 80% of diabetics
a major killer of women and people in the prime of life (14). succumbing to some form of heart or blood vessel disease
An estimated 58 million Americans live with some form of (16).
the disease, and almost 10 million Americans aged 65
years and older report disabilities caused by heart disease.
Stroke is also a leading cause of disability in the United ROLE OF DIET IN CARDIOVASCULAR DISEASE
States, affecting more than 1 million people nationwide
(14). The health burden of this condition is rivaled by the Improper eating habits accompanied by the lack of exercise
economic burden, which has a profound impact on the increase the risk of gaining excess weight, a major risk
health care system. factor for heart disease, high blood pressure, and diabetes
Extensive clinical and epidemiological studies have (14). Diet also affects plasma cholesterol levels. Choles-
identified several major and contributing risk factors of terol is carried in the blood associated with two major types
heart disease and stroke (16). The major risk factors are of lipoproteins; LDL and HDL. LDL cholesterol has been
listed in Table 7. Some such as increasing age, male gen-
are often regarded as modern disorders despite the fact They are constantly preoccupied by thoughts of food, but
that similar conditions have been recognized in medicine their pattern of eating alternates between fasting and
for more than a century. gorging. Patients are extremely secretive about their bu-
Anorexia nervosa is a condition of self-engendered limic episodes. It is this secrecy that makes the condition
weight loss whose occurrence was originally thought to be difficult to diagnose.
restricted to young women. It also occurs in young men Both conditions occur predominantly in industrialized,
who are concerned with their body image such as dancers developed countries and are rare elsewhere (43). Immi-
and models. The diseases appear to be largely confined to grants are more likely to develop eating disorders than
affluent societies that espouse Western cultural ideals. their peers in their country of origin, probably indicating
Diagnostic criteria include: refusal to maintain mini- the importance of sociocultural factors in the etiology and
mally normal body weight for age and height; intense fear distribution of these disorders (43).
of gaining weight or becoming fat, even though already un-
derweight; undue influence of body weight or shape on self-
evaluation; and denial of the seriousness of the current low CONCLUSION
body weight with amennorhea often occurring in postmen-
archal females (41). Associated symptoms include: de- The chronic, nutritionally related diseases just described
pressed mood, irritability, social withdrawal, loss of sexual are major causes of death and disability in rich industri-
libido, preoccupation with food and rituals, as well as re- alized countries. American and North European diets have
duced alertness and concentration (42). tended to be high in animal foods (meat, dairy, fish, eggs)
One form of the disease invokes restrictive feeding be- and low in foods of plant origin (grains, fruits, and vege-
havior commonly associated with normal dieting, such as tables). It is claimed by Garrow (44) that most of the
undereating, refusal to take high-energy foods, and stren- chronic diseases in the Western society are the manifes-
uous exercise. This behavior is abnormal only in the degree tation of the high availability and variety of foods leading
to which it is pursued. Restlessness is very common once to overconsumption. Only a small proportion of income is
emaciation sets in and continues until physical deteriora- now required to be spent on food in the industrialized coun-
tion leads to weakness and lassitude. The "purging" form tries (45). Excessive intake of animal foods leads to a die-
involves more dangerous behaviors, such as self-induced tary pattern that is high in saturated fat and cholesterol
vomiting, and laxative or diuretic use. and low in fiber.
Bulimia nervosa is a variant of anorexia nervosa and In contrast, the southern European or the Mediterra-
shares many of its clinical and demographic features. It is nean diet comprises fruits, vegetables, and grains with
closely related to the purging form of anorexia nervosa. smaller amounts of meat, fish, eggs, and dairy products
One of the major differences is that bulimic patients main- (46,47). Olive oil is often the major lipid, so that the diet
tain normal weight. The condition generally involves per- is low in cholesterol and saturated fat and high in mono-
sistent dietary restriction that is eventually interrupted by unsaturated fatty acids. A comparative study between
episodes of binge eating with compensatory behaviors such Italians and Americans was performed in the early 1950s.
as vomiting and laxative abuse. Behavioral disturbances It was found that Italian diets were remarkably low in fat
often become the focus of intense guilt feelings. In the early (20% of energy) or just half of the proportion observed in
stages of the disease, all patients attempt to control their the diets of comparable American groups. The typical
weight by dieting and abstaining from high-energy foods. American diet, rich in meat and dairy fats was thus, to-
gether with higher concentrations of blood cholesterol, BIBLIOGRAPHY
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AFLATOXINS. See MYCOTOXINS.
AGGLOMERATION
AND AGGLOMERATOR SYSTEMS
ual particles and dry preagglomerates bound mainly by "Filtermat" by GEA Niro AIs (Soeborg, Denmark), with in-
van der Waals forces. The effectiveness of this method de- tegrated perforated belt drier (Fig. 4a), and spray drying
pends on a variety of process parameters influencing in- with integrated fluidized bed and fines recycling (Fig. 4b).
terparticle collision frequency, relative velocities of the In the "Filtermat" process, the product is partially dried
particles, interparticle contact forces between wetted par- in the spray-dry section of the machine to a moisture con-
ticles, and strain on the agglomerates (8). tent of approximately 16 to 25%, whereupon it is deposited
by gravity onto the perforated belt and further dried to
Drying Processes approximately 5 to 10% moisture. Sufficient moisture is
The second main group of processes for agglomerating food present in the intermediate dried product so that agglom-
powders comprises special drying processes. Two examples erates are formed on the belt. These are then classified
are shown schematically in Figure 3, a spray drier with and/or size-reduced to the desired size (9).
fluidized bed and a freeze drier. These methods allow production of very loose, but still
Spray drying is one of the most widely used processes sufficiently strong agglomerates (5) with good instant
in food powder technology. The concentrate/slurry, either properties and have been widely used in the food industry.
in the form of a suspension or a solution, is finely distrib-
uted using a nozzle or an atomizer disc, dried, and cooled
in a connected fluidized bed from which the product is Further Methods
withdrawn in agglomerated form. The fluidized bed also
serves the purpose of removing the fines, which are col- Pressure agglomeration is rarely applied to the production
lected in a cyclone and recycled into the spray drier. Ag- of redispersible products, because the resulting agglom-
glomeration occurs in the vicinity of the nozzle or atomizer, erates are so compact that they show insufficient disper-
where the fine dry particles collide with the slurry drop- sibility. Substances dispersing readilydue to a bursting
lets. In many cases the product is also after-dried in the effect of special additivescan be agglomerated using die
fluidized bed, a process referred to as two-stage drying. pressing or low pressure extrusion processes. If no great
Freeze drying is relatively expensive but especially use- demands are set upon the redispersibility, roll pressing is
ful for products sensitive to high temperatures. Another a useful and inexpensive process. Mostly low-pressure
advantage is the possibility to vary the porosity of the ag- ring-roller presses are used in which the moistened powder
glomerates over a wide range by foaming the concentrate is pressed through holes and thereby shaped into agglom-
before freezing (this can be achieved in a spray drier, too, erates.
by gassing the slurry immediately before atomization). As A special kind of agglomeration is coating, to improve
a novel technology, microwave drying in a vacuum cham- the wetting behavior of the particles. Usually the particles
ber can be used instead of freeze drying. are coated by pure liquids, solutions, or suspensions that
harden on the surface of the solid material. A novel tech-
Combined Methods nology is coating with submicron particles by "mechano-
Two examples for combined agglomeration methods are fusion" (10) to improve the wettability and for other appli-
presented in Figure 4. These are special spray driers, the cations (11).
Freezing
Spray dryer Cyclone Crusher
Vacuum
(condenser)
Freeze dryer
Fluidized bed
Heating
Figure 3. Principles of production of instantized
powdered foods by spray drying (a) and freeze drying
(b). A, agglomerates; C, concentrate; F, fines; G, gas.
Cyclone
Figure 4. Principles of combined agglomeration
processes for the production of instantized pow-
dered foods: "Filtermat" spray drier with perfo-
rated belt drier (a) and spray drier with integrated
fluidized bed and fines recycling (b). A, agglomer-
ates; F, fines; G, gas; SL, slurry.
COO' ? + NAD+
' CH2 + CoA
+
if H2O QJJ + Thiamin pyrophosphate
HCi A_ri
G\j + Lipolic acid
coo- i
C
Fumarate
a-Keto
glutarate
0
Il /i /
^-s
COO- C-S-CoA /(
\ CH2 CH2 ^/ ^ Q02
FAD+ CH2 CH2 +
^-
COO "^ /7 TOO-
^^ u
+ GDP NADH
Succinate * Succinyl
GTP CoA
+ CoA
Other fruits may also be fermented to wine, but only 5% alcohol by volume (4% by weight). So-called malt li-
apple juice, as cider, has found even limited acceptance. quors contain about 6% alcohol by volume.
Mead
Beer
As honey is about 82% solids, it must be diluted to about
The solution from which beer is made, called wort, is made 20Brix and then fermented. The high price of honey and
at the brewery and not in nature. As such, its concentra- the rather weak flavor of its fermented solution has not
tion and fermentability (see BEER) are designed for the permitted mead to be more than a historical curiosity.
beer being made and may vary widely. But the concentra-
tion of the wort only varies between 12 and 18Brix, and Distilled Spirits
the fermentability between about 60% and 90%. So beer is These spirits are distilled at a rather high proof, be they
never as high in alcohol as wine. Typically, beer contains from grains (whiskey or vodka), molasses (rum), or wine
(brandy), and are diluted to a marketable strength. The Nonalcoholic women Alcoholic women
normal concentration is about 80 proof or 40% by volume
or 32% by weight. Whiskeys are usually consumed after
mixing with water, often carbonated, and also flavored. As
purchased, wine is 2 stronger than beer, and whiskey is 3
or more times stronger than wine.
Effects of Alcohol on the Central Nervous System Interaction of Alcohol and Other Nutrients
The primary effect of alcohol in the body is a sequential Alcohol and its primary metabolite, acetate, serve as ex-
depressant action on the central nervous system. From the cellent sources of energy. Alcohol and acetate penetrate the
spinal cord rises the medulla oblongata, the pons, and the blood-brain barrier almost as efficiently as glucose. Every-
midbrain, the control centers for the autonomic nervous where, alcohol is used in preference to all other energy
system, which regulates reflexes and those functions be- sources. Acetyl CoA, the entry point of all energy sources
yond control of the will. Above the midbrain lies the thal- into the citric acid cycle, is most easily produced from al-
amus and hypothalamus, whose dominion includes func- cohol.
tions not willfully regulated, such as body temperature, Also, while all other energy sourcesfatty acids, glu-
metabolism of fats, and blood sugar level. cose, and amino acidscan be stored in polymolecular
Above all this, and more recent in the evolution of the forms, alcohol and acetate cannot be stored. Neither do
species, lie the cerebellum and the cerebral cortex. The for- they act as substrates for conversion to glucose, amino ac-
mer has sway over voluntary muscular movements and ids, or lipids. Alcohol must thus be metabolized as it be-
manual skills, as well as balance and speech. The cerebral comes available (8).
cortex, the corolla of the mind, is master of all that distin-
guishes humans and makes them distinguished. Effect on the Digestive Tract
Alcohol, which has ready access to all cells and crosses Alcohol slightly increases gastric and intestinal mobility.
the almost impenetrable blood-brain barrier as if it were a It also has a slight positive but very transient effect on
sieve, exerts its earliest action on the cerebral cortex. Its ' appetite. It has no effect on the absorption of fats or cho-
action is not as a stimulant but as a tranquilizer or de- lesterol from the intestinal tract. Some of the very slight
pressant. It lessens inhibitions and increases confidence. appetite stimulation may not even be due to alcohol, but
It replaces discontent with discovery, bashfulness with to other factors present in some alcoholic beverages
bravado, and cowardice with courage. Alcohol negates a no juniper in gin, bitters in some aperitifs, hops in beer.
and affirms a yes.
These effects, which people had sought long before the Effect on Cardiovascular System
tensions of modern life were imposed on them, occur at
blood levels between 0.02 and 0.05%. Whatever pressures Alcohol slightly dilates peripheral capillaries, leading to
and problems were mankind's lot in Biblical days, they blushing and a feeling of warmth. The effects are transi-
were surely different in scope and pervasiveness than tory and meager.
Moderate alcohol consumption reduces the risk of cor- quility. Furthermore, as a controlled way to peace and
onary heart disease. It also reduces the risk of cardiac mor- pleasure, alcohol has no peer.
tality. Its action is probably mainly due to its effect on rais- Regulations in the United States prohibit any declara-
ing the HDL levels in the blood, as well as lowering the tion of therapeutic value for any alcoholic beverage, so each
triglyceride levels. Physical activity has the same effect, generation must rediscover the value of alcohol. Many
and the effects are additive. countries permit some therapeutic claim for alcohol, such
Moderate drinking is taken to be between 25 and 80 g as a bedtime relaxer or tension reducer.
of alcohol a day (two to six 12-oz. bottles of beer, 5% alcohol As medicine, alcohol differs from drugs. All drugs are
by volume; 250-750 ml of table wine [12% alcohol]; or 70- detoxified in the liver, ie, the liver so chemically modifies
250 ml of whiskey [80 proof]). the drug as to render it inactive and able to be excreted,
The LDL in the blood (the "bad" cholesterol) is now be- usually by the kidneys. This detoxification usually involves
lieved to have its malign effect on atherosclerosis after it oxidation, hydrolysis, or sulfation. But alcohol is not de-
is oxidized. And so antioxidants have been shown to have toxified, it is metabolized, just as is any foodstuff. No drug
a protective effect. This is the so-called French Paradox: supplies energy; alcohol does. It may be more valid to con-
the French consume diets high in cholesterol and satu- sider alcohol as a food that has effects on the body rather
rated fats and yet have very low coronary artery disease. than as a drug. As was pointed out earlier, alcohol has free
The explanation is their relatively high consumption of al- entrance to every cell in the body; no drug has. All drugs
cohol, mainly in the form of red wine. Many of the poly- operate by attaching themselves to a specific cellular re-
phenals, gallic acid, rutin, epicatechin, and quercitin pres- ceptor; alcohol needs none and has none.
ent in red wine are potent antioxidants (9). Such phenolics Alcohol has at least one clinically proven and prescribed
are also present in oak-aged whiskey and in full-bodied medicinal function. It is the only antidote to poisoning with
and darker beers. ethylene glycol (antifreeze). Quick administration of alco-
Alcoholic beverages therefore have a two-pronged effect hol, usually intravenously, makes all alcohol dehydroge-
on reducing coronary heart disease, raising the "good" nase sites act on the alcohol, harmlessly, instead of acting
HDL and keeping the LDL from becoming "bad." on the glycol, which produces very toxic oxalic acid. The
glycol, not oxidized, is slowly excreted by the kidneys. The
Effect of Alcohol on Men versus Women preferential reaction of alcohol dehydrogenase with alcohol
permits this therapeutic action.
Alcohol per se has the same effects on either sex. However, There are foods other than alcohol that affect the brain
a given amount of alcohol has a greater effect on women and human behavior. The amino acid tryptophane is a sop-
than on men for several reasons. orific and has been used as such. Meals high in carbohy-
First, women are usually smaller than men, so a given drates produce high tryptophane blood levels. This they do
volume of an alcoholic beverage will have a greater effect by producing an influx of insulin into the blood, which in
on the smaller person. turn mobilizes some amino acids from plasma to muscle,
Second, women have a lower water content in their bod- leaving a higher concentration of tryptophane in the
ies than do men. Thus the alcohol, which is only soluble in plasma. Histidine, threonine, tyrosine, and choline also are
water and not in fat, will reach a higher concentration in neuroactive, but their action is compromised by complex
women. This difference in water content, on an equal factors.
weight basis, is about 12%. There are no confirmed allergies to alcohol per se. Its
And last, and probably most important, women have a free entrance to all cells and ubiquitous presence mitigate
lower gastric activity of alcohol dehydrogenase than do against any allergic reaction.
men. They therefore do not destroy as much alcohol in
their stomach as do men, allowing more of it to be absorbed Alcohol the Day After
into the blood. This phenomenon, only recently discovered
(1), is known as first-pass metabolism. It may differ by 20- The day after a serious session of drinking is often one of
30% between men and women. Thus the bioavailability of mental and physical fatigue and headache. In the United
alcohol is considerably greater in women than in men. States, these symptoms are lumped together and called a
However, men over 50 years of age begin to lose the high hangover. In other languages the term is more descriptive,
alcohol dehydrogenase activity in their stomachs and be- a wooden mouth in French, for example. The symptoms
come equal to women in their first-pass metabolism (10). relate to the known constituents of alcoholic beverages and
the known physiology of alcohol.
Alcohol as Medicine Alcohol masks fatigue, so a night of drinking will lead
to excessive activity, which will be revealed by fatigue and
Before the advent of the modern pharmacopoeia, alcohol malaise the next day. Rest always allows return to the nor-
was prescribed for many human ills. It dulls pain, sum- mal state. The dry mouth or excessive thirst is the result
mons sleep, soothes the spirit, and tames the teeming of the diuretic effect of alcohol (and possibly the very salty
mind. Each of these functions can now be accomplished by nibbles that often accompany drinking). Drinking water or
a coterie of drugs, so alcohol is rarely recommended for fruit juice, and a little time, alleviate this condition.
these ills. But no one substance does all of what alcohol The headache may result from the fatigue and the de-
does, and people in all cultures have found alcohol to be hydration but may also result from the congeners of dis-
the preferred, and possibly less noxious, means to tran- tilled spirits and of wine. The congeners are simple com-
pounds produced by yeast concomitant with alcohol. They Prenatal alcohol abuse can lead to birth defects known
range from ethyl acetate to amyl alcohol. Also, particularly as fetal alcohol syndrome. The most benign symptom is low
in some wines, and in brandy, there may be measurable birth weight, and the most serious is impaired brain de-
amounts of methyl alcohol. These levels of methyl alcohol velopment and mental retardation. The most severe effects
are not toxic per se, but when metabolized to formaldehyde are known to occur in chronic alcoholics, but because it is
may produce headaches. The drinking of a small amount neither known what the safe lower limit of alcohol intake
of some alcoholic beverage the next day, possibly beer or is nor when during the pregnancy alcohol is most likely to
vodka, will induce the liver to return to oxidizing alcohol harm the fetus, it is generally recommended to avoid al-
and allow the methanol to be eliminated by the kidneys. cohol during pregnancy (11,12).
Physical Properties
GENERAL REFERENCES Most alkaloids are colorless crystalline solids with a de-
fined melting point or decomposition range (eg, vindoline
C. Leake and M. Silverman, Alcoholic Beverages in Clinical Med- and morphine). Some alkaloids are amorphous gums and
icine, World Publishing Co., Cleveland, 1966. some are liquids (eg, nicotine and conine) and some are
National Research Council (U.S.), Diet and Health, National
Academy of Sciences, National Academy Press, Washington,
colored (eg, berberine is yellow and betanidine is red).
D.C., 1989. The free base of the alkaloid is normally soluble in an
D. A. Roe, Alcohol and the Diet, AVI Publishing Co., Westport, organic solvent; however, the quaternary bases are only
Conn., 1979. water soluble, and some of the pseudo- and protoalkaloids
E. Rubin, "Alcohol and the Cell," Annals of the New York Academy show substantial solubility in water. The salts of most al-
of Sciences 492, p. 1-7, 181-190 (1987). kaloids are soluble in water.
F. A. Seixas, K. Williams and S. Eggleston, "Medical Consequences The solubility of alkaloids and their salts is of consid-
of Alcoholism," Annals of the New York Academy of Sciences erable significance in the pharmaceutical industry, both in
252, p. 11-19, 63-78, 85-100 (1975). the extraction of the alkaloid from plant or fungus and in
F. A. Seixas, and S. Eggleston, "Alcohol and the Central Nervous the formulation of the final pharmaceutical preparation.
System," Annals of the New York Academy of Sciences 215, p.
10-36; 325-330 (1973).
Solubility is also of considerable significance in the clinical
distribution of an alkaloidal drug.
Cocaine
Pelletierine Lupinine
Senecio Alkaloids. Senecio alkaloids possess a pyrroli-
zidine nucleus and occur in the genera Senecio (Composi- Anthranilic Acid-Derived Alkaloids
tae), Heliotropium and Trichodesma, and Crotalaria. They
Anthranilic acid-derived alkaloids exhibit great structural
are biosynthetically derived from two units of ornithine in
diversity. This group includes dictamnine, platydesmine,
a manner similar to some of the lupin alkaloids. Certain
vasicine, cusparine, and rutecarpine. Vasicine has oxytocic
of the alkaloids having an unsaturated nucleus are potent
activity.
hepatotoxins.
Nicotine. Nicotine is toxic, soluble in water, and a con- Phenylalanine- and Tyrosine-Derived Alkaloids
stituent of tobacco. The lethal human dose is ca 40 mg/kg. Phenylalanine- and tyrosine-derived alkaloids are by far
Pharmacologically, there is an initial stimulation followed the most numerous group of alkaloids, ranging from simple
by depression and paralysis of the autonomic ganglia. The phenethylamines to the very complex dimeric benzyl-
biosynthesis of nicotine is well established. isoquinolines and the highly rearranged Cephalotaxus al-
kaloids.
Physostigmine
Cephalotaxine R = H Physostigmine, found in the perennial West African woody
OH OH climber, Physostigma venenosum Balfour, is pharmacolog-
i i ically similar to pilocarpine and is a reversible cholines-
Harringtonine R = COC(CH2)2 C(CH3)3
terase inhibitor used to treat glaucoma.
CH2CO2CH3
OH The Ergot Alkaloids
Deoxyharringtonine R =COC(CH2)2CH(CH3) The ergot alkaloids are obtained from ergot, the dried scle-
rotium of the fungus Claviceps purpurea (Fries) Tulsane
CH2CO2CH3 (Hypocreaceae). Ergot alkaloids are produced by isolation
from the crude drug grown in the field, by extraction from
Securinine saprophytic cultures, and by partial and total synthesis.
The ergot alkaloids act pharmacologically to produce
Securinine, isolated from Securinega suffruticosa Rehd, is
peripheral, neurohormonal, and adrenergic blockage, and
similar to strychnine in action, but exhibits lower toxicity,
to produce smooth-muscle contraction as well. The two me-
stimulates respiration, raises blood pressure, and in-
dicinally important ergot alkaloids are ergotamine and er-
creases cardiac output. The chemistry, pharmacology, and
biosynthesis of securinine and related compounds have gonovine.
been reviewed.
Tryptophan-Derived Alkaloids
Tryptophan-derived alkaloids, which occur in the families
Apocynaceae, Rubiaceae, and Loganiaceae, have recently
become of great interest, particularly those derived from
tryptamine and a monoterpene unit. There are many di-
verse structural types in this group. Attempts to determine
the important details of the biosynthetic interconversions
of these compounds have been reported.
The simplest indole alkaloids are derived from Lysergic acid
tryptamine itself. These include indole-3-acetic acid, a
potent plant-growth stimulator; serotonin (5-hydroxytryp- Three main groups of ergot alkaloids exist:
tamine), a vital mammalian product that inhibits or stim-
ulates smooth muscles and nerves; AT-acetyl-5-methoxy- 1. The clavine type, a group of over 20 alkaloids, which
tryptamine (melotonin), a constituent of the pineal gland is water insoluble and does not give lysergic acid on hy-
with melanophase-stimulating properties; 5-methoxy- drolysis. This group includes elymoclavine, agroclavine (a
N,AT-dimethyltryptamine, a constituent of the hallucino- potent uterine stimulant), and chanoclavine-I.
genic Virola snuffs; psilocybine, a hallucinogenic found in 2. The aqueous lysergic acid derivatives such as ergo-
the mushroom Psilocybe mexicana Heim. novine, which in its maleate salt (or as methyl ergonovine
The harmala alkaloids, such as harmine and harma- maleate) is the drug of choice to treat postpartum hemor-
line, are powerful monoamine oxidase inhibitors, previ- rhage.
3. The peptide ergot alkaloids, a group of water insol- Histidine-Derived Alkaloids
uble lysergic acid derivatives. This group includes ergot- Histidine-derived alkaloids include pilocarpine and saxi-
amine, ergocornine, and ergocryptine. Ergotoxine, a mix- toxin. Pilocarpine stimulates parasympathetic nerve end-
ture of three peptide ergot alkaloids, possesses strong ings and is used to treat glaucoma. The main commercial
sympatholytic action and is used as a peripheral vasodi- source of pilocarpine is Pilocarpus microphyllus Stapf.,
lator and antihypertensive. Dihydroergotoxine is used for known as Marnham jaborandi. Saxitoxin is an extremely
vascular disorders in the aged. toxic neuromuscular blocking agent found in the so-called
coastal red tides of North America.
Some ergot alkaloids (eg, 2-bromo-a-ergocryptine) stim-
ulate prolactin release and are being evaluated for treat- Monoterpenoid Alkaloids
ment of breast cancer. Monoterpenoid alkaloids include chaksine, a guanidine al-
kaloid from Cassia lispikula Vahl, which induces respira-
Catharanthus and Vinca Alkaloids tory paralysis in mice; /?-skytanthine, which is tremori-
genic; cantleyine, derived from a monoterpene before
Catharanthus and Vinca alkaloids, usually discussed to-
loganin; and those derived from secologanin, such as gen-
gether, are quite distinct. The most important alkaloids of
tianine, which exhibits hypotensive, anti-inflammatory,
the Catharanthus genus are vincaleukoblastine, leurocris-
and muscle-relaxant actions, gentioflavine, gentiatibetine,
tine, and leurosine, all antileukemic agents. Vincaleuko-
pedicularine, and actinidine, a potent feline attractant.
blastine and leurocristine are used clinically. The most im-
portant alkaloid of Vinca is vincamine, used to treat Diterpene Alkaloids
hypertension, angina, and migraine headaches. Alkaloids
Diterpene alkaloids are not of commercial or therapeutic
of this type produce marked hypotensive effects and
curare-like action. The ethers of vincaminol are potent significance, but some have potent pharmacological activ-
ity, eg, aconitine and Erythrophleum alkaloids.
muscle relaxants.
Steroidal and Triterpene Alkaloids
Rauwolfia Steroidal and triterpene alkaloids are found in the plant
Rauwolfia alkaloids include reserpine, the first tranquil- families Solanaceae, Liliaceae, Apocynaceae, and Buxa-
izer, rescinnamine, and deserpidine. Reserpine is a seda- ceae. There are four main groups based on the botanical
tive and tranquilizer useful in treating hypertension. It is source: the Veratrum, Solanum, Holarrhena and Funtu-
also used as a rodenticide. mia, and Buxus alkaloids.
The Veratrum alkaloids include jervine, protoveratrine
Strychnine A, and protoveratrine B; the latter two produce pro-
nounced bradycardia and a fall of blood pressure by stimu-
Strychnine, from the seeds of many Strychnos species, is a lation of vagal afferents. The Solanum alkaloids are of in-
widely known poison (although, in fact, it is only moder- terest as potential sources of steroids. Examples of these
ately toxic). Pharmacologically, strychnine excites all por- alkaloids are tomatidine and solanidine. Some Solanum
tions of the CNS; it is a powerful convulsant and death alkaloids exhibit fungistatic activity. Biosynthetically,
results from asphyxia. It has no therapeutic uses in West- the alkaloids are derived from acetate and mevalonate.
ern medicine, although its nitrate is used in treating
chronic aplastic anemia.
Cinchona Alkaloids
Cinchona alkaloids, derived from the dried stem or root
bark of various Cinchona species, include quinine and
quinidine. These alkaloids are bitter tasting white crys-
talline solids, sparingly soluble in water. Quinine is toxic
to many bacteria and other unicellular organisms and was
the only specific antimalarial remedy until the Second Tomatidine
World War. It is a local anesthetic of considerable duration.
Quinine is commonly used as the sulfate and dihydro-
chloride. Quinidine, produced by the isomerization of qui-
nine or found in Cuprea bark, is more effective on cardiac
muscle than quinine and is used to prevent or abolish cer-
tain cardiac arrhythmias.
Camptothecine
Camptothecine, isolated from the Chinese tree Campto-
theca acuminata Decsne, is used to treat cancer in the Peo-
ple's Republic of China. Solanidine
Table 1. Effects of Natural Food Alkaloids on Humans and Animals
Alkaloid(s); identified or potential food sources
Clinical effects
Toxic symptoms
Amatoxins (a-, /3-, y-amanitins, amanin, amamillin); toxic mushrooms [Death Cup (Amanita phalloides, A. verna, A. virosa)]
Liver and kidney damage (man)
Delayed vomiting, abdominal pain and diarrhea, coma, death; LDa (man, oral) = 0.11 mg/kg
Arecoline; Areca nut or Betal nut (Areca catechu)
Parasympathomimetic agent, cathartic (horses); cholinergic (man)
Flushing, perspiration, bronchial spasms, contraction of pupils, diarrhea, dyspnea, and collapse; LDa (mouse, subcutaneous)
= 102 mg/kg
Caffeine; coffee, tea, cola nuts, guarana
Cardiac, respiratory, and psychic stimulation, diuresis; vascular cephalalgesia (man)
Nausea, restlessness, vomiting, insomnia, tremors, tachycardia, cardiac arrhythmia (man); LD50* (rat, oral) = 19.6 mg/kg
Capsaicine; red peppers
Skin irritant
Sweating, salivation (mammals)
Carapine; papaya (Carica papaya)
CNS depression (mammals)
Bradycardia (mammals)
Caulerpicin; marine algae (Caulerpa sertulariodes C. racemosa var. clavifera)
Anesthesia (mammals)
Numbness of lips and tongue (man)
Chavicine; black and white pepper (Piper nigrum)
Sharp peppery taste (man)
No information
Choline; brain, egg yolk, bivalve mollusks (Callista brevisiphonata), areca nut
Lipotrophic agent, antihypercholesterolemic agent
Nausea, vomiting, diarrhea (man); LDa (rabbit, subcutaneous) = 450 mg/kg
Convicine; fava bean (Vicia sativa or V. fava)
Inhibition of glucose-6-phosphate dehydrogenase, decreased or reduced glutathione levels in red blood cells
Hemolysis, growth retardation (rat), hemoglobinemia (dog)
Curry alkaloids (murrayanine, mukoeic acid, girinimbine murrayacine, koenimbine, koenine, koeniginine, koenigine, mahanimbine,
Cyclomahanimbine, curryanine); curry plant (Murraya koenigii Spreng)
For skin eruptions
No information
Cystisine; milk [contaminated from Cystisus laburnum, Sophora secundiflora (mountain laurel)
No information
Excitement, sweating, incoordination, convulsion, death (man, pig, cattle, horse); LDa (as nitrate, dog, subcutaneous)
- 4.3 mg/kg
3,4-Dihydroxy-L-phenylalanine (DOPA); fava bean (Vicia fava)
Decrease in reduced glutathione in red blood cells (man)
No information
Dopamine; banana, avocado, cephalopods
Hypertensive agent, increased cardiac output
No information
Dioscorine; wild yam (Dioscorea hirsutus, D. hispida)
CNS stimulation: analeptic, diuretic, expectorant
Sialorrhea, nausea, vomiting, diarrhea, confusion, cold sweat, pallor, clonic convulsion, paralysis, asphyxia (man), emetic
hemolytic agent; LDa (mouse, intraperitoneal) = 130 mg/kg
Eptatretin; Pacific hagfish (Polistotrena stouti)
Cardiac stimulant (frog, dog)
None, due to rapid detoxication
Ergot alkaloids (Eorgonovine, ergotamine, ergosine, ergocristine, ergocyptine, ergocornine, ergosinine, ergocristinine, etc); Barley, rye
(contaminated from ergot produced by the fungi Claviceps paspali and C. pupurea)
Uterine stimulation, analgesic for migraine headache
Tachycardia, hypertension, vomiting, diarrhea, mental confusion, hallucinations, convulsions, gangrene, gastrointestinal (GI)
disturbance; LDa ergotamine, rat, intravenous) = 60 mg/kg
Gelsemine; Honey [contaminated from yellow jasmine] (Gelsemium sempervirens) nectar]
Uterine stimulation, CNS stimulant
Dizziness, dimness of vision, mydriasis, nausea, muscular debility, unusual prostration, weak pulse, dyspnea (man); minimum
LD (rabbit, subcutaneous) = 0.15 mg/kg Glucobrassicin; broccoli, brussels sprouts, cabbage, cauliflower, kohlrabi, radish,
rutabaga
Goitrogenesis (rabbit, rat)
Hyperplasia of the thyroid; kidney and liver enlargement (rabbit, rat)
Table 1. Effects of Natural Food Alkaloids on Humans and Animals (continued)
Alkaloid(s); identified or potential food sources
Clinical effects
Toxic symptoms
Goitrin; cabbage, rape, rutabaga
Goitrogenesis (rat)
Hyperplasia of thyroid, liver and kidney enlargement (rat)
Gramine; barley (Hordeum vulgare)
Vasoactivity, stimulation of intestines and uterus (rabbit)
Hypertension, clonic convulsion, and excitation of respiratory center
Histamine; derived from beer, chocolate, fish, sauerkraut, wine, and yeasts
Vasoactivity (mammals)
Headache (man), hypotension (man, mammals); LD506 (mouse, intraperitoneal) = 12.7 g/kg, LDa (monkey, intravenous) = 52
mg/kg
Hordenine; germinated barley (Hordeum vulgare}, sorghum (Sorghum vulgare}, millet (Panicum miliaceum)
Sympathomimetic intestinal stimulation, respiratory stimulation (cat, dog); uterine stimulation (guinea pig)
Hypertension (man, dog), psychostimulation, convulsion, respiratory inhibition (man), LD0 (as sulfate, dog, oral) = 1.9 g/kg
Islanditoxin; rice (contaminated from Penicillium islandicum}
Carcinogenic hepatotoxin (mouse)
Liver damage, liver cancer (mouse, rat); LD506 (mouse, oral) = 5.0 mg/10 g
Laminine; marine algae (Laminaria spp) and others
Hypotension (rabbit); depression of contraction of smooth muscles (mouse, guinea pig)
Hypotension (rabbit)
Methyl pyrazine (various derivatives); green peas (Pisum sativum}
No information
No information
Methyl pyrroline; black pepper (Piper nigrum)
No information
No information
Mimosine; Leucaena glauca
No information
Alopecia (mammals)
Murexine (urocanyl choline); shellfish (Muricidae spp.)
Excitation of respiratory center, neuromuscular blocking, muscle relaxation (vertebrates and invertebrates)
Muscular and respiratory paralysis (vertebrates and invertebrates); LD10Q (as oxalate, mouse, subcutaneous) = 310 mg/kg
Muscaridine; mushroom fly agaric (Amanita muscaria}
Uterine stimulation (rabbit, guinea pig)
Hashish or alcohol-like intoxication (man)
Muscarine; mushroom fly agaric (Amanita muscaria and other mushrooms)
Uterine stimulation (rabbit, guinea pig)
Sialorrhea, lacrimation, diaphoresis, nausea, vomiting, bradycardia, convulsions, coma, death; LD100 (mouse) = 16 ug/day
Nicotine; tomato
Respiratory stimulation (man); uterine stimulation (cat, rabbit, pig); cerebral and visceral ganglial stimulation (man)
Hypotension (dog); respiratory depression and paralysis (cat); hyperglycemia, convulsion, dizziness, nausea (man), etc; LD
(man, oral) = 40 mg/70 kg; LD506 (rat, oral) = 60 mg/kg
Norepinephrine; banana (particularly the pulp), orange (trace), potato
Vasoactivity sympathomimetic, adrenergic
Hypertension
Pahutoxin; fishes [Hawaiian boxfish (Pahu), Ostraciontidae family]
Neuromuscular effects (mammals)
Hemolysis (mammals); ataxia, respiratory distress, coma (mouse); minimum LD" (mouse, intraperitoneal) = 0.25 mg/g
Phallotoxins (phalloidin, phalloin, phallisin, phallicidin); toxic mushrooms [Death Cup, (Amanita phalloides, A. verna, A virosa}]
Liver and kidney damage (man)
Vomiting, abdominal pain, diarrhea, coma, and death (man); LD (man, oral) = 3 mg/kg
/?-Phenylethylamine; Mushrooms, bitter almonds
Respiratory stimulation, intestinal relaxation, symphatomimetic (man)
Hyperventilation, hypertension, hypotension (cat); LD50 (mouse, intraperitoneal) = 350 mg/kg
Pipeline; black pepper (Piper nigrum}
No information
No information
Pyrrolizidine alkaloids; wheat and other cereals, legume (contaminated from Crotalaria laburnifolia, C. striata}
No information
Liver damage, carcinogenesis, venoocclusive disease (mammals); glaucoma (rat, mouse); LD506 (mouse) = 20 mg/kg
Sanguinarine; mustard oil and cereal grains (contaminated from Argemone mexicana)
Expectorant; for chronic eczema and skin cancers
LD0 (as sulfate, intraperitoneal, rat) = 450 mg/kg
Table 1. Effects of Natural Food Alkaloids on Humans and Animals (continued)
Alkaloid(s); identified or potential food sources
Clinical effects
Toxic symptoms
Saxitoxin; shellfish, bivalve mollusks, and other pelecypods (contaminated from the dinoflagellates Gonyaulax catenella and G.
tamarensis)
Neural stimulation (mammals); hypotension (cat and rabbit); myocardial and respiratory depression (mammals)
Peripheral paralysis, tingling and numbness of lips, respiratory failure (man and other mammals); LD506 (man, oral) = 10-20
/*g/kg
Serotonine; avocado, banana, pineapple, octopus, papaya, plantain, passion fruit, red plum tomato
Respiratory stimulation (dog); respiratory inhibition (cat)
Hypertension (man); CNS depression (most animals); inhibition of ovulation (rabbit); teratogenesis (mouse)
Solanine (solanidine); Irish potato (Solanum tuberosum\ tomato (Lycopersicon esculentuni)
Acetylcholine esterase inhibition (mammals)
Drowsiness, hyperesthesia, dyspnea, vomiting, diarrhea (man); LDa (rabbit, intravenous) = 25 mg/kg
Tetrodotoxin; Pufferfish (Tetradontidae and Diodontidae families)
Neuromuscular blocking (mammals); hypotension (cat); respiratory inhibition, hypothermia (dog)
Weakness, dizziness, pallor and paresthesia, nausea, vomiting, sweating, salivation, muscular paralysis, cyanosis, respiratory
paralysis, death (man); minimum LD (cat, subcutaneous) =11 mg/kg; LD506 (mouse, oral) = 325 mg/kg
Tetramine; shellfish (Buccinidae and Cymatidae families)
Curare-like effects, hypotension, bradycardia (mammals, frog)
Salivation, lacrimation, miosis, peristalsis (mouse); motor paralysis (mammals)
Threobromine; cacao bean; cola nuts; tea
Diuresis, myocardial stimulation, vasodilation, respiratory stimulation (cat)
GI distress; LD506 (cat, oral) = 220 mg/kg
Theophylline; tea
Diuresis, hypertensive cephaloanalgesia (man)
Nausea and vomiting, vertigo, insomnia, flushing, convulsions, death; LD506 (mouse, oral) = 550 mg/kg
Tomatine; tomato juice
No information
LD (rat, oral) 1 g/kg
Toxoflavin; Indonesian bongkrek (contaminated from Pseudomonas cocovenenans)
No information
LD506 (mouse, oral) = 800 mg/kg LD506 (mouse, intravenous) = 2.0 mg/kg
Trigonelline; green peas (Pisum sativum), coffee, soybeans, potatoes
No information
LD6 (rat, subcutaneous) = 4.9 g/kg
Tryptamine; plum (red and blue), orange, tomato
Vasoactivity, musculotropic (rabbit); intestinal and uterine contraction (rabbit, guinea pig)
Hypertension, headache (man)
Tyramine; avocado, banana, octopus, orange, spinach, potato, tomato
Respiratory stimulation (rat, cat); vasoconstriction (mammals)
Paroxysmal hypertension, intracerebral hemorrhage (man); mydriasis, bradycardia (dog); hypothermia (cat); LD (rabbit,
intravenous) = 250 mg/kg
Vicine; fava bean (Vicia sativa or V. favd)
Inhibition of glucose-6-phosphate of dehydrogenase; decrease in reduced glutathione
Hemolysis, growth retardation (rat); hemoglobinemia (dog)
Source: Ref. 1; see also reference under S. W. Pettetier.
0
LD = lethal dose.
6
LD50 = median lethal dose.
Slaughtered
animal
Rendering
Condensed steam
from raw material
Digester Pre-breaker
Cooker
Strainer Intermediate
tank
Greaves Fat, water,
for Press Tank and fines for
drying purification Decanter
Figure 2. Wet-rendering system. Process
water to
cooker
systems depend on cooker volume, cooker heat-transfer ca- Separator
pability, and the characteristics and feed-rate of the raw Dryer
material. Cooker contents are discharged into a percolator
to remove free-draining fat; then the solid material is
pressed (a continuous operation) or centrifuged (a batch Tallow Meal to
operation) to remove additional fat. The material is then mill
ground into meat meal. The fat is polished in disc centri-
fuges to remove fines and moisture. Figure 3. Semicontinuous wet-rendering system.
Batch dry rendering has the following advantages:
Grinder
Rendering
vessel Decanter
Screen
Acid
Sludge
Tallow
Dryer Separator surge
tank
tries) include hydrolysis using proteolytic enzymes or en- Fats can be almost white, yellow, or green (from contact
siling (12). with chlorophyll in digested plant material), or red or
brown (from overheating or from contact with blood). Pro-
Uses of Fat cessing parameters during rendering (temperature, time)
influence fat color. Some color components can be removed
Animal fats are composed of triglyceridesthree fatty ac- by bleaching with activated clay, and the color of the
ids esterified to glycerol. Fat quality is measured by titer; bleached sample read in a Lovibond tintometer. Fat
free fatty acid (FFA); FAC color (standard set by the Fat bleachability indicates the temperature and handling con-
Analysis Committee of the American Oil Chemists Soci- ditions that the tallow has been subjected to; the cleaner
ety); bleach color; and moisture, insoluble impurities, and the raw material and the lower the temperatures used, the
unsaponifiable matter (MIU). Other tests that can be spec- lighter the bleach color.
ified include saponification number, iodine value, peroxide The MIU value indicates fat purity. Moisture content
value, and smoke point. should be as low as possible, because microbial and en-
The fatty acid chain length and degree of saturation of zymic activity can hydrolyze fat at fat-water interfaces.
the carbon bonds affect the fat's hardness or melting point Insoluble impurities such as protein fines, ground bone,
(titer); the longer the chain length and the more saturated manure, and so on that were not completely removed dur-
the fatty acid, the higher the titer. Fats of different species ing processing may form colloidal fines that are not re-
of animals and from different sites in the body have differ- moved by settling or centrifuging. Trace amounts of copper,
ent titers. TyP6 of feed can affect the titer, but rendering tin, and zinc can cause fat oxidation, and any polyethylene
method does not. that has melted during rendering can adversely affect in-
When fat molecules break down, free fatty acids are re- dustrial processes that utilize fats. Unsaponifiable matter
leased, so FFA content, which is usually expressed as per- is fatty components such as cholesterol and gums that can-
centage of free oleic acid, indicates the degree of spoilage not be converted into soap by the use of alkali. Such matter
that has occurred. To minimize FFA values, poor-quality reduces soap yields and affects catalyst efficiency. Un-
raw material should be segregated from good-quality ma- saponifiable matter can also impart objectionable odors.
terial, and material should be processed promptly. If ma- The saponification number indicates the average length
terial cannot be processed promptly, the raw material of fatty acid chains, and the iodine number indicates the
should be kept whole (unbroken) as long as practicable, to degree of unsaturation. These values can be used to iden-
minimize microbial and enzymic activity, and preserved by tify types of fats and oils. The peroxide value indicates the
cooling, or by adding acid. Processing equipment and stor- degree of rancidity. Tallow that is not rancid and with good
age tanks should be kept clean. oxidative stability will have a low peroxide value. The
The factors affecting the color of fats include: animal smoke point is directly related to FFA and is the tempera-
breed, feed, age, and condition; source of the raw material; ture to which the fat can be heated before it begins to
and presence of contaminants (feces, gut contents, etc). smoke.
Raw material
Draining conveyor
Solids
Pre-breaker Twin-screw press
Pre-heater
Liquid
Press solids
Press
Solids Decanter liquid
Separator
Figure 6. Wet pressing low-temperature-
Meal to mill Stickwater Tallow rendering system.
The two important fats of (land) animals used commer- able amounts of tallow are still used for soap making. Gly-
cially are lard (fat from pigs) and tallow (fat from sheep cerine, a coproduct of soap or fatty acid production, can be
and beef animals). Lard is made from specified, clean, purified and used as a chemical in its own right.
sound tissues of healthy pigs, whereas rendered pork fat Edible tallow and lard can be used in margarine, short-
can be made from any fatty tissue. Edible tallow (dripping) enings, and cooking fats. Tallow tends to give a better fla-
is manufactured from specified edible fatty tissue. Oleo vor to fried foods and is more stable during the cooking
stock (premier jus) is a high-grade tallow prepared by low- process than vegetable oils. However, because hard fats
temperature wet rendering of the fresh internal fat from such as tallow can be associated with heart disease, the
beef. Inedible tallows (usually defined as fat with a melting overall consumption of edible tallow has declined.
point >40C) and greases (melting point <40C) are pro-
duced in many grades from inedible fatty tissue and dead Uses of Meals
stock.
Many different grades of tallow can be produced, and The material remaining after water and fat have been re-
most countries have their own trading standards for tallow moved can have one of many names, depending on the ren-
and grease. Tallow price reflects the prices obtained for dering method and/or raw material used. These names in-
other oils and fats, especially soy and palm oil. Vegetable clude tankage, meat-meal tankage, digester tankage,
oils are usually used for edible purposes and tend to be wet-rendered tankage, or feeding tankage (finely ground,
higher priced than tallow, which is used mainly for inedible dried residue from wet-rendering material low in hair,
processes such as soap manufacture, oleochemical produc- hoof, horn, manure, and paunch contents), digester tank-
tion, and as an energy source in animal feed. Beef tallow age with bone, meat and bone meal digester tankage, meat
is the largest component of bath bar soaps because of its and bone meal tankage, or feeding tankage with bone (of
economics and availability and its chemical composition. higher phosphorus content than feeding tankage); meat
Fats are a useful component of animal feeds, as they have meal (usually from dry rendering processes); and meat and
about twice the energy content of protein and carbohy- bone meal or meat and bone scrap (of higher phosphorus
drates. They also reduce dust, improve color and texture, content than meat meal). Feather meal is made from finely
enhance palatability, increase pelleting efficiency, and re- ground, wet-rendered feathers. This material is very di-
duce machinery wear during feed production. Tallow can gestible, but not well balanced nutritionally. Steamed bone
be used as an oleochemical feedstock. The resulting deriv- meal (from wet rendering), or bone meal (from dry render-
atives can be used to make abrasives, candles, cement ad- ing), is defatted, dried, and ground bones suitable for ani-
ditives, cleaners, cosmetics, paints, polishes, perfumes, de- mal feeding. Poultry meal has a similar composition, ap-
tergents, plastics, synthetic rubber and water-repellent pearance, and nutritional value to meat meal but is made
compounds. Tallow can be fractionated into its various from poultry by-products. Fish meal is another high-
components by crystallization, supercritical extraction, quality meal similar to meat meal.
solvent extraction, or detergent fractionation. Tallow and The type of raw material rendered and the rendering
its methyl esters can also be used as a fuel oil. Consider- process used influence the composition of the meal pro-
duced. Meals made from proteinaceous material are high poses is converted into pet food or is rendered to yield meat
in nitrogen (the crude protein content is usually >50%) meal and tallow.
and also contain calcium, phosphorus, and fat. Bone meal
and low-quality meat meals are made from material with
a high bone content and have a relatively small market. PET FOOD
One main use is as a fertilizer, but these meals are now
being replaced by mineral fertilizers. Meals with a higher Inedible animal tissue and rendered material can be used
protein content are sold as meat and bone meal for use in in both wet and dry pet foods. Pet foods require high-
animal feed formulations. They have a typical composition quality ingredients, which means that Tenderers may have
of 50% minimum crude protein, 4 to 10% moisture, 8 to to segregate raw material. Generally, pet-food manufac-
16% fat, and 20 to 30% ash. The price received for a given turers are using less fatty tissue and tallow and more
meal usually depends on its crude protein content, al- protein-rich tissue and/or meat meal in their formulations.
though some buyers may specify a minimum digestibility
and availability of amino acids.
Bovine spongiform encephalopathy (BSE), commonly BIBLIOGRAPHY
known as mad cow disease, was identified in the 1980s.
Because of the belief that BSE transmission is via feeding- 1. American Meat Institute Committee on Textbooks, By-
rendered ruminant protein to other ruminants, some coun- Products of the Meat Packing Industry, Institute of Meat
tries introduced legislation banning the use of ruminant- Packing, University of Chicago, Chicago, 1958.
derived animal proteins in animal feeds. This can have a 2. A. Levie, The Meat Handbook, 2nd ed., AVI Publishing Co.,
great economic impact on the rendering industry. Re- Westport, Conn., 1967.
searchers are developing economic sterilization processes 3. F. Gerrard, Meat Technology, Leonard Hill, London, 1971, pp.
and/or developing methods to monitor the sterilization ef- 65-77.
fect of rendering processes (13,14). 4. P. Filstrup, Handbook for the Meat By-Products Industry,
Alfa-Laval Slaughterhouse By-products Department, Den-
mark, 1976.
FINE CHEMICALS AND PHARMACEUTICALS 5. C. W. Dill and W. A. Landmann, "Food Grade Proteins from
Edible Blood," in A. M. Pearson and T. R. Dutson, eds., Edible
Animals have ductless (endocrine) glands that secrete hor- Meat By-Products, Vol. 5, Advances in Meat Research, El-
mones, and ducted glands and organs that release en- sevier Applied Science, New York, 1988, pp. 127-145.
zymes and other biologically active molecules. Many bio- 6. C. L. Knipe, "Production and Use of Animal Blood and Blood
logical chemicals can be recovered. A description of the Proteins for Human Food," A. M. Pearson and T. R. Dutson,
animal glands and the medicinal and pharmaceutical uses eds., Edible Meat By-Products, Vol. 5, Advances in Meat Re-
search, Elsevier Applied Science, New York, 1988, pp. 147-
of by-products is given in References 15 to 17.
165.
The glands and tissues used for producing fine chemi-
cals represent a small portion of the animal's live weight. 7. V. M. Gorbatov, "Collection and Utilization of Blood and Blood
Proteins for Edible Purposes in the USSR," A. M. Pearson and
Age, sex, and species of the animal determine the content T. R. Dutson, eds., Edible Meat By-Products, Vol. 5, Advances
of the active material. Most glands are very perishable and in Meat Research, Elsevier Applied Science, New York, 1988,
must be processed quickly to limit autolysis and microbial pp. 231-274.
activity. The logistics of collecting sufficient raw material 8. J. Vrchlabsky and J. Budig, "Animal Blood as Feed-Chemical
to operate a fine chemical plant or process usually limit Preservation," Meat Focus Int. 5, 82-83 (1996).
operations either to larger meat plants or to centralized 9. Q. T. Pham, "Behaviour of a Conical Spouted-bed Dryer for
processing of material from many small plants. Animal Blood," Canadian J. Chem. Eng. 61, 426-434 (1983).
10. J. E. Swan, "Maximising Yields from Conventional Blood Pro-
cessing," MIRINZ Food Technology and Research Ltd. Bulle-
SAUSAGE CASINGS tin No. 10, Hamilton, New Zealand, 1985.
11. T. Fernando, "The MIRINZ Low-Temperature Rendering Sys-
Intestines can be processed into natural casings used in tem," Proc. of the 22nd Meat Industry Research Conference,
sausage manufacture (18). Casing quality is affected by MIRINZ Food Technology and Research Ltd. Publ. No 816,
handling and cleaning procedures. Factors such as the age Hamilton, New Zealand, 1982, pp. 79-84.
and species of the animal, breed, fodder consumed, and the 12. B. Urlings, Fermentation of Animal By-Products, ADDIX,
conditions in which the animals are raised also affect cas- Wijk Bij Duurstede, The Netherlands, 1992.
ing quality and value. Animal casings naturally come in a 13. H. Heubel, "The Continuous Sterilization Process for Slaugh-
wide variety of different shapes and sizes. The preference terhouse By-Products," in B. A. P. Urlings, ed., Upgrading of
for a particular type of casing varies from country to coun- Slaughter By-Products for Animal Nutrition, ECCEAMST,
try. Utrecht, The Netherlands, 1995, pp. 33-37.
Reconstituted casings are manufactured from hide 14. D. M. Taylor, S. L. Woodgate, and M. J. Atkinson, "Inactiva-
pieces (19), and artificial casings are often made from cel- tion of the Bovine Spongiform Encephalopathy Agent by Ren-
lulose. Animal intestines are also used for the manufacture dering Procedures," Veterinary Record 137, 605-610 (1995).
of surgical sutures, and strings for musical instruments 15. H. W. Ockerman and C. L. Hansen, Animal By-Product Pro-
and tennis rackets. Intestinal tract not used for these pur- cessing, Ellis Horwood, Chichester, England, 1988.
16. R. J. Banis, "Pharmaceutical and Diagnostic By-Products," in sheep) are efficient utilizers of the millions of acres of land
J. F. Price and B. S. Schweigert, eds., The Science of Meat and in the United States too rough or dry to grow crops.
Meat Products, 3rd ed., Food and Nutrition Press, Inc., West-
port, Conn., 1987.
Agriculture is the largest industry in the United States,
accounting for 15% of the gross national product. About 2
17. A. M. Pearson and T. R. Dutson, eds., Inedible Meat By-
Products, Vol. 8, Advances in Meat Research, Elsevier Applied
million people are directly involved in production agricul-
Science, New York, 1992. ture with ca 1.37 million agricultural operations involving
beef or dairy cattle (2).
18. R. E. Rust, "Production of Edible Casings," A. M. Pearson and
T. R. Dutson, eds., Edible Meat By-Products, Vol. 5, Advances
in Meat Research, Elsevier Applied Science, New York, 1988, Beef Cattle
pp. 147-165. The beef cattle industry is the largest segment of American
19. L. L. Hood, "Collagen in Sausage Casings," A. M. Pearson, agriculture, accounting for almost 25% of all farm market-
T. R. Dutson, and A. J. Bailey, eds., Collagen as a Food, Vol. ings (3). Indeed, nearly 26 billion Ib of beef were produced
4, Advances in Meat Research, AVI Publishing Co., New York, in 1997 (4). Cattle are raised in every state, including Ha-
1987, pp. 109-129.
waii and Alaska. Commercial cattle operations tend to be
large and diverse enterprises that involve many types and
GENERAL REFERENCES breeds of cattle. The beef cattle industry in the United
States is distinctly segmented into three production
References 11 and 17 give a good overview. schemes: cow-calf (both commercial and purebred), stocker
T. Fernando, "Blood Meal, Meat and Bone Meal and Tallow," in A. (intensive grazing), and feedlot. The term feeders is some-
M. Pearson and T. R. Dutson, eds., Inedible Meat By-Products, times used to describe cattle, pigs, and lambs going into
Vol. 8, Advances in Meat Research, Elsevier Applied Science, intensive feeding programs. Feeder cattle production is the
New York, 1992, pp. 81-112. goal of commercial (nonpurebred) cow-calf and stocker
J. F. Price and B. S. Schweigert, eds., "Meat Animal By-Products operations. Feeder cattle may be either steers or heifers
and Their Utilization," The Science of Meat and Meat Products, and are the animals of highest value in terms of beef pro-
3rd ed., Food and Nutrition Press, Inc., Westport, Conn., 1987. duction. The singular goal of purebred cattle production is
D. Swern, ed., Bailey's Industrial Oil and Fat Products, VoIs. 1-3,
the selective breeding and selection of superior offspring
4th ed., Wiley, New York, 1982.
I. A. WoIfF, ed., "Red Meat and Meat Products," CRC Handbook of to attain distinguishable characteristics of the breed, such
Processing and Utilization in Agriculture, Vol. 1, Animal Prod- as carcass merit, production efficiency, or reproductive
ucts, CRC Press, Boca Raton, FIa., 1982. traits.
Stocker cattle are weaned calves grazed on grass for
inexpensive growth. This period is characterized by growth
J. E. SWAN
of lean tissues and frame size. In the Midwest, stocker cat-
University of Waikato
Hamilton, New Zealand tle may be grazed on small grain pastures, grain stubble,
or legume pastures before being placed in feedlots for fat-
tening. Stocker cattle are usually owned for less than 1
year.
ANIMAL SCIENCE Fattening steers and heifers in feedlots involves feeding
AND LIVESTOCK PRODUCTION nearly market-sized cattle moderately high to high energy
rations (grain) until they have reached a sufficient finish
The discipline of animal science is concerned with the ap- (fattening) to produce a carcass that will grade USDA
plication of the biological and physical sciences to the ef- choice. Large feedlots predominate in the Western states
ficient production of livestock. Food and fiber are the pri- and account for a large percentage of fed-beef marketings.
mary products of livestock production in the United States. Midwestern feedlots tend to be more plentiful, but are gen-
Examples of products derived from animal agriculture in- erally smaller and produce a smaller percentage of fed-beef
clude meat, milk, eggs, wool, mohair, leathers, pharmaceu- marketings. Most fat steers and heifers are slaughtered at
ticals, and products used in research laboratories through- 15-24 months of age.
out the world. Bulls are sometimes fed for slaughter and are usually
referred to as bullocks. Bulls generally gain weight more
BUSINESS ASPECTS OF LIVESTOCK PRODUCTION rapidly and are more feed efficient than steers or heifers.
Bulls also tend to be leaner. Older cows culled from beef or
dairy cow herds are also sometimes fed grain for short pe-
Livestock are raised on a wide variety of terrains, climates,
riods of time before slaughter to increase the palatability
and management systems. However, concentrations of
(juiciness and tenderness) characteristics of the meat.
livestock raising often border on regions of grain raising
(cattle and pigs are heavily concentrated in the Midwest-
ern states of Iowa, Kansas, Nebraska, and Texas) or lo- Dairy Cattle
cated near population centers (dairy cattle are concen- Dairy farms are highly specialized agricultural enter-
trated in the Northeastern states, Wisconsin, Idaho, and prises, with considerable financial and labor input and re-
California) (1). Fifty percent of the land area of the United turns. Dairying as a secondary enterprise on farms and
States is classified as grazing or range area that cannot be ranches is uncommon. The number of dairy farms and
used to cultivate crops (2). Ruminant livestock (cattle and dairy cattle in the United States has steadily declined dur-
ing the past 20 years. The number of farms with dairy cat- The trend in pork production, as in other agricultural
tle decreased about 92% from 2 million in 1950 to 164,000 operations, has been toward larger and more specialized
in 1992 (1,5,6). However, the decrease has been offset by a operations. There is also a trend toward more confinement
significant increase in milk production (Fig. 1). Modern units in the production of pigs. Swine production systems
dairy cattle produce an average of 16,400 Ib of milk per usually can be described by one of three basic systems:
lactation (7). farrowing to finishing, feeder pig production, and finishing
The price dairy farmers receive for whole (fluid) milk feeder pigs.
has been, historically, on hundred weight basis according Finished pigs are usually sold directly to the processor
to the percentage of butterfat. However, as the value of by the producer. Selecting the market and timing the pre-
butterfat has declined as the most valuable component of sentation of pigs for slaughter are two of the most impor-
whole milk, the price differential has increased less than tant decisions made by the swine producer. Most pigs are
the price per pound. The decrease in demand for butterfat sold on a live-weight basis, but some are sold based on
is directly attributable to the introduction of margarine carcass yield and grade. Computerized hog-marketing sys-
(containing plant oils), increased consumption of cheeses tems are also being used in some parts in the United
(made from whole milk), and processed food containing States.
nonfat dry milk. Also, there has been a strong trend for
health-conscious people to eat and drink only low fat and
Sheep
non-fat dairy products such as low fat cottage cheese, low
fat yogurt and skim milk. The products of sheep production businesses are primarily
Locations of dairy farms have traditionally been close lambs and mutton for meat and wool. Most of the sheep in
to major markets. This is because of the high cost of trans- the United States are raised in the Western states. Texas,
porting whole milk, which contains a high proportion of California, Colorado, South Dakota, Wyoming, and Utah
water, and because milk is relatively perishable. However, account for more than 50% of the sheep produced (10).
in recent years location of dairies near consumers has been Sheep production systems are generally classified as farm
a less important consideration than the high cost of real flocks or range flocks. Predators, such as coyotes and wild
estate near major markets. Also, conflicts between large dogs, and disease are some of the common problems asso-
dairies and home owners over water quality, dust, flies, ciated with raising sheep. Lamb mortality rates as high as
and odors have forced dairy farms to relocate to less pop- 20% are not uncommon. Most feeder lambs are sold to feed-
ulated areas. Improved processing techniques and more lots weighing between 65-80 Ib. Ewes culled from flocks
rapid transportation networks also have contributed to de- are also marketed for slaughter. The seasonality of breed-
creased costs in moving milk to markets. ing for sheep unfortunately causes a shortage of fresh lamb
during certain times of the year.
Swine
Swine production units are located in every state of the
United States, but are generally concentrated in or near THE DISCIPLINE OF ANIMAL SCIENCE
feed-grain-growing regions of the central United States.
The corn belt states of Iowa, Illinois, Minnesota, Indiana, The multiple and interdisciplinary needs of farm animal
and Nebraska are leaders in market hog production (1,9). production that focus on growth, reproduction, and lacta-
Swine farrowing was traditionally a spring and fall opera- tion are at the center of animal science programs in re-
tion, but with the development of improved housing and search, teaching, and extension. Animal science is primar-
nutrition, production of swine is a year-round business. ily an applied science that incorporates advances in science
This has tended to equalize the monthly marketings of pigs and technology from all disciplines. Nearly all land-grant
and reduced the seasonal fluctuations in market price. universities, as well as several state and private colleges
with agricultural programs, offer a bachelor of science de-
gree in animal science. Most animal science departments
in land-grant universities also offer graduate programs
Milk production Milk per cow leading to master of science (M.S.) and doctor of philosophy
Number of cows degrees (Ph.D.). The Ph.D. degree is a research-based sci-
Percent of 1955
ence degree.
Curriculum at the undergraduate level is designed to
prepare students for professional careers in animal agri-
culture. The student majoring in animal science usually
takes specialized courses, which include nutrition, breed-
ing and genetics, biochemistry, animal reproduction, agri-
cultural economics, animal health, meat science, dairy sci-
ence, and animal production and products courses.
The Journal of Animal Science. The Journal of Dairy
Science, and Meat Science serve as the repository for ad-
Figure 1. Index of milk production, milk per cow, and cow num- vances in the science of livestock production as well as
bers in the United States. Source: Refs. 5, 6, and 8. their products.
PRINCIPLES OF ANIMAL REPRODUCTION hormone testosterone), excretory ducts (epididymis, vas
AND BREEDING deferens, and ejaculatory duct), and accessory structures
(prostate, seminal vesicles, bulbourethral glands, and
Productivity of livestock depends on reproductive effi- penis). The scrotum, containing two testes, provides for ef-
ciency and is usually measured by the number of offspring ficient regulation of testicular temperature. Descent of
produced by an animal or herd per unit of time. Therefore, both testes from the abdomen to their proper scrotal loca-
management of reproductive cycles is critical for obtaining tion is necessary for maximal fertility. Failure of one or
maximum efficiency of reproducing animals. both testes to descend is a common reproductive organ de-
fect in livestock, especially in swine, where the condition
Animal Reproduction is a hereditary defect transmitted by the male and is re-
ferred to as cryptorchidism (13).
Dairy and beef cattle are derived from common ancestors Reproductive management of the male primarily in-
and thus have common reproductive characteristics. The volves maintenance of health and nutrition to optimize
period of time from one ovulation to the next ovulation is sperm production and libido. Methods for assessing indi-
called the estrous cycle. The estrous cycle in cattle is on vidual male fertility, such as breeding soundness evalua-
average 21 days in length and is characterized as being tions, are subjective and poorly correlated with pregnancy
one in which the cow does not permit mating to occur ex- rates.
cept at the time of ovulation. This period of time in which
mating is permitted is relatively short, being in the order
Breeds of Livestock
of 16-18 h. The estrous cycle in cattle is continuous (poly-
estrous) throughout the year and is not seasonal as is the Decisions about breeding are some of the most important
case in some other ruminant-type animals such as sheep, decisions a livestock producer must make. The livestock
deer, antelope, and elk. Cattle ovulate 10-14 h after the breeder must consider the heritability of a characteristic,
end of estrus, and normally one follicle ovulates per estrous such as prolificacy, feed conversion, milk yield, or carcass
cycle. The gestation period is 283 days, and twins occur merit, for example. The livestock breeder also must con-
only 1% of the time. sider the merits of inbreeding, outbreeding, crossbreeding,
Sheep are generally seasonally polyestrous, with recur- and the relative merits of different breeds of animals.
ring estrous cycles during the fall of the year followed by The development of modern breeds of livestock began
a prolonged quiescent period. Some breeds of sheep that in the 170Os. The origin of cattle and sheep breeds can be
originated in equatorial regions and are subject to less var- traced to Europe and the British Isles. For classification
iations in temperature and photoperiod have longer breed- purposes there are four basic categories of modern beef and
ing seasons. The period of sexual receptivity in sheep lasts dairy cattle. The classification system for cattle is not con-
for 24-36 h, but may vary widely. The length of the estrous sistent because two of the categories reflect geographical
cycle is 14-19 days. Seasonal breeding in animals is as- origin of the cattle and the other two reflect the purpose of
sociated with an increased frequency and size of episodic the cattle.
releases of luteinizing hormone (11). Ovulation normally
occurs near the end of estrus. Ovulation rate is influenced
by breed and nutrition, but twinning is extremely common 1. British and continental breeds (beef): Includes
in sheep. Gestation is 150 days in length. Angus, Hereford, Shorthorn, Charolais, Limousin,
The pig, like the cow, is polyestrous. The period of sex- Chianina, Gelbvieh
ual receptivity in pigs lasts about 40-60 h and may be in- 2. North American breeds (beef): Brahman, Brangus,
fluenced by season, breed, and endocrine dysfunction (12). Beefmaster, and Santa Gertrudis
The length of the estrous cycle is 21 days. Ovulation rates 3. Dual-purpose breeds (beef and dairy): Ayrshire,
are strongly influenced by weight of the gilt at breeding Milking Shorthorn, Red Poll, and Brown Swiss
and the amount of inbreeding. Gestation in the pig is 114
4. Dairy breeds: Guernsey, Holstein, and Jersey
days and average litter size is in the order of 9-12 pigs per
litter.
The estrous cycle in all livestock is characterized by pro- The foundation of modern-day pigs can be traced to Eu-
found changes in behavioral patterns and blood hormone ropean and Asiatic strains of pigs. Modern swine are raised
profiles. Cyclic changes during the estrous period reflect to produce lean high-quality pork. However, not long ago,
the secretory functions and interdependence of the ovary, breeds of swine were classified as lard-type and bacon-
uterus, hypothalamus, and pituitary gland. The estrous cy- type. Although the individual breeds of swine continue to-
cle is controlled by ovarian hormone secretions (estrogens day, all swine producers strive for the same high-quality
and progesterone) and may be subdivided into a follicular meat-type pig.
phase, an ovulatory phase, and a luteal phase (Fig. 2). The As in the case of cattle, the classification system for
ovary functions to provide fertilizable ova and a balanced breeds of sheep is inconsistent. The Rambouillet and Me-
ratio of steroid hormones to facilitate development of the rino breeds were developed for the production of the fine
reproductive tract for migration of the early embryo and wool characteristic, but much lamb and mutton comes
successful implantation in the uterus. from these breeds. Likewise, income derived from wool
The male reproductive system in livestock is comprised represents a significant portion of the value of the meat-
of two testes (producing both sperm and the male sex type breeds.
Follicle-stimulating hormone
gonadotropic hormones
steroid hormones
Progesterone
Estradiol
Luteinizing hormone
Abomasum
(18). To facilitate rapid chilling of the carcass, beef car- stamp informs the buyer the meat was processed in a fed-
casses are entirely split along the backbone, while pig car- erally approved plant and is wholesome and safe for hu-
casses are usually split to the neck. man consumption. Additionally, the carcass may be graded
The term carcass is what remains after dressing and for meat yield and quality. The yield grade is an estimate
usually refers to both sides of the same slaughtered ani- of the portion of the carcass that is edible meat. Quality
mal. A side is one of the two halves of a split carcass. Beef grades are intended to identify meat on the basis of pal-
quarters are the portions remaining after splitting a side atability and cooking attributes. Factors used to establish
of beef between the 12th and 13th rib. Wholesale cuts are quality grades include kind or species of animal, class or
divisions of the quarters including the round, full loin or physical attributes, maturity, marbling, firmness of flank,
short loin and sirloin, flank, rib, short plate, chuck, brisket, color and structure of lean, and conformation, fleshing, and
and fore shank. Primal cuts are any of the wholesale cuts finish of the carcass. USDA quality grades for various
except for short plates, briskets, flanks, and fore shanks. kinds of meat are given in Table 3.
The principal cuts of beef, pork, and lamb are shown in The Food and Drug Administration (FDA) is responsi-
Figures 4, 5, and 6. Most beef is sold as carcass sides or ble for ensuring the safety of the drugs used in livestock
quarter or wholesale cuts to retailers, wholesalers, chain- production and food additives. Both the FDA and the Fed-
store breaking plants, and restaurants. However, an in- eral Trade Commission have been involved with monitor-
creasing portion of beef is sold as 60-80 Ib saw- or knife- ing and regulating claims made during advertising of food
ready subprimal cuts shipped in boxes. Processors nearly products.
always reduce pork carcasses to wholesale and retail cuts
at the plant because hams and bellies, and sometimes
other cuts, are smoked and cured. Most lamb is sold as MILK PRODUCTION
intact carcasses, but some carcasses are reduced to whole-
sale cuts. Dairy cattle are normally milked two or three times per
Significant quantities of beef are ground, tested for lean 24-h day. Following freshening (parturition), maximum
content, and blended to meet federal and state quality re- milk production is normally reached after 45 days. A slow,
quirements for fat content. Low-quality carcasses, such as but steady decline in milk produced by the cow occurs after
cutter and canner grades of beef, pale and soft pork car- peak yield until she is dried. Normal lactation periods for
casses, and cull grades of lamb and mutton, are not sold commercial dairy farms are 305 days lactation and 60 days
as wholesale or retail cuts but are instead boned-out at the dry (Fig. 7). The dry period allows for the cow to replenish
plant. The edible meat from these carcasses may be sold her body reserves and rest her mammary tissue. Because
as hamburger, or used in the preparation of a variety of a calf must be produced every 12.5 to 13.5 months in order
meat products, such as canned meat products or sausage. to meet this idealized production schedule, cows are bred
The USDA through the Food Safety and Inspection Ser- at approximately 80-90 days of lactation.
vice (FSIS) is responsible for ensuring the wholesomeness Feeding dairy cattle represents approximately 50% of
of the meat supply. FSIS assurance includes antemortem the cost of milk production. The percentage of protein and
and postmortem inspection and compliance with sanita- fat may be influenced by feeding and management prac-
tion and temperature, ingredients, and label require- tices on dairy farms. Dairies may select feeding programs
ments. Meat bearing the U.S. "inspected and passed" to produce fat and produce percentages that best suit milk
BEEF CHART
RETAIL CUTS OF BEEF WHERE THEY COME FROM AND HOW TO COOK THEM
Boneless Shoulder
Pot-Roast or Steak Cross Rib Boneless Bottom Round
Top Loin Steak Wedge Bone Sirloin Steak Roast or Steak1" Cubed Steak*
tot-fast
enderloin
Rib Eye (Delmonico) (Filet Mignon)Steakor
Beef for Stew Ground Beef** Roast or Steak Roast (also from Sirloin 13) Boneless Sirloin Steak Eye of Round* Ground Beef**
CHUCK RIB SHORT LOIN SIRLOIN ROUND
Braise, Cook in Liquid Roast, Broil, Panbroil, Panfry Roast, Broil, Panbroil, Panfry Broil, Panbroil, Panfry Braise, Cook in Liquid
Short Ribs
Shank Cross Cuts Fresh Brisket Skirt Steak Rolls
Ground Beef Rank Steak* Tip Roast*
Tip Steak*
Pork Cubes Blade Chop Rib Chop Loin Chop Sirloin Chop
Cubed Steak* Boneless Leg Sliced Cooked
(Fresh Ham) "Boiled" Ham
Ground Pork*
fresh Arm Picnic Smoked Arm Picnic Arm Roast Spareribs Slab Bacon
*My be nuuto from Boston ShouMor, Picnic Shoulder, Loin or L*g. This chart approved by
National Live Stock and Meat Board
Cubes Frenched Rib Chops Leg Chop (Steak) Combination Leg Center Leg
forKabobs Boneless Blade Chops Loin Chops
(Saratoga)
Arm Chop
DJWIA(MAA FVu ikin Sirloin Half of Leg Shank Half of Leg
Cushion Shoulder Crown Roast DOnei cSS UOUD(B
Loin Roast Boneless Sirloin
Roast
Square Shoulder Neck Slices Rib Roast Loin Roast Sirloin Roast French-Style Leg (tench-Style Leg,
Sirloin Off
Fore Shank Breast Rolled Breast Stuffed Breast Hind Shank (Urge Pieces) Lamb for Stew* (Small Pieces)
RiWets Boneless Ribtets Spareribs Stuffed Chops Cubed Steak Lamb Patties Ground Lamb
* Lamb for stew or grinding may be made from any cut This chart approved by
**^faboba or cube eteaks may be made from any National Live Stock and Meat Board
thick solid piece of boneless Lamb.
a-Tocopherol
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TECHNICAL DIVISIONS basis to purchasers of the book.
No Yes
Feasible? Changes?
Yes No
Detailed current Give up
practices
Need to generate
new alternatives
Proposed practices
Evaluate
Need to select a
new practice
Select
If nonsatisfactory Savings?
Design details
Cost
Evaluate
extension agents, and with researchers. As a first step, sev- raceways, tanks, and cages. Although construction mate-
eral alternative designs may be generated and evaluated rials for the various types of holding systems differ de-
to select the most promising one for further development. pending on specific requirements, they should have gen-
After evaluation and selection, the details of the design are eral characteristics, including being corrosion resistant,
completed, including estimated costs and preparation of nontoxic, with smooth and nonabrasive surfaces, strong
construction documents. Evaluation of the plans and fa- and lightweight, resistant to ultraviolet radiation, and low
cilities should be carried out at the various stages of the in cost (5,6). Typically, no material satisfies all criteria op-
process to minimize the probability of errors, as well as to timally, and selection is based on the particular constraints
ensure maximum functionality and operational efficiency of a given project.
for the investment. Evaluation of the completed installa-
tion will serve in the preparation of future designs or in Ponds
the possible expansion of the facility.
Pond size, shape, and construction technique varies widely
(7,8). Ponds tend to be shallow, less than 1.5 m deep, and
HOLDING SYSTEMS vary in area between less than 100 m2 to more than 10 ha
(Fig. 2). The pond bottom is sometimes covered with con-
The types of impoundments or holding systems used in crete or plastic liners to prevent water losses to infiltration.
aquaculture are determined by the requirements of the The ponds may be built by excavation, by construction of
particular species and by the production and management dikes, or more commonly by a combination of the two tech-
practices being employed. Typical systems include ponds, niques. In all cases, pond design should incorporate struc-
common shapes are round, square with rounded corners,
hexagonal, and octagonal (5,9,10) (see Fig. 4). The choice
is often made on the basis of space availability and con-
struction materials, as there aren't large differences in the
hydraulic properties of the various shapes. Tank size
ranges from an equivalent diameter of less than 1 m to
more than 10 m. Water depth is normally maintained be-
tween 0.5 m for the smaller tanks and 1 to 2 m for the
larger tanks. The two most common materials used for
tanks are fiberglass and concrete.
The size and shape of tanks used in aquaculture vary
greatly, but the common characteristic is that flow ap-
proaches the ideal continuously stirred tank reactor
(CSTR) model in which water quality within the tank is
Figure 2. Pond being used for the culture of shrimp with supple-
approximately uniform. To achieve this uniformity, water
mental mechanical aeration. is introduced along the periphery of the tank through one
or more inlets that normally inject the water tangentially,
and the water effluent is collected from the center of the
tures for water inflow for filling and maintenance flows, tank (10,11). Contrary to raceways, it is possible to achieve
and for effluents including flows during pond drainage and a certain degree of independence between water flow rate
emptying. and water velocity in a tank by manipulating the inlet and
outlet characteristics and location. An important feature
Raceways is that by adjusting the circulation pattern and water ve-
locity to maintain particulate matter in suspension, tanks
Raceways are relatively narrow, long channels with water
may be made to be "self-cleaning" (10,11).
constantly entering through one end of the channel and
A recent development in tank culture is the introduc-
leaving through the opposite end (Fig. 3). Raceways are
tion of "double drains" in which two water streams are cre-
often built of concrete, and the normal dimensions are in
a ratio of approximately 30:3:1 (length:width:depth). Race- ated in the drain, one constituting a large percentage of
the flow containing a very small fraction of the solids re-
ways are the most common holding system for the produc-
leased to the tank water (fish feces and uneaten feed), and
tion of trout and are usually approximately 30 m long.
the second stream conveying no more than 5 to 10% of the
Flow in a raceway approaches plug flow characteristics,
total flow from the tank, but containing up to 90 or 95% of
creating a gradient of water quality along the raceway; wa-
the tank solids (10,11). These new double drains offer op-
ter quality is best near the head of the raceway where the
portunities for improved water utilization efficiency and
water enters and degrades toward the drain side of the
water treatment systems, with the high flow-low solids
raceway. Raceways are often constructed in series of up to
stream being relatively easy to treat for reuse, and the low
six raceways with reaeration between raceways to replen-
ish some of the oxygen used by the fish. flow-high solids stream being suitable for treatment prior
to disposal. Flow rates in tanks are normally selected to
Tanks
result in residence times ranging from 10 to 15 min to sev-
eral hours, and the value used depends on the level of wa-
Aquaculture tanks are normally designed to optimize the ter treatment (normally aeration) taking place within the
movement of water around the center of the tank. As such, tank and on the fish biomass being held.
Figure 3. Farm that uses raceways for the culture of trout. The Figure 4. Round concrete tanks used for the culture of striped
raceways are laid out in series and in parallel to optimize land bass. Water in the tanks is reoxygenated using pure oxygen injec-
and water use. tion systems and aerated for carbon dioxide removal.
Cages As a starting point in the description of important pro-
cesses in an aquaculture operation, one can consider how
Although cages have been used in aquaculture for many a fish relates to its environment. Fish consume oxygen
years, they have received a great deal of attention recently, from the water and release water products from their me-
especially with the development of the salmon industry in tabolism back into the water. The main waste products of
Norway and other countries (Fig. 5). Conventional cage concern are ammonia, carbon dioxide, and particulate and
technology is based on a rigid frame that is either floating dissolved organics. Depletion of dissolved oxygen below a
or fixed, and to which a cage made of some type of netting certain level, which is species and size dependent, results
material is attached. Traditionally, cages had been rectan- in increased stress to the fish and may ultimately result in
gular and relatively small, with total volumes of less than suffocation. Similarly, the accumulation of waste products
10 m3. The recent growth of the industry, the availability may reach toxic levels, as in the case of ammonia and car-
of new materials and technologies, and the presence of bon dioxide; it may alter the pH of the water, again as a
competing users for coastal resources have resulted in the result of carbon dioxide accumulation; it may affect growth
development of large cage systems suitable for open sea and reproductive behavior as a result of the accumulation
deployment (6,12). Some of these cages may be more than of dissolved organics such as hormones; or it may affect the
50 m in diameter, 30 m deep, with production volumes of overall oxygen balance of the system by the oxygen de-
more than 50,000 m3, and are designed to hold up to mand created by the decomposition of particulate and dis-
1,000,000 kg offish (6,12). Engineering contributions into solved organics.
the design, construction, and anchoring of cages becomes A major difference between aquaculture and land-based
very specialized as the cage size increases and as cages are food production systems is that in an aquaculture system
placed in more exposed locations. Cages are subjected to the animal or plant takes its nutrients and oxygen and
static and dynamic loads. Static loads are relatively easy releases its waste products into the same environment: the
to quantify and are caused by the weight of the fish and water. Maintaining water quality in an aquaculture sys-
the structure itself, but transient loads caused by wind, tem is based on providing sufficient oxygen to satisfy the
waves, and currents may be orders of magnitude greater needs of the fish, and in removing metabolites to prevent
than static loads and are very difficult to determine accu- their buildup to toxic levels. Design of systems to achieve
rately (6). Frequent cage maintenance is required to pre- those goals requires the quantification of processes that
vent fouling of the net from restricting the flow of water. take place within the system, especially those related di-
Exchange of water through the net must be sufficient to rectly to the target species. The relative importance of the
maintain adequate water quality for the fish. various consumption and production processes depends on
the type of aquatic production system being considered. In
QUANTIFYING PROCESSES general, the shorter the residence time of the water in the
production system, the more important are the fish-related
As was mentioned in the definition of aquacultural engi- processes with respect to other biological processes taking
neering, many engineering disciplines can be applied to place. If, on the other hand, the residence time is long
the design of aquaculture systems. In this section, some of (more than one day and as long as one year), as is the case
the critical processes that are unique in an aquaculture in most ponds, biological and chemical processes that are
system and that define design parameters will be de- not directly associated with the target product's metabo-
scribed. The key processes in the design of aquatic systems lism become very important in determining water quality.
have to do with the primary water quality factors that af- As an example, dissolved oxygen in a tank with a short
fect the cultured organism and with how the organism af- residence time will be determined by the concentration in
fects water quality. the influent water, the fish biomass being held in the tank,
the amount of oxygen being added to the system through
aeration mechanisms, and the oxygen consumption by the
fish. In a pond, on the other hand, many processes can have
significant effects on dissolved oxygen concentration.
These processes include photosynthetic oxygen production,
respiration by all the organisms in the ponds (phytoplank-
ton, zooplankton, fish, bacteria, and sediment decomposi-
tion processes), and gas exchange between the water and
the atmosphere.
Quantification, design, and management of aquaculture
production systems are most predictable in those systems
with short residence times, where the majority of water
quality changes are associated with fish activity. Pond sys-
tems, often with long residence times, are difficult to quan-
tify and their management remains very much an art
rather than a science.
Design of systems is ultimately based on mass balances
Figure 5. Cages used for the culture of Atlantic salmon in Nor- on the critical water quality factors already mentioned.
way. The general form of the mass balance equation for a par-
ticular substance (eg, dissolved oxygen or ammonia) in a for the species of interest and for the feed and culture sys-
control volume can be written as tem being used.
where TEMP is the water temperature (0C). ^Reaer = 0.03 X V - 0.0132 X Vw + 0.0015
Equation 12 and tables of dissolved oxygen saturation 1
X i^dnh" ) (13)
are normally prepared for an atmosphere of 20.9% oxygen.
Oxygen enrichment of the atmosphere will result in a cor- vw is the wind velocity (m s"1), and D is the pond depth
responding increase in saturation dissolved oxygen con- (m).
centration. Enrichment may be achieved by aerating with An implicit assumption in equation 13 is that conditions
"pure" oxygen. in the pond are uniform and there is a minimum of strat-
An important difference between aeration systems used ification.
for aquaculture and those used in water and wastewater
treatment is that the "driving force" (DOSat DO) in aqua-
Ammonia Removal
culture tends to be lower, reducing the rate of oxygen
transfer for a given aerator. The lower driving force is Ammonia is toxic to aquatic animals and is also the waste
caused by the requirement of most fish for dissolved oxy- product of their protein metabolism. The sensitivity of
gen concentrations above 3 to 4 g m~ 3 , compared with the aquatic animals to ammonia concentration depends on
usual limit of just above zero in wastewater treatment. species, live stage, level of stress, and on other environ-
mental conditions. Ammonia exists in water as the equi- and a number of filters have been developed that incor-
librium product of ammonium ion and unionized ammonia: porate some form of automated cleaning (eg, drum or disk
filters). Simple settling tanks or ponds with overflow rates
NH4+ ++ NH3 + H + pKa = 9.25 at 250C (14) between 40 and 80 m d"1 can result in total suspended
solids removal rates of 65 to 85% (25). Aquaculture settling
Unionized ammonia (NH3) is the toxic form of ammonia ponds traditionally have been operated with infrequent
(5,14). Approximate estimates of the concentration of un- sludge removal, relying on biological decomposition to pre-
ionized ammonia in fresh water can be obtained form mea- vent excessive accumulation of sludge.
sures of total ammonia (NH3 plus NH4f concentrations) Recent concerns with the possible release of nutrients,
and pH as (5): especially phosphorus, from aquaculture operations to nat-
ural waters have caused a reevaluation of techniques
[NH3] - [TA] X (l/10(p^-pH)) (15) available for solids removal. Given the technical difficul-
ties and expense associated with treating aquaculture ef-
where [NH3] is the unionized ammonia concentration fluents, a combination of nutritional and engineering ap-
(mol/L) and [TA] is the total ammonia concentration proaches are being studied to reduce the solids (and
(mol/L). nutrient) content in effluents.
Removal of ammonia from aquaculture systems may be
achieved by ion exchange or by biological nitration. Ion ex- FUTURE DEVELOPMENTS
change is carried out with a natural zeolite (clinoptilolite)
that has a high affinity for ammonium ions. Removal ca- The aquaculture farm of the future will take many forms.
pacity of the resin varies widely, but a common design The difference with today's farms will be in the level of
value is around 1 mg NH4f (g clino)"1 (22). Clinoptilolite intensity of water use, in the degree of control over the
resin may be regenerated with brackish or salt water, mak- culture environment exerted by the operator, and in the
ing the use of the resin suitable for fresh water applica- predictability of growth and overall production rates. The
tions only. Ion exchange columns need to be designed to application of engineering will become more and more im-
incorporate the downtime involved with the recharging portant as the aquaculture industry continues to grow and
and reconditioning. In addition, unless properly main- diversify. Developments will be in new culture systems,
tained, these columns have a tendency to be colonized by materials, equipment, and water quality monitoring,
bacteria and become biological filters. treatment, and control. The efficient use of natural re-
The biological removal of ammonia by the process of sources, especially water, will be a primary constraint on
nitrification is carried out by two groups of bacteria: nitro- new aquaculture operations. To make more efficient use of
somonas, which take ammonia to nitrite; and nitrobacter, water, higher fish biomass will be maintained per unit of
which complete the reaction to nitrate. Nitrate is toxic to water volume and per unit of water use by the implemen-
fish only at very high concentration and therefore is a suit- tation of water treatment and recirculation systems. The
able end product for ammonia and nitrite, forms of nitro- safe rearing of these large biomasses will require contin-
gen toxic to fish. The nitrification process is relatively slow uous monitoring of water quality, and the use of alarms
and sensitive to temperature, pH, and ammonia concen- and backup systems. In most cases these will be all com-
tration. To achieve practical nitrification rates, high bac- puter controlled.
terial biomass must be maintained, which is normally Improvements in water treatment are also needed to
achieved with some form of attached growth filter (23,24). make possible reductions in water use and the commercial
Many types of filters are used for ammonia removal: down- viability of culture systems based on water reuse. New,
flow, upflow, rotating disks, submerged, trickling, fluidized more efficient and reliable filtration systems for the re-
beds, and soon (23,24). Removal rates are highly variable, moval of particulate and dissolved organics and of ammo-
and this is an area of active research at the present time. nia will be developed.
Systems for inventorying and handling fish are needed.
Solids Removal Obtaining accurate estimates of number and size offish in
Removal of solids produced by aquaculture may be at- a culture system are practically impossible today as they
tempted for making the water suitable for reuse, or to meet are based on sampling or on the use of growth functions
discharge guidelines. Solids account for a high percentage and initial stocking values. Equipment and techniques
of the biochemical oxygen demand (BOD) in aquaculture that can be used to count animals and estimate their size
effluents; they tend to be highly variable in size and break with a minimum of disruption and stress to the fish will
up easily if subjected to mechanical forces. Solids are have to be developed.
formed from uneaten feed and fecal material. Their density
tends to be very close to that of water. BIBLIOGRAPHY
Removal is achieved by filtration with particulate (eg,
sand) or microscreen (eg, stainless steel) filters, or by sed- 1. R. D. Mayo, "A Format for Planning a Commercial Model
imentation (25). The high organic content of the particu- Aquaculture Facility," paper presented at Northeast Fish and
lates make them highly biodegradable, and filters need to Wildlife Conference, February 25-28,1974, Grate Gorge, N. J.
be backwashed frequently to prevent clogging by a mat of Technical Reprint No. 30. Kramer, Chin and Mayo, Inc., Con-
biological slime. Screen filters are common in aquaculture sulting Engineers, Seattle, Wash., 1974.
2. C. M. Brown and C. E. Nash, "Planning an Aquaculture 19. B. J. Watten, "Aeration and Oxygenation," in M. B. Timmons
FacilityGuidelines for Bioprogramming and Design," Aqua- and T. M. Losordo, eds., Aquaculture Water Reuse Systems:
culture Development and Coordination Programme Report Engineering Design and Management, Elsevier, Amsterdam,
ADCP/REP/87/24, United Nations Development Programme, 1994, pp. 173-208.
Food and Agriculture Organization of the United Nations, 20. G. Hackney and J. Colt, "The Performance and Design of
Rome, 1988. Packed Column Aeration Systems for Aquaculture," Aqua-
3. S. S. Nath et al., "Applications of Heat Balance and Fish cultural Eng. 1, 275-295 (1982).
Growth Models for Continental-Scale Assessment of Aqua- 21. R. B. Banks and F. F. Herrera, "Effects of Wind and Rain on
culture Potential in Latin America," in D. Burke et al., eds., Surface Reaeration," J. Environ. Eng. Div. ASCE 103(EE3),
Pond Dynamics I Aquaculture Collaborative Research Support 489-504 (1977).
Program, Fourteenth Annual Technical Report, PD/A CRSP
Office of International Research and Development, Oregon 22. W Bruin, J. W Nightingale, and L. Mumaw, "Preliminary Re-
State University, Corvallis, Oreg., 1996. sults and Design Criteria from and On-line Zeolite Ammonia
Removal Filter in a Semi-closed Recirculating System," in
4. Food and Agriculture Organization of the United Nations L. J. Allen and E.G. Kinney, eds., Proc. of the Bio-Engineering
(FAO) Fisheries Department, Aquaculture Development, FAO Symposium for Fish Culture, American Fisheries Society, Be-
Technical Guidelines for Responsible Fisheries, No. 5, Rome, thesda, Md., 1981, pp. 92-96.
1997.
23. F. W. Wheaton, et al., "Nitrification Filter Principles," in M.
5. T. B. Lawson, Fundamentals of Aquacultural Engineering, B. Timmons and T. M. Losordo, eds., Aquaculture Water Reuse
Chapman & Hall, New York, 1995. Systems: Engineering Design and Management, Elsevier, Am-
6. M. C. M. Beveridge, Cage Aquaculture, 2nd ed. Fishing News sterdam, 1994, pp. 101-126.
Books Ltd., Surrey, England, 1996. 24. F. W. Wheaton, et al., "Nitrification Filter Design Methods,"
7. C. R. dela Cruz, "Fishpond Engineering: A Technical Manual in M. B. Timmons and T. M. Losordo, eds., Aquaculture Water
for Small- and Medium-Scale Coastal Fish Farms in South- Reuse Systems: Engineering Design and Management, Else-
east Asia," South China Sea Fisheries Development and Co- vier, Amsterdam, 1994, pp. 127-171.
ordinating Programme Manual No. 5, United Nations Devel- 25. S. Chen, D. Stechey, and R. F. Malone, "Suspended Solids Con-
opment Programme, Food and Agriculture Organization of trol in Recirculating Aquaculture Systems," in M. B. Timmons
the United Nations. Manila, Philippines, 1983. and T. M. Losordo, eds., Aquaculture Water Reuse Systems:
8. H. S. Egna, and C. E. Boyd, eds. Dynamics of Pond Aquacul- Engineering Design and Management, Elsevier, Amsterdam,
ture, CRC Press, Boca Raton, FIa., 1997. 1994, pp. 61-100.
9. F. W. Wheaton, Aquacultural Engineering, Wiley, New York,
1977.
10. S. Skybakmoen, "Fish Rearing Tanks," Aquaculture Series RAUL H. PIEDRAHITA
Brochure, AGA AB, Lidingo, Sweden, 1993. University of California
Davis, California
11. M. B. Timmons and S. T. Summerfelt, "Advances in Circular
Culture Tank Engineering to Enhance Hydraulics, Solids Re-
moval, and Fish Management," in M. B. Timmons and T. M.
Losordo, eds., Advances in Aquacultural Engineering, Aqua- AROMATHERAPY
cultural Engineering Society Proceedings III. Northeast Re-
gional Agricultural Engineering Service, NRAES-105, Ithaca, Aromatherapy is a branch of the alternate medicine ap-
New York, 1997, pp. 66-84. proach that uses herbal remedies to improve an individ-
12. J. Gunnarsson, "Bridgestone HI-SEAS Fish Cage: Design and ual's health and appearance and to alter one's mood. The
Documentation," in H. Reinertsen et al., eds., Fish Farming alleged benefits from aromatherapy range from stress re-
Technology, Proc. of the First International Conference on Fish lief to enhancement of immunity and the unlocking of emo-
Farming Technology, Trondheim, Norway, August 9-12,1993, tions from past experience. The concept has ancient roots
A. A. Balkema, Rotterdam, 1993, pp. 199-201.
but is primarily used today by the cosmetics, fragrance,
13. J. Colt and K. Orwicz, "Modeling Production Capacity of and alternative-medicine industries.
Aquatic Culture Systems under Freshwater Conditions," The proponents of aromatherapy claim that the tools of
Aquacultural Eng. 10, 1-29(1991).
the trade, such as wood-resin distillates and flower, leaf,
14. T. M. Losordo and H. Westers, "System Carrying Capacity," stalk, root, grass, and fruit extracts, contain antibiotics,
in M. B. Timmons and T. M. Losordo, eds., Aquaculture Water
Reuse Systems: Engineering Design and Management, Else- antiseptics, hormones, and vitamins. Some proponents go
vier, Amsterdam, 1994, pp. 9-60. even further and have characterized the essential oils,
15. S. E. J0rgensen, Fundamentals of Ecological Modelling, El-
which are volatile, aromatic, and flammable, as the soul or
sevier, Amsterdam, 1986. spirit of plants. One of aromatherapy's promises is that the
16. D. E. Brune and J. K. Wang, "Recirculation in Photosynthetic essential oils have a "spiritual dimension" and can restore
Aquaculture Systems," Aquaculture Magazine 24(3), 63-71 "balance" and "harmony" to one's body and to one's life.
(1998). One of its principles is the "doctrine of signatures," which
17. J. Colt, "Computation of Dissolved Gas Concentrations in Wa- claims that a plant's visible and olfactory characteristics
ter as Functions of Temperature, Salinity, and Pressure," reveal its secret qualities. For example, the violet suggests
American Fisheries Society Special Publication No. 14, Be- shyness so the proponents conclude that the scent of violets
thesda, Md., 1984. engenders shyness and modesty. Aromatherapy encom-
18. H. L. Elmore and T. W. Hayes, "Solubility of Atmospheric Ox- passes topical application of essential oils, bathing in wa-
ygen in Water," J. Sanitary Eng. Div. ASCE 86(SA4), 41 ter containing essential oils, sniffing them, or actually in-
(1960). gesting them. Products supporting this concept include
shaving gels, aftershaves, facial cleansers, bath salts, ARTIFICIAL INTELLIGENCE
shower gels, shampoos, hair conditioners, body masks,
moisturizers, sunscreen preparations, lipsticks, deodor-
BACKGROUND
ants, candles, lamps, diffusers, pottery, massage oils, mas-
sage devices, and jewelry such as lockets and pendants for Artificial intelligence is defined as the application for com-
carrying essential oils. puter technology to resemble human thought and action.
The most common aromatherapy applications are aes- It is also the branch of computer science concerned with
thetic, where a sense of well-being is derived from enjoying
the development of machines having this ability. Artificial
perfumes, scented candles and baths, and other fra-
intelligence was widely acclaimed in the 1980s as revolu-
grances. At the opposite end of the spectrum is medical tionary technology. However, when expectations went un-
aromatherapy, also known as aromatic medicine, which in-
realized, its popularity faded. More recently it is reemerg-
cludes massage therapists, naturopaths, some nurses, and ing with revamped development tools and languages and
some medical doctors. The alleged beneficial effects are nu- advanced flexibility. The restrictions of expensive, large
merous: essential oil from bergamot normalizes emotions; machines and obscure languages have been overcome.
essential oil from roses or sandalwood increases confi- Many of the lofty early claims have been dismissed and
dence; essential oil from eucalyptus alleviates sorrow, and replaced with more pragmatic and profitable applications.
oil from patchouli creates a desire for peace. Eucalyptus The use of artificial intelligence is subtly in place for a va-
oil and peppermint oil have been used to treat respiratory riety of industrial, business, and consumer applications.
diseases. But it is conceded that some oils can be harmful. Areas of artificial intelligence include robotics, machine
Concentrated oils from cloves, cinnamon, nutmeg, and gin- vision, voice recognition, natural language processing, ex-
ger can burn the skin and ingestion of oil from pennyroyal
pert systems, neural networks, and fuzzy logic. The term
can cause miscarriages. One of the obvious applications of
artificial intelligence was first used in 1956 at a conference
aromatherapy involves the sense of smell, and one re- held at Dartmouth College in Hanover, New Hampshire.
searcher believes that the lack of ability to smell is corre-
The basis of the conference was the conjecture that every
lated with a gain in weight. Others believe that the ability feature of intelligence can be so precisely described that a
to smell or even the ability of the body to produce certain machine can be made to simulate it (1). Since that time
odors indicates certain diseases or impairments. If this the field has grown, evolved, fragmented, developed, and
proves to be true, it would be an interesting diagnostic tool. in many ways become incorporated into mainstream soft-
The concept behind aromatherapy is accepted in parts ware.
of Europe. For example, in France, medical students are
taught how to prescribe essential oils, and in Britain, hos-
Robotics
pital nurses use aromatherapy to treat patients suffering
anxiety and depression and to make terminal-care pa- Robotics, along with computer vision, have been applied in
tients more comfortable. Dorene Peterson, principal of the food-processing operations for sorting and evaluation. Ro-
Australasian College of Herbal Studies, commented, bots are used in manufacturing, performing such functions
"There is a philosophical difference between hard-core sci- as welding and painting. Labor-intensive, repetitive tasks
ence and the approach that believes there's vibrational en- such as those found in packaging have been prime appli-
ergy that's part of the healing process. Alternative medi- cations for robots. Even routine lab testing has incorpo-
cine is offered now in quite a number of medical schools. I rated robotics when the volume of samples justifies the
think a lot of hard-core scientists and doctors who have expense. Through artificial intelligence techniques robots
been trained in the data-oriented scientific approach are can function in unstructured situations, performing tasks
realizing there's more to heaven and earth than we really such as identifying objects and selecting and assembling
know about." However, she admits that empirical evidence them into a unit.
is necessary for widespread acceptance. In the United
States, there are no legal standards concerning the edu- Machine Vision
cation in aromatherapy, or the certification or occupational
Machine vision is the ability of a machine to look at or see
practice of aromatherapy. Several nonaccredited organi-
objects and to differentiate between those objects intelli-
zations offer short courses or correspondence courses, but
gently. A vision system can observe defects even at micro-
no accredited educational institutions offer majors in aro-
scopic levels. Because of its success, the implementation of
matherapy. It is safe to say that aromatherapy remains
machine vision is extensive. In the food industry, machine
outside the mainstream of medical therapy, but it is well
vision is used for sorting purposes in quality control appli-
ensconced in the cosmetic area.
cations. Machine vision, coupled with neural network-
based products, is being used to recognize patterns, optical
GENERAL REFERENCE characters, and bar codes.
C. A. Sweet, "Scents and Nonsense," Priorities 9, 30-33 (1997). Voice Recognition
F. J. FRANCIS Voice recognition systems respond to the human voice in-
Editor-in-Chief stead of a keyboard or other input. In certain industrial
University of Massachusetts settings such as package routing, voice recognition has
Amherst, Massachusetts been successful. Initially, because of the wide variety in
human voice patterns, voice recognition was constrained developing an expert system need to be established. If the
to a narrow range of applications or subjects. The technol- problem is very simple or if ample resources are already
ogy has since advanced to common usage in telecommu- available to solve the problem within the company, then
nications for automated information exchange. the investment may not be worthwhile. Some problems are
too broad or general to be solved by an expert system. To
Natural Language Processing be solved by an expert system, the problem would have to
be solvable to start with by a human expert in the field.
Natural language processing allows computer software to
Expert systems work well with programs where symbolic
understand normal conversational commands. Natural
logic and rules are required.
language is gaining strength in foreign language transla-
Expert systems can benefit problem-solving situations
tion. Although syntax often suffers, at least approximate
in which humans suffer from cognitive overload or fail to
translations can be commercially provided and are readily
monitor all available information. It can be difficult to si-
available by means of the Internet. In database applica-
multaneously manipulate all relevant information to ob-
tions, natural language programs translate queries from
tain the optimal solution. An expert system may be more
natural language to some database query language. Nat-
consistent in certain situations in which there is little time
ural language processing is steadily developing in order to
to think. Expert systems can often deliver solutions more
facilitate the user/computer interface.
quickly than their human counterparts. They are also
readily available at any time. Human experts are then able
Expert Systems
to better use their skills on more difficult problems beyond
Expert systems are computer programs designed to solve the ability of the expert system. The process of building a
problems requiring experts. In the field of artificial intel- knowledge base can help to clarify and organize an expert's
ligence, knowledge-based expert systems received most of logic and thinking process. A disadvantage of an expert
the early attention. An expert system includes a knowl- system is that it can be costly to develop. It also needs to
edge base and an inference engine. The knowledge base is be maintained and updated to remain current.
the accumulation and representation of knowledge specific
to a particular task. It is often constructed in the form of Neural Networks
rules, but methods such as frames and semantic nets are
Neural networks attempt to figuratively model the neu-
also used. Rule-based expert systems rule statements nor-
rological processes of the brain, in a stimulus/response
mally include a premise and a conclusion, using If and
structure. Neural networks essentially recognize patterns
Then statements. The inference engine is the system's ma-
in data leading from initial events to results. These pro-
chinery for selecting and applying knowledge from the
grams are well suited to systems in which traditional sta-
knowledge base to the specific problem. An inference en-
tistics are not applicable. The technology's power lies in its
gine uses the knowledge base along with responses from
ability to analyze large combinations of variables very
the user to solve problems. The inference engine takes in-
quickly. The neural network is trained by observing a mul-
formation and proceeds forward through the knowledge
titude of patterns. For many processes indications of prod-
base looking for a valid path. The engine may either take
uct quality parameters, such as moisture, color, texture,
information and proceed forward through the knowledge
concentration, or taste, cannot be measured at the point of
base looking for a valid path, or start with goals and work
control. Quality labs check samples from the end of the
backward until a clear path is found. In conventional pro-
line, which is too late for process control, resulting in con-
grams the knowledge base is part of the program, but with
siderable scrap or costly rework. Neural networks can be
an expert system it is separate. This distinction makes it
trained to predict quality parameters from on-line process
possible to substitute a new knowledge base for a new task
data at the point of control. This information can then be
in place of the existing knowledge base. Expert systems
used either manually or automatically for controlling the
can also be updated readily as new knowledge is discov-
process. Whenever product quality needs to be controlled
ered. Expert systems take advantage of an expert's heu-
based on measurements taken after the process, neural
ristics or knowledge from experience. The combination of
networks are useful.
heuristics and learned principles helps account for the
value of an expert. Usually an expert system is developed
Fuzzy Systems
through an iterative process where an initial program is
prepared and then developed and improved with addi- Fuzzy systems are distinguished primarily by their sup-
tional items of knowledge. Expert systems cannot exactly port for a gradual and continuous transition rather than a
model human problem-solving processes, but rather they sharp and abrupt change between binary values. Infor-
attempt to interact with expert thought concerning specific mation obtained in food process control may be noisy, in-
areas of knowledge. Most expert systems allow confidence complete, scrambled, erroneous, or generally uncertain (2).
factors in order to express uncertainty. Uncertainty may Fuzzy systems are most suitable for uncertain or approx-
arise from either the stored knowledge base or user re- imate reasoning, particularly systems with a mathemati-
sponses. cal model that is difficult to derive. Designers are able to
Although an expert system is useful for arriving at a represent descriptive or qualitative expressions such as
solution from numerous options, its range of focus needs "slow" or "moderately fast" and incorporate them with
to be narrow to avoid an excessively complex system. The symbolic statements. Integrated circuit manufacturers
economic advantages of going to the time and expense of have fabricated chips with built-in fuzzy logic capabilities.
EXAMPLES gression (PCR) and partial least-squares (PLS) regression.
It was concluded that neural networks cannot replace PCR
The addition of an expert system can advise a process con- and PLS for linear relationships but do offer potential for
troller when to make adjustments. These devices use pat- modeling nonlinear relationships (7).
tern recognition algorithms, calculate control loop perfor- Questions regarding expansion of neural networks
mance on-line, and readjust operator intervention. Expert when necessary have prompted research on network con-
systems can help monitor a process and notify operators of figuration. Learning rates for neural networks, which were
an out-of-specification situation. Self-tuning controllers expanded by coupling modules, rather than simply directly
can also use model-based references where the difference expanding the existing network were improved. Coupled
in response between the process and the model is used to neural networks were found to improve food starch iden-
tune the controller and also update the model. A classic tification (8).
expert system for process control was designed for advisory The relationships between process parameters and flow
control of thermal processing in a major soup company (3). rates through ultrafiltration membranes have been ex-
The expertise of a retiring staff member for troubleshoot- amined using fuzzy mathematics (9). Main parameters in
ing, start-up, and shutdown of hydrostatic and rotary ster- the permeate flow were identified. Fuzzy logic has been
ilizers was captured in an expert system program, saving used in many familiar applications including, home appli-
the company up to US$3 million per year. An expert sys- ances, video cameras, automobiles, robots, and aircraft.
tem can respond to user questions, query the user for ad- One company has developed a hybrid product combining
ditional information, and provide a report of the interac- neural networks, fuzzy logic, genetic algorithms, and chaos
tion along with a process and instrumentation diagram. theory (Neuristics, Baltimore, Md.). The company main-
Fault analyzers respond to alarms and other process in- tains this design overcomes limitations of neural networks,
puts to diagnose abnormal conditions. They can find a pre- explaining the logic behind its forecasts.
viously determined pattern in a set of alarm messages. Regarding business applications, neural networks have
Rather than receiving a number of alarms, the operator been successfully used for bank loan applications. A pro-
will receive a simplified message stating the recommen- gram called Countrywide Loan Underwriting Expert Sys-
dation. Corrective action can then be taken. tem, or CLUES (Brightware, Inc, Novato, CA), evaluates
A widely used rule-based expert system from Gensym a loan file's strengths and weaknesses in human terms.
Corp (Cambridge, Mass.), among other applications, has Loans can be approved in less than 2 min compared with
been useful in controlling wastewater treatment. The ar- 50 min for human underwriters. Benefits include person-
rangement of equipment and controls is a complex, time- nel cost savings and better quality and consistency in un-
consuming assignment and many factors need to be con- derwriting. Neural networks can be used to set up intelli-
sidered. With control-system configuration, operating gent agents for information services. These agents are able
conditions and parameters, objectives, and constraints to automatically locate and retrieve competitive intelli-
such as equipment limitations can be entered into a pro- gence information. Consumer electronics industries have
cess model. The configuration best satisfying all require- developed software programs with the ability to operate
ments is then presented to the user. autonomously, performing operations ranging from elec-
Neural networks can predict patterns in process data, tronic shopping to getting data over the Internet. The
which in turn can be used to control the process as desired. growth of the Internet may create new artificial intelli-
With neural network pattern recognition software, re- gence applications.
sponses are observed and necessary control adjustments
are made. Applications have been reported across a wide
variety of industries. Pattern recognition methods have ADVANTAGES/FUTURE DEVELOPMENT
been used for the identification of flours (4). BrainMaker
(Nevada City, Calif.) has reported a wide variety of appli- The many facets of artificial intelligence are able to reduce
cations for its neural network product including invest- labor costs, improve productivity and quality, and remove
ment advising, heart attack diagnosis, beverage quality human bias. Expert systems can act as training tools, both
testing, chemical structure recognition, and protein se- during the process of development, as well as during im-
quence pattern recognition. The application of neural net- plementation. Advanced computer-aided systems can im-
works in the dairy industry was recently discussed in an prove food safety, reduce processing times, and achieve
Australian seminar (5). Reports included neural networks higher quality and yields at minimal costs if applied cor-
in ultrahigh temperature (UHT) operations, natural lan- rectly to the food processing system (10). Human talents
guage computer control of crucial steps in cheese making, and abilities can be better utilized and even assisted as
and fermentation processes. The effects of transmembrane these programs are made available for process control and
pressure and cross-flow velocity on cross-flow filtration analysis.
were modeled using a neural network approach. Modeling The large number of computing techniques within the
was obtained after only five experimental trials for either very broad terms of artificial intelligence will continue to
raw cane sugar remelt or natural gum solution (6). The use drive many of the advanced applications in science, indus-
of neural networks for modeling instrumental-sensory re- try, and consumer products. Products will continue to im-
lationships has been investigated. The advantages and dis- prove in data assimilation and communication, replacing
advantages of using neural networks were compared with an increasing number of tasks previously requiring human
multivariate linear methods of principal components re- intervention.
Artificial intelligence will continue in importance as it Aseptic describes a condition in which there is an ab-
becomes embedded in mainstream systems. The different sence of microorganisms, including viable spores. In the
components of artificial intelligence are each finding their food industry, the terms aseptic, sterile, and commer-
own particular embedded applications. cially sterile are often used interchangeably.
Aseptic system refers to the entire system necessary to
BIBLIOGRAPHY produce a commercially sterile product contained in a
hermetically sealed container. This term includes the
1. E. Charniak and D. McDermott, Introduction to Artificial In- product processing system and the packaging system.
telligence, Addison-Wesley, Reading, Mass., 1985. Aseptic processing system refers only to the system that
2. T. Eerikainen et al., "Fuzzy Logic and Neural Network Appli- processes the product and delivers it to a packaging sys-
cations in Food Science and Technology," Trends Food Sd. tem.
Technol 4, 237-242 (1993).
Aseptic packaging system refers to any piece of equip-
3. R. K. Tyson and R. A. Herrod, "Capturing 32 Years on Com- ment that fills a sterile package or container with sterile
puter," Chilton's Food Eng. 57, 69-71 (Dec. 1985).
product and hermetically seals it under aseptic condi-
4. P. Zagrodzki et al., "Characterisation of Flour by Means of tions. These units or systems may also form and ster-
Pattern Recognition Methods," Food Chem. 53, 295 (1995).
ilize the package.
5. J. A. Hourigan, "Artificial Neural Networks in the Dairy In-
dustry," Ausl J. Dairy Technol 49, 110-121 (1994).
6. M. Dormer et al., "Interest of Neural Networks for the Opti- BASIC ASEPTIC SYSTEM
mization of the Crossflow Filtration Process," Lebensmittel-
Wissenschaft Technol. 28, 300-309 (1995). Figure 1 is a diagram of a simplified aseptic system. Raw
7. C. Wilkenson and D. Yuksel, "Using Artificial Neural Net- or unprocessed product is heated, sterilized by holding at
works to Develop Prediction Models for Sensory-Instrumental high temperature for a predetermined amount of time,
Relationships: An Overview," Food Quality Preference 8,439- then cooled and delivered to a packaging unit for packag-
445 (1997).
ing. Commercial sterility is maintained throughout the
8. Y. W. Huang et al., "Modular Neural Networks for Identifi- system, from product heating to the discharge of hermet-
cation of Starches in Manufacturing Food Products," Biotech-
nol. Progr. 9, 401-410 (1993). ically sealed containers.
9. P. Vaija et al., "Prediction of the Flux through an Ultrafiltra-
tion Membrane Using Fuzzy Mathematics," J. Membrane Sd. DESCRIPTION OF THE ASEPTIC PROCESSING SYSTEM
83, 173-179 (1993).
10. S. Linko, "Expert Systems: What Can They Do for the Food Although the equipment for aseptic processing systems
Industry?" Trends Food Sd. Technol 9, 3-12 (1998).
varies, all systems have certain common features:
Product cooler
Back
pressure
device
Flow
diversion Filler
valve
Product
Sealer
supply
tank Container
sterilizer
Metering
device
Aseptic filler Figure 1. Simplified diagram of an asep-
tic processing system.
product heater and then pumped through all downstream the minimum time specified by the scheduled process. This
piping and equipment up to (and generally past) the filler constant flow rate is generally achieved with a pump,
valve on the packaging unit. All product contact surfaces called a timing or metering pump.
downstream from the product heater must be maintained Timing pumps may be variable speed or fixed rate. The
at or above a specified temperature by continuously cir- pumping rate of the fixed-rate pump cannot be changed
culating the hot water for a required period of time. without dismantling the pump. Variable-speed pumps are
Surge tanks are generally sterilized with saturated designed to provide flexibility and allow for easy rate
steam rather than hot water owing to their large capacity. changes. When a variable-speed pump is used, it must be
Although sterilization of surge tanks may occur separately, protected against unauthorized changes in the pump speed
it is usually conducted simultaneously with hot water ster- that could affect the rate of product flow through the sys-
ilization of the other equipment. tem.
To control aseptic system sterilization properly, it is
necessary that a thermometer or thermocouple be located Product Heating
at the coldest point(s) in the system to ensure that
the proper temperature is maintained throughout. Thus, A product heater brings the product to sterilizing tem-
the temperature-measuring device is generally located at perature. There are two major categories of product heat-
the most distant point from the heat exchangers. Timing ers in aseptic food processing: direct and indirect.
of the sterilization cycle begins when the proper tempera- Direct heating, as the name implies, involves direct con-
ture is obtained at this remote location. If this temperature tact between the heating medium (steam) and the product.
should fall below the minimum, the cycle should be re- Direct heating systems can be one of two types: steam in-
started after the sterilization temperature is reestab- jection and steam infusion.
lished. Steam injection introduces steam into the product in an
injection chamber as product is pumped through the cham-
Flow Control ber (Figure 2). Steam infusion introduces product through
a steam-filled infusion chamber (Fig. 3). These systems are
Sterilization time or residence time, as indicated in the currently limited to homogeneous, low-viscosity products.
scheduled process, is directly related to the rate of flow Direct heating has the advantage of very rapid heating,
of the fastest-moving particle through the system. The which minimizes organoleptic changes in the product. The
fastest-moving particle is a function of the flow character- problems of fouling or burn-on of product in the system
istics of the food. Consequently, a process must be designed may also be reduced in direct heating systems compared
to ensure that product flows through the system at a uni- with indirect systems.
form and constant rate so that the fastest-moving particle There are also some disadvantages. The addition of wa-
of food receives at least the minimum amount of heat for ter (from the condensation of steam in the product) in-
Product inlet gasketed, and a series of plates are held together in a
press. The number of plates can be adjusted to meet spe-
Heated cific needs.
Steam product Tubular heat exchangers employ either two or three
inlet outlet concentric tubes instead of plates as heat-transfer sur-
faces. Product flows through the inner tube of the double-
tube style and through the middle tube of the triple-tube
style, with the heating medium in the other tube(s) flowing
in the opposite direction to the product. In a shell and tube
Steam heat exchanger (considered a type of tubular exchanger),
Product the tube is coiled inside a shell. Product flows through the
tube while the heating medium flows in the opposite di-
Product and condensed rection through the shell. As with plate heat exchangers,
steam mixture tubular heat exchangers are used for homogeneous prod-
Figure 2. Steam injection.
ucts of low viscosity.
Scraped-surface heat exchangers are normally used for
processing more viscous products (Fig. 4). The scraped-
surface heat exchanger consists of a mutator shaft with
scraper blades concentrically located within a jacketed, in-
sulated heat exchange tube. The rotating blades continu-
ously scrape the product off the wall. This scraping reduces
buildup of product and burn-on. The heating medium flow-
ing on the opposite side of the wall is circulating water or
steam.
Some systems incorporate the use of product-to-product
heat exchangers. These devices are either plate or tubular
heat exchangers with product flowing on both sides of the
plates or through both sets of tubes. This process allows
the heat from the hot, sterile product to be transferred to
Steam the cool incoming, nonsterile product. Energy and cost sav-
Product
in ings can be significant by recycling the heat from sterile
product.
When a product-to-product regenerator is used, the re-
generator must be designed, operated, and controlled so
that the pressure of the sterilized product in the regener-
ator is at least 1 psi greater than the pressure of any non-
sterilized product in the regenerator. This pressure differ-
ential helps ensure that any leakage in the regenerator
will be from sterilized product into nonsterilized product.
Figure 3. Steam infusion.
Hold Tube
Once the product has been brought to sterilizing tempera-
creases product volume. Because this change in volume ture in the heater, it flows to a hold tube. The time required
increases product flow rate through the hold tube, it must for the fastest product particle to flow through the hold
be accounted for when establishing the scheduled process. tube is referred to as the residence time. The residence
Depending on the product being produced, water that was time must be equivalent to or greater than the time nec-
added as steam may need to be removed. Water removal essary at a specific temperature to sterilize the product
is discussed under product cooling. Steam used for direct and is specified in the scheduled process. Hold-tube vol-
heating must be of culinary quality and must be free of ume, which is determined by hold-tube diameter and
noncondensable gases. Thus, strict controls on boiler feed length, combined with the flow rate and flow characteris-
water additives must be followed. tics of the product, determines the actual residence time of
The other major category of product heaters is indirect the product in the hold tube. Because the hold tube is es-
heating units. Indirect heating units have a physical sep- sential for ensuring that the product is held at sterilization
aration between the product and the heating medium. temperatures for the proper time, certain precautions
There are three major types of indirect heating units: must be followed:
plate, tubular, and swept-surface heat exchangers.
Plate heat exchangers are used for homogeneous liquids
of relatively low viscosity. The plates serve as both a bar- 1. The hold tube must have an upward slope in the di-
rier and a heat-transfer surface with product on one side rection of product flow at least 0.25 in./ft to assist in
and the heating medium on the other. Each plate is eliminating air pockets and prevent self-draining.
Mutator Media
inlet
Product inlet
Product Media
outlet outlet
Heat-transfer media
Figure 4. Scraped-surface heat ex-
Product changer.
2. If the hold tube can be taken apart, care should be use indirect heating, the cooler will be a heat exchanger
taken that all parts are replaced and that no parts that may be heating raw product while cooling sterile prod-
are removed or interchanged to make the tube uct. Those systems that use direct heating will typically
shorter or different in diameter. Such accidental al- include a flash chamber or vacuum chamber. The hot prod-
terations could shorten the time the product remains uct is exposed to a reduced pressure atmosphere within the
in the tube. chamber, resulting in product boiling or flashing. The prod-
3. If the hold tube can be taken apart, care should be uct temperature is lowered, and a portion or all of the
exercised when reassembling to ensure that the gas- water that was added to the product during heating is re-
kets do not protrude into the inner surface. The tube moved by evaporation. On discharge from the flash cham-
interior should be smooth and easily cleanable. ber, product may be further cooled in some type of heat
4. There must be no condensate drip on the tube, and exchanger.
the tube should not be subjected to drafts or cold air,
which could affect the product temperature in the Maintaining Sterility
hold tube. After the product leaves the hold tube, it is sterile and
5. Heat must not be applied at any point along the hold subject to contamination if microorganisms are permitted
tube. to enter the system. One of the simplest and best ways to
6. The product in the hold tube must be maintained prevent contamination is to keep the sterile product flow-
under a pressure sufficiently above the vapor pres- ing and pressurized. A back-pressure device is used to pre-
sure of the product at the process temperature to vent product from boiling or flashing and maintains the
prevent flashing or boiling because flashing can de- entire product system under elevated pressure.
crease the product residence time in the hold tube. Effective barriers against microorganisms must be pro-
The prevention of flashing is usually accomplished vided at all potential contamination points, such as rotat-
by use of a back-pressure device. ing or reciprocating shafts and the stems of aseptic valves.
Steam seals at these locations can provide an effective bar-
The temperature of the food in the hold tube must be rier, but they must be monitored visually to ensure proper
monitored at the inlet and outlet of the tube. The tem- functioning. If other types of barriers are used, there must
perature at the inlet of the tube is monitored with a tem- be a means provided to permit the operator to monitor the
perature recorder-controller sensor that must be located at proper functioning of the barrier.
the final heater outlet and must be capable of maintaining
process temperature in the hold tube. A mercury-in-glass Aseptic Surge Tanks
thermometer or other acceptable temperature-measuring
device (such as an accurate thermocouple recorder) must Aseptic surge tanks have been used in aseptic systems to
be installed in the product sterilizer hold tube outlet be- hold sterile product before packaging. These vessels, which
tween the hold tube and the cooler inlet. An automatic re- range in capacity from about 100 gal to several thousand
cording thermometer sensor must also be located in the gallons, provide flexibility, especially for systems in which
product at the hold tube outlet between the hold tube and the flow rate of a product sterilization system is not com-
cooler to indicate the product temperature. The tempera- patible with the filling rate of a given packaging unit. If
ture-sensing device chart graduations must not exceed 20F the valving that connects a surge tank to the rest of the
(I0C) within a range of 1O0F (60C) of the required product system is designed to allow maximum flexibility, the pack-
sterilization temperature. aging and processing functions can be carried out indepen-
dently, with the surge tank acting as a buffer between the
two systems. A disadvantage of the surge tank is that all
Product Cooling
sterile product is held together, and if there is a contami-
Product flows from the hold tube into a product cooler that nation problem, all product is lost. A sterile air or other
reduces product temperature before filling. In systems that sterile gas supply system is needed to maintain a protec-
tive positive pressure within the tank and to displace the sealed shelf-stable product. As with aseptic processing sys-
contents. This positive pressure must be monitored and tems, certain features are common to all aseptic packaging
controlled to protect the tank from contamination. systems. The packaging units must do the following:
Electrode
Product to
be Alternating
heated current
i power
supply
Electrode
Product Air
inlet
Aseptic
Catch surge
tank vessel
Ohmic
heater
To filler
Recycle for
ClP and/or
sterilization
Figure 3. Ohmic plant line diagram. Product pump
the particulate, should they be markedly different, by ma- Fresher tasting, more nutritional products can be
nipulation of the dissolved ionic contents of the two pro- produced containing large particulates.
cessing streams. This assists in ensuring that both partic- There is ability to heat food product in continuous flow
ulates and carrier fluid are heated at the same rate. without the need for any hot heat transfer surfaces.
After cooling, product enters the main storage reservoir Process is ideal for shear-sensitive products.
prior to aseptic filling. It is not usually necessary to carry Risk of fouling is considerably reduced.
out intermediate cleaning and/or resterilization of the Heat can be generated in the product solids without
plant when several different products are processed. This reliance on thermal conductivity through liquid.
is due to the almost complete absence of fouling with most System is quiet in operation.
food materials. After one product is processed, the plant is Maintenance costs are lower.
flushed with a food-compatible liquid or base sauce before Process is easy to control and can be started or shut
introducing the next product. The catch tank is used to down instantly.
collect product/sauce interfaces. There are potential savings in processing and
When food processing is complete, the power is turned packaging costs.
off and the plant rinsed with water. This is followed by
cleaning with a 2% (w/v) solution of caustic soda recircu- Figure 4. Advantages of electrical resistance heating.
lated at 60 to 7O0C for 30 min. Heating of the cleaning
solution is by standard methods and not using the ohmic
principle. This is because the electrical conductivity of the
cleaning solution is too high for the ohmic principle to be uct virtually simultaneously; this provides a high degree
applied. of microbiological security, as there is a very narrow range
of lethality from the surface to the center of the particu-
lates.
PRODUCT QUALITY In a 1996 publication by Kim et al. (2), a team involving
the U.S. Army Soldier and Biological Chemical Command
Included in the list of perceived advantages of continuous and APV UK Ltd., had demonstrated that not only the cen-
aseptic processing (Fig. 4) is that of improved product qual- ter temperature of a particulate rises faster than the sur-
ity, with the basic standard being set by products sterilized face, but also particulates could heat faster than fluid in
by traditional canning methods. ohmic heating. A higher temperature of the particulates
These quality standards include microbiological safety provided additional heat to the surrounding fluid as both
(ie, process lethality), cooking effects, and nutrient/ phases exited the ohmic column and entered the holding
vitamin retention. Unlike other processes requiring heat tube. Therefore a higher temperature reading was regis-
penetration, either from the outside to the center of a can tered at the outlet than that at the inlet of holding tube
(in-can sterilization) or from the outside of the particulate (Fig. 5). They also suggested that lethality estimation of
to the center (tubular or swept surface), ohmic has the abil- microorganisms based on fluid temperature at the ohmic
ity to provide exceptionally fast heating of all of the prod- column outlet would be very conservative. This is a very
and higher degrees of overcook to achieve satisfactory F0
values at the center.
Continuous systems using heat penetration will also
have wide variations in F0 values from the center of the
Temperature (0C)
Equivalent liquid F0
proval of such novel technology.
Challenge tests carried out (on now commercially avail-
able products) by the Campden Food and Drink Research
Association have involved particulates of meat and vege-
table up to 19 mm cube. An average of 10 million spores of
Bacillus stearothermophilus per particle embedded in a
food/alginate mixture were included in batches of mince
and mushrooms in bolognese sauce, and in kidney, peas,
and gravy, in order to determine the lethality at the center
and throughout particles of various sizes from 3 mm to 19
mm.
The results obtained (Table 1) demonstrate the high
level of microbiological security of the process and the very Particular diameter (mm)
narrow range of lethality from the surface to the center of
the particulates. Figure 6. Liquid F0 necessary to obtain F0 = 5 in center of par-
ticulate.
The cook value (C0) of a process is also a function of time
and temperature (dependent upon the viscosity of the
product). For small cans, F0 values for viscous products can
typically range from 5 to 300 resulting in high cook values.
Larger cans will show even greater variations in F0 values
Time to reach F0 = 5 min
Run 2
Pea (5 mm) 28 33.7-46.4 38.5 2.8 Temperature (0C)
Kidney (19 mm) 30 47.-62.S 54.8 3.8
Kidney (3 mm) 20 45.6-56.2 50.2 3.2
Figure 7. Time taken to reach F0 = 5 in center of particulate.
where y is the [(0C - WQ)/Z] and T is the time, min. Ster-
ilization at 14O0C to a virtually uniform F0 of 24 equates
to a likewise uniform C0 value of less than 5.
This relationship allows such products as diced potato
Cooking value (C0)
BAKERY LEAVENING AGENTS in, say, a cake batter when baking is begun, then the CO2
that is formed by the chemical reactions in the batter has
All baked foods are leavened. Even unleavened bread such no place to go, because a new bubble cannot form (with a
as matzoh is raised by the steam generated during baking. zero radius the surface tension is infinite). If the cake bat-
Normally, leavening is thought of as being due to the prod- ter contains relatively few air bubbles, the CO2 diffuses to
ucts of fermentation (carbon dioxide, alcohol) or to CO2 these, and the resulting cake has a coarse, open grain, of-
generated by chemical reactions. However, the expansion ten accompanied by tunnels. With many small air nuclei,
of air incorporated into a dough during mixing and the for- the grain is fine and close.
mation of steam, from water in the dough, also cause the Surfactants aid incorporation and subdivision of air into
baking piece to expand. If this does not happen, the prod- dough (2). Emulsifiers help incorporate air into shortening
uct is dense and unappetizing. This article discusses leav- during the preparation of cookie doughs and cake batters.
ening obtained by chemical reactions as well as from yeast In all cases the presence of many air bubbles for nucleation
fermentation. is an important part of any leavening action.
Steam
CHEMICAL LEAVENING
The formation of steam by evaporation of water would
seem to be important only when the temperature in the
The common form of chemical leavening involves a food baking piece exceeds 10O0C in items such as cookies, crack-
acid and soda (sodium bicarbonate). The soda dissolves ers, and snacks such as tortilla chips. Also, it has been
readily in the aqueous phase of the dough or batter. When suggested that the water present in roll-in margarine,
the acid dissolves, the hydrogen ion reacts with bicarbon- used in making puff pastry, evaporates and helps to give
ate ion, releasing carbon dioxide (CO2), which expands the the characteristic open structure of this product. Extruded
baking piece. Water-vapor pressure increases as the inter- goods, of course, depend almost entirely on steam for their
nal temperature of the bakery item increases. Air incor- expansion.
porated during dough mixing also expands. Finally, certain The vapor pressure of water increases with increasing
materials, notably ammonium bicarbonate, decompose on temperature, and this increased pressure can expand the
heating and generate gases that leaven the product. gas bubbles in cake batter and in bread. In calculations of
the expansion of sponge-cake batter (which contained no
Air soda for chemical leavening), it was found that the theo-
During dough mixing air is incorporated as numerous retical curves (which took into account the thermal expan-
small bubbles (1,2). The actual amount varies, but with an sion of the air) fitted the experimental measurements
ordinary horizontal mixer a bread dough contains about 15 within a few percent (5). When theoretical expansion for
to 20% air by volume. If yeast fermentation is occurring, bread dough in the oven (see "Oven Spring") was calcu-
this volume shrinks by 20% owing to oxygen depletion (3), lated, it was concluded that water evaporation accounted
and during baking, the nitrogen remaining expands by for 60% of the total volume increase (6).
17% owing to temperature rise, so the net leavening con-
tribution due to air is nil. In the absence of yeast, thermal Ammonium Bicarbonate
expansion is still only 17%, so the overall effect is small. Ammonium bicarbonate is often used as a supplementary
In cookie doughs and cake batters the amount of air leavening agent for cookies and snack crackers. At room
retained is variable. In a standard sugar cookie dough, for temperature, dissolved in the dough water, it is stable, but
example, the dough contains about 10% air by volume (4). when the temperature reaches 4O0C (1040F) in the early
Cake batter specific gravity may vary from 0.60 to 1.10 stages of the oven, it decomposes:
g/mL, depending on the formulation and emulsifier system
used. The density of air-free batter is about 1.30 g/mL (5), NH4HCO3 -> NH3 + CO2 + H2O
so the amount of air in the batter may range from 15 to
55% by volume. Even at the highest level, however, the One mole of ammonium bicarbonate (79 g, or 2.8 oz) gives
thermal expansion of this air contributes only slightly to 2 mol of gas (44.8 L, or ca 1.6 ft3).
the final volume of the cake. This potential for extensive gas formation means that
Nevertheless, it is important to get good air incorpora- ammonium bicarbonate must be uniformly distributed
tion in the dough or batter during mixing, because the air throughout the dough; the presence of small undissolved
bubbles serve as nuclei for other leavening gases. The in- pieces would give rather large blowouts in the product.
ternal pressure produced by the surface tension of a gas Ammonium bicarbonate is usually dissolved in a few
bubble is inversely related to bubble diameter. If a small quarts of warm water and then added to the mixer along
bubble and a large bubble are near each other, the gas with the other water.
diffuses from the small one to the large one, and the small Because ammonia is water soluble, this leavener is ap-
bubble disappears. If no gas bubbles are already present plicable only in low-moisture products. If the finished
13
moisture is above 5% (say, in a soft cookie), the water will application. If the ingredient is added at the mixer, and
retain some of the NH3 and the product has a character- the dough or batter will be processed fairly quickly, then
istic ammonia taste. In contrast to this general rule, am- rapid dissolution is wanted and No. 3 (fine powdered) or
monium bicarbonate is sometimes added to eclair and pop- No. 1 (powdered) would be appropriate. At the other ex-
over doughs (pate de choux). In this case the combination treme is the inclusion of soda in a dry mix (eg, cake, cake
of high baking temperatures, thin walls, and a large inter- doughnut) that is packaged and stored for a period of time
nal cavity allows enough space for ammonia to diffuse out before use. In this case thermal decomposition of the dry
of the baked good. powder becomes a factor. Grade No. 1 (powdered) decom-
poses 50% faster than grade No. 5 (coarse granular) in this
Sodium Bicarbonate situation. A loss of 2 to 4% per week at 5O0C (1220F) and
0.5 to 1% at 3O0C has been reported. A common practice is
Baking soda (sodium bicarbonate) has been the workhorse to add 5 to 10% more than needed when the dry mix is
chemical leavener of baked goods for well over a century. blended, in the hope that when the mix is used (with un-
In most cases it is combined with a leavening acid to form controlled variables of age and storage temperatures), the
CO2, but soda itself undergoes thermal decomposition: amount of soda will be adequate to perform as expected. It
would be preferable to use grade No. 4 (granular) or No. 5
2NaHCO3 + heat - Na2CO3 + CO2 + H2O (coarse granular) for this application and reduce the
amount of overage in the dry mix.
This reaction usually requires rather high temperatures
(>120C) to happen at an appreciable rate, so using soda Potassium Bicarbonate
as a sole leavening agent is restricted mainly to cookies
and snack crackers in which the internal temperatures can Recently this material has become commercially available
approach this range. as a substitute for sodium bicarbonate; it is functionally
The more usual reaction is with hydrogen ions from equivalent but lowers the sodium content of the finished
leavening acids: product. As shown in Table 1 the granulation grade cur-
rently offered is intermediate between No. 4 (granular)
NaHCO3 + H + - ^ Na + + CO2 + H2O and No. 5 (coarse granular) sodium bicarbonate. The effect
on pH and the reactions to CO2 are the same. Because the
Soda is readily soluble in water (saturation solubility of molecular weight is greater (100.11 for KHCO3 vs 84.01
6.5% at O0C, 14.7% at 6O0C) and dissolves in the dough or for NaHCO3), 19% more is required to get the same effect;
batter water during mixing. The rate of reaction is gov- 10 Ib of sodium bicarbonate is replaced with 11.9 Ib (11 Ib
erned by the rate of dissolution of the leavening acid (see 14-1/4 oz) of potassium bicarbonate.
"Leavening Acids"); no H + is present until the acid dis- A review of bicarbonates for leavening has been pub-
solves and ionizes. Of course, the soda can react with acidic lished (7).
ingredients in the formula such as buttermilk and even
Leavening Acids
flour itself. Chlorinated cake flour, which is more acidic
than ordinary pastry flour, will neutralize about 0.27 g of The traditional acidulants for baking were vinegar (acetic
soda per 10Og of flour. Soda is a mild alkali; the pH of an acid), lemon juice (citric acid), cream of tartar (potassium
aqueous solution is about 8.2. Increasing the amount of acid tartrate), or sour milk (lactic and acetic acids). In all
soda in a formula raises the pH of the dough, for example, cases the acid reacted with the soda as soon as they were
in raising the dough pH of saltine crackers to 7.4. Excess mixed and the baker relied on batter viscosity to retain the
soda (more than that neutralized by available leavening CO2 until the cake or cookie was baked in the oven. In 1864
acid) is added to devil's food cake batter to raise the pH of monocalcium phosphate hydrate was patented for use in
the finished cake crumb to about 7.8 and generate the dark making a commercial baking powder. Later (ca 1885) so-
chocolate color desired (cocoa is lighter colored in mild acid, dium aluminum sulfate began to be used; this compound
darker colored in mild alkali). has a low solubility in water at room temperature and es-
Sodium bicarbonate is available in various granulations sentially none in the aqueous phase of a batter, so it does
(Table 1); it is important to choose the correct one for the not release CO2 until late in the baking cycle. The combi-
Figure 1. The rate of reaction of various leavening acids as a function of temperature. The width
of the triangles indicates the rate of reaction. MCP is the fastest-acting acid, while DCP.Di is the
slowest leavening acid. Source: Ref. 9 (data for MGP from B. Heidolph, personal communication).
though the basic molecule is the same in all cases, Ca+ + dium aluminum sulfate is reported to contribute to rancid-
slows the dissolution rate of SAPP granules. Thus the in- ity in dry cake mixes stored for a long time. Calcium ion
clusion of milk in a SAPP-leavened formulation (eg, a pan- also helps set protein structure and contributes to fine
cake batter) delays the time of leavening slightly. The vari- grain in cakes and cake doughnuts. One leavening acid
ous reaction grades are made by intentionally adding a may be selected over another with an equivalent reaction
certain amount of Ca+ + to the disodium salt during man- rate just to take advantage of these ion effects.
ufacture (adjustments in granule size also control disso- Developing a formulation with a properly balanced
lution rate). The grade designations used by Monsanto chemical leavening system is partly science and partly
Chemical Co. range from SAPP-43 (the fastest) through 40, artpreplanning followed by trial and adjustment. The se-
37, and 28 to 21 (formerly called SAPP RD-I, the slowest). lection of timing of the leavening acids, the ratio between
The corresponding grades marketed by Stauffer Chemical the various ones that might be used, the total amount of
Co. (now a division of Rhone-Poulenc) are named Perfec- CO2 required, and the amount of excess of sodium bicar-
tion, Donut Pyro, Victor Cream, BP Pyro, and SAPP #4. bonate desired are all factors that interplay with other in-
The slowest grade is used in making refrigerated biscuits gredients and structural functionalities in the baked
and doughs, whereas for other uses (cakes, cake dough- goods. Achieving the correct leavening balance in a partic-
nuts, biscuits, and pancakes) a combination of SAPP acids ular formula requires a certain amount of trial and error.
is used to get continuous leavening throughout the baking
cycle. Baking Powder
The high reaction rate of MCP may be moderated by In the latter part of the nineteenth century, baking pow-
coating it with a somewhat insoluble material. This coat- ders were developed that combined both parts of the chem-
ing dissolves slowly with time, allowing the MCP to then ical leavening systembaking soda and a leavening acid.
dissolve and form H + . Instead of 70% of the reaction oc- The first baking powder contained only one leavening acid,
curring during the first 10 min after mixing, coated MCP anhydrous MCP, and reacted fairly quickly in cake batters,
typically gives 20% reaction immediately and then the biscuits, and so on. Soon afterward, sodium aluminum sul-
other 50% over the next 30 min. fate was incorporated; this gives leavening action during
The slow-reacting SAlP and DMP leavening acids are the middle of the baking process, in addition to the early
useful in pancake and waffle batter for restaurant use, action due to the MCP. This double-acting baking powder
where little or no evolution of CO2 is desired during the was a great success. In Table 3 some typical compositions
holding period between uses. of baking powders are shown. In addition to the soda and
acid, various fillers and calcium salts are also included.
Formula Balance. Some of the ions found in leavening The level of potential leavening gas is nearly constant: it
acids may influence other properties of certain baked is the amount of CO2 equivalent to 28% sodium bicarbon-
goods. The pyrophosphate ion gives a certain taste that is ate in the single-acting powder, and carbon dioxide equiv-
detectable by some people. Aluminum ion plays a role in alent to 30% soda in all the double-acting types. Thus these
developing optimum layer cake structure (15), and SAlP powders are interchangeable from the standpoint of the
and/or SAS is useful as part of the leavening system. So- amount of leavening achieved during baking.
Table 3. Baking Powder Compositions
Double-acting types
Single-acting Household Commercial
Sodium bicarbonate, granular 28.0 30.0 30.0 30.0 30.0 30.0 30.0
Monocalcium phosphate, hydrate 8.7 12.0 5.0 5.0 5.0
Monocalcium phosphate, anhydrous 34.0
Sodium aluminum sulfate 21.0 21.0 26.0
Sodium acid pyrophosphate 38.0 44.0 38.0
Cornstarch, redried 38.0 26.6 37.0 19.0 24.5 26.0 27.0
Calcium sulfate 13.7
Calcium carbonate 20.0
Calcium lactate 2.5
Note: Composition given in percentage of each ingredient in the baking powder.
No shortening
BIOLOGICAL LEAVENING
ENGLISH MUFFINS
PRETZELS
The nomenclature of this item is anomalous, as it was de-
Considered to be the world's oldest snack foods, pretzels veloped in the United States; the term English applied to
reputedly originated around the year 600 in a monastery them is a highly successful marketing ploy. They are a disc-
in the Italian Alps. Supposedly, the monk in charge of the shaped baked product, usually around 3 to 4 in. diameter
bakery formed strips of bread dough into a shape intended and about three-quarters in. high. A good general descrip-
to resemble arms folded across the breast in prayer. When tion is: "Good eating muffins are relatively tough, chewy,
baked, these pretiola (little reward in Italian) were given and honeycombed with medium to large size holes (1/8-
to children who learned their prayers properly. Later, these 1/4 in. diameter). Flavor is bland and somewhat sour. Side
baked bread snacks became popular north of the Alps, walls are straight and light colored. The edge between the
where the name was germanicized to bretzels, a spelling sides and the flat, dark brown top crust is gently rounded,
still used by some pretzel bakers. not sharp." They are baked in a covered griddle cup on a
Soft pretzels, presumably identical with those made by highly automated line. The main features of importance
the Italian monk, are still popular today. They have a mois- are that the dough must be soft so it flows to fill the cup,
ture content similar to that of bread and a short shelf life. and the formulation must lead to the formation of the large
Hard pretzels were supposedly discovered when a baker's internal holes.
apprentice forgot to remove the last trays of pretzels from A typical English muffin dough contains 83 to 87% wa-
the oven at the end of the day, and the overnight residence ter (flour basis equals 100%), 2% sugar, 1.5% salt, 5 to 8%
in the cooling oven dried them, giving them a hard, crisp yeast, and 0.5 to 0.7% calcium propionate. Vital wheat glu-
texture. The rest of this discussion concerns itself with the ten at 1 to 2% is sometimes added to increase the chewi-
low-moisture (2-3%) hard pretzel. ness of the finished muffin. At this absorption level the
Pretzel dough is extremely stiff, made with a low- dough is very soft, and it must be cold (2O0C, 680F) when
protein flour (that from soft white winter wheat is pre- taken from the mixer so that it does not stick when it is
ferred), and only 38 to 42% water. The only other ingredi- divided, rounded, and deposited from the intermediate
ents are yeast (ca 0.25%) and roughly 1% each of salt, proofer into the griddle cups. Dusting material, usually a
shortening, and dry malt. This dough is mixed in a hori- blend of corn flour and cornmeal, is used rather liberally
zontal sigma-arm mixer, allowed to ferment for up to 4 h, (3-4% of the dough weight) to facilitate the various trans-
then processed. fers.
The dough is divided into small pieces, elongated into a Fermentation of the dough piece after it is divided and
thin strip, and twisted into the typical pretzel shape by a rounded is rather short, usually about 30 min. Three
special machine. The formed pretzels receive a short in- factorsshort time, cold dough, and high calcium propio-
termediate proof, then are carried through a caustic bath, nate levelsall tend to retard fermentation, so a rather
which contains 1.25 0.25% sodium hydroxide, held at high yeast level is required. Leavening in the griddle cups
about 19O0F. After exiting this bath, salt is sprinkled on is due to CO2, ethanol, and steam; in addition, some bakers
the tops and the pretzels enter the oven. Here they are add 0.5% baking powder to get an early kick in the cups
baked at about 45O0F for 4 to 5 min. The caustic bath so that the mold is quickly filled by the dough. The finished
gelatinizes the starch on the surface of the pretzel, giving English muffin has a rather high moisture content (about
the crisp, shiny crust. In the oven all residual caustic is 45%) and is prone to mold formation. Calcium propionate
converted to sodium bicarbonate. The baked pretzels are is used at the elevated level mentioned to help overcome
then piled onto slower-moving conveyors that carry them this problem, and it is also added to the dusting flour. An-
through a drying stage, where they remain for 30 to 90 other method is to spray the muffin with a potassium sor-
min (depending on the size of the piece) at a temperature bate solution as it leaves the oven. If this is done, the pro-
of approximately 25O0F. This treatment slowly reduces the pionate may be omitted from the dough, which in turn
moisture to about 2% and also allows equilibration so that allows a decrease of about 1% in the amount of yeast.
the finished pretzel does not check (form small cracks on In some instances the internal grain porosity is still less
its surface). than desired, and the addition of protease enhances the
Variations on this production scheme are many. A ma- openness of the crumb. This additive also increases pan
chine is available that extrudes the dough through a die flow, so absorption might be reduced by 1 to 2%, which
already shaped in the twisted form, so tying is not neces- might or might not be desirable. Sometimes a tangy, acidic
sary. By changing the die the machine will also make taste is wanted (sourdough muffins), and a dry sour base
straight rods, which are a popular form for this snack. Also, or vinegar (acetic acid) is added to the dough, The in-
the exact dough formulation and extent of fermentation creased acidity (lower pH) of the finished product enhances
varies among manufacturers, the details being closely held the antimold action of calcium propionate. Another popu-
as proprietary information, each company sure that its lar variety contains raisins, added in amounts equal to 25
particular formula makes the best possible pretzel. As with to 50% of the flour weight.
DOUGHNUTS and also acts as a water binder that reduces fat absorption
and lengthens shelf life.
Doughnuts are fried in deep fat rather than baked in an Leavening in cake doughnuts is by 1.5% soda (flour ba-
oven as are most other bakery products. They are related sis) and 2.1% sodium acid pyrophosphate (SAPP). The fast-
to another product, fritters, which are made with a soft, reacting grades of SAPP are required, from SAPP-37 to
rich dough containing pieces of fruit (apples) or vegetables SAPP-43 (the fastest grade). When the doughnut is first
(corn), dropped by spoonfuls into hot fat. An apocryphal deposited in the hot (19O0C, 3750F) frying fat, the ring of
story relates that a nineteenth-century Yankee ship cap- dough sinks and is supported on a bottom plate. Leavening
tain loved apple fritters but had trouble holding onto them begins, and after 3 to 7 s the doughnut rises to the surface
when at the ship's wheel during high seas. His cook, anx- and frying of the first side commences. As heat penetrates
ious to please, got the idea of making the fritters with a the dough piece it slowly expands; after the first side is
hole in the center so the captain could stick them on the fried, the doughnut is flipped and the second side is fried.
handspokes of the wheel during busy moments. Although During this time expansion continues, but the diameter of
there is a certain implausibility about this story, the fact the doughnut has been fixed because the first side has set
remains that doughnuts, in one form or another, are ex- (the starch has gelatinized and proteins have denatured).
tremely popular sweet snacks or desserts. Thus, second-stage expansion tends to be into the center
There are three basic types of doughnuts: cake dough- hole and the typical star is formed (or the doughnut balls
nuts, yeast-raised doughnuts, and French crullers. Cake and fills the center hole if conditions are incorrect).
doughnuts are chemically leavened, yeast-raised dough- When the finished doughnut is cut crosswise, three
nuts use a sweet yeasted dough, and French crullers are regions are readily seen. The central core is surrounded by
steam leavened. These will be discussed separately. a more porous leavened ring, but this porosity tends to be
greater on the second side than the first. If the core is in-
Cake Doughnuts adequately leavened, it will be dense and gummy, and the
doughnut will not have a good eating quality. Part of the
Batters for this product are a leaner, lower-sugar version art of the doughnut formulator is in choosing leavening
of layer cake batters. A typical regular cake doughnut mix acids that strike the best compromise to achieve moderate
contains (on 100% flour basis) about 40% sugar and 13% porosity of the two sides along with at least some opening
nonemulsified shortening. Other ingredients frequently up of the core.
found in doughnut mixes are defatted soy flour, nonfat dry
milk, potato starch, and dried egg yolk. These ingredients Yeast-Raised Doughnuts
give a tender eating quality to the finished product, as well
These doughnuts are made using a rather lean, sweet
as limiting fat absorption during frying. The protein ingre-
dough. After full development of the dough, it is sheeted,
dients decrease fat absorption, while potato starch helps
cut into rings, and the doughnuts are proofed for 30 to 45
retain moisture in the finished doughnut and gives a
min. The raised doughnuts are then introduced into the
longer shelf life. Lecithin is sometimes used to enhance the
fryer, where they are fried for about 1 min on each side.
wetting of the dry mix during batter preparation, and oc-
(Because they are already leavened, they float on the fat
casionally monoglyceride is added to make a more tender
throughout the frying cycle.) They are then removed, the
final product. Other emulsifiers are not used, as they in-
surface fat is drained, and the fried doughnuts are (most
crease fat absorption without conferring any quality en-
often) glazed with a simple sugar/water glaze. If they are
hancement.
to be iced or otherwise coated, they are usually cooled be-
Most cake doughnuts are produced by extruding (or de-
fore these operations are carried out.
positing) the batter from a reservoir directly into the hot
Yeast-raised doughnuts can be made in many different
fat fryer. Bench-cut doughnuts are made using the same
shapes. In addition to rings, the dough is also frequently
recipe, but with a reduced amount of water. This gives a
cut into strips and twisted into various fanciful shapes be-
dough (rather than a batter) that can be rolled out on the
fore proofing and frying. In the form of rectangles about 2
workbench and cut into rings using a doughnut cutter. This
by 4 in., they are iced and topped with chopped nuts or
process takes much more hand labor than depositing and
fruit to make Long Johns. In the form of discs, the fried
is usually used only in home baking or in small, traditional
piece can be filled with jelly or custard. This product, filled
doughnut shops.
with raspberry-flavored jelly, is known as a Berliner in
In commercial bakeries and most doughnut shops,
Austria and Germany. (This explains why the Germans
doughnut batter is deposited through a cutter into the fry-
roared with laughter when, in 1963, President Kennedy
ing fat. Proper batter viscosity is extremely important to
proclaimed, "Ich bin ein Berliner." He was telling them
attain uniformity of flow through the cutter and uniform
that he was a jelly-filled doughnut.)
spread in the fryer. Batter viscosity is governed by the
amount of water used in mixing (usually about 70% based
French Crullers
on flour, or 38-44% based on total dry mix weight) and the
way that water is partitioned between flour, sugar, soy These doughnuts are made using eclair dough (see the next
flour, and the other ingredients present. Sometimes high- section). The dough is deposited in a ring shape onto a
viscosity gums (guar, locust bean, sodium carboxymethyl- sheet of parchment paper, and after a few moments to al-
cellulose) are added to the dry mix at levels of 0.1 to 0.25%. low it to set, the parchment is dipped into the frying fat
The gum helps give uniform viscosity from batch to batch and the rings of dough are loosened from the paper. The
dough can also be deposited using a specially shaped cutter some care in the roll-in process to obtain a flaky final prod-
that produces a fluted surface on the ring of dough. The uct.
dough piece expands to a much greater extent than does The dough for this product is a flour/water dough (no
cake doughnut batter, and the finished piece is much less yeast), containing about 6% shortening and 6% whole eggs.
dense than other doughnuts. It is frequently glazed with a After it is fully developed it is sheeted out, fat is spread
butter/rum flavored glaze. over two-thirds of the dough, which is then folded to give
a sandwich having three layers of dough separated by two
layers of fat. This is sheeted out and folded as already de-
ECLAIRS scribed. Usually the dough is refrigerated after the second
sheeting and folding, to keep the fat in the plastic state. If
The dough for eclairs and French crullers (pate de choux) the dough becomes too warm, the fat melts and gets incor-
is a paste made in a rather unusual procedure. Water (two porated into the dough itself, and the layering effect is lost.
parts) and shortening (one part) are placed in a kettle and The fat usually used is a special puff-paste margarine, hav-
brought to a rolling boil. After the fat is melted, a pinch of ing a broad plastic range, and containing about 15% water.
salt is added, flour (1-1.5 parts) is added, and the mixture In the oven the water (which is finely emulsified in the fat)
is stirred briskly. The gelatinized flour paste is cooled to forms steam, which helps give the puff to puff pastry. Thus,
about 15O0F, and two parts whole egg are added in several puff pastry is a steam-leavened product.
increments, with continuous stirring. A small amount of
ammonium bicarbonate, dissolved in one-half part milk, is Croissants
stirred in. The final paste should be soft enough to deposit Croissants are another legacy of the siege of Vienna. The
from a pastry bag, yet firm enough to hold its shape once story is that the Turks were busy digging a tunnel under
deposited. If it is too stiff, it may be softened by the addi- the city walls but were overheard by a baker in the early
tion of a small amount of milk or water. hours of the morning, as they were digging under his shop.
The finished dough is deposited on sheet pans lined He alerted the authorities, and a countertunnel foiled the
with parchment paper, then baked in a hot (4250F) oven plot. After the siege was lifted, the baker made rolls in the
until the eclairs are crispy. Leavening action is due to the shape of a crescent (the emblem on the Turkish flag), which
formation of steam in the interior of the piece. If inade- were sold to celebrate the victory, and which became a Vi-
quate leavening occurs, a small amount of ammonium bi- ennese tradition. Marie Antoinette introduced these Kip-
carbonate (no more than 1% of the weight of the water feln to the French court, and they became popular under
used) may be dissolved in a little water and mixed in at the French name croissant.
the end of the dough-making procedure. The finished piece A typical croissant dough is basically a straight dough,
should be crisp on the outside, hollow on the inside, and containing 10% sugar, 1% salt, and 4% margarine (flour
with no soggy layer on the interior wall. basis), with a fairly high (9%) yeast level and slightly below
Eclairs are usually filled with a chilled custard, either normal absorption. Croissant dough is mixed cold (18-
plain or a French custard (butter-flavored). They are then 2O0C, 64-680F). This practice, together with the slight un-
iced, with chocolate being the most popular flavor, or derabsorption, retards fermentation. Proofing tempera-
dusted with confectioners' (very finely powdered) sugar. To tures are also relatively low, not exceeding the melting
prevent bacterial growth, custard-filled eclairs should be point of the fat (ca 370C, 980F). For these reasons a rather
refrigerated until served. high level of yeast is used in the dough. Numerous varia-
tions on the basic mixing, sheeting, and roll-in process are
LAYERED DOUGH PRODUCTS used, most of which seem to be based more on tradition
than on actually yielding superior product. After mixing,
Numerous bakery products have a unique texture, in that the dough is allowed to ferment for up to 1 hr, then the fat
the baked dough is present in many thin layers rather than is rolled in, essentially as described for puff pastry. The
one continuous matrix. This effect is obtained by placing a traditional fat for croissants is unsalted butter, although
layer of fat between two layers of dough, rolling out this many commercial companies today use a bakers' marga-
sandwich to a thin sheet, folding the sheet over onto itself rine that does not get as hard as butter at retarder tem-
into three or four layers, and repeating this rolling and peratures and so spreads more uniformly during the sheet-
folding process two or three more times. If done properly, ing and folding process. The usual fat-to-dough ratio is
the final sheet consists of 50 to 100 layers of dough inter- about 25%, that is, 1 Ib of butter to 4 Ib of dough.
spersed with an equal number of layers of fat. When baked, The rolled-in dough is sheeted out, then cut into trian-
the dough layers set up more or less independently, giving gles having a height about twice the width of the base. This
the flaky texture of the finished product. triangle is rolled up, starting from the base, the shaped
dough piece is placed on a sheet pan, and the ends are
Puff Pastry pulled down to give the typical crescent shape. After proof-
ing for 1 to 3 h, it is baked and cooled. Care must be taken
Puff pastry dough is used for a large number of culinary that the piece is not underproofed, otherwise the finished
items, from basic pastries such as fruit turnovers and na- product loses its flakiness and is tough, chewy, and unpal-
poleons, to patty shells for holding a variety of fillings for atable. Croissants are frequently sliced horizontally and
appetizers, to dough for enclosing fish or meat, such as beef used to make sandwiches, with a wide variety of fillings
Wellington. It needs no fermentation but does require being offered by various specialty shops.
Danish Pastry dough is gently mixed until the flour is wetted and the
dough forms a lumpy, slightly sticky ball. The dough
Danish dough is a rich, sweet, yeasted dough made with a
should then be allowed to rest for a time, preferably in a
higher than usual absorption. The dough is quite soft,
refrigerator, to allow the water to equilibrate with the flour
mixed cold (62-640F), and not fully developed in the mixer.
protein.
Gluten development takes place during the roll-in process.
An amount of this dough just sufficient to form the crust
The dough is divided into pieces of a suitable size (eg, 16
(either top or bottom) is then rolled out into a circle. An
Ib) and then retarded for several hours. Some fermentation
absolute minimum of dusting flour is used, and it is best
takes place during this time. The cold dough is then
to use cloth sleeve on the rolling pin and a flat cloth on the
sheeted out and fat is rolled in, as already described. Spe-
bench top, both of which have been rubbed with flour and
cialty shops use butter or bakers' margarine for the roll-in
the excess flour removed. Once the desired diameter of
fat, but all-purpose shortening works equally well. The
crust is achieved, the circle of dough is loosely rolled up on
dough sheet is usually given the first two sheetings and
the rolling pin and transferred to the pie pan, where it is
folds, then returned to the retarder for 6 to 12 h. It is then
gently shaped and the edges sealed (if it is the top crust,
given one more sheeting and three-fold, and returned to
and the filling is in place).
the retarder for 24 to 48 h for further fermentation.
The main mistake in making a flaky, tender pie crust
Danish pastry is almost invariably made by sheeting
lies in excessive working of the dough and consequent de-
out the rolled-in dough, cutting into various shapes, then
velopment of the gluten in the flour. This can happen if too
adding some sort of sweet filling (fruit, nuts, cinnamon,
much water (or water that is warm) is added to the dough,
etc) and folding or rolling up the dough to retain this filling
and it is mixed until the water disappears. Also, excessive
during proofing and baking. The variety of shapes and fill-
dusting flour, and rolling the dough more than once, will
ings is limited only by the ingenuity of the baker. The
contribute to gluten formation. In large-scale pie produc-
proofed pieces are sometimes washed lightly with diluted
tion (either in a commercial bakery, or in an institutional
egg just before baking, to give a shine to the finished piece.
setting) the dough just described may be too tender for the
Alternatively, the piece may be sprayed with a light sugar
kind of handling it receives, and a certain amount of gluten
syrup as it exits the oven, to give the same effect. If a Dan-
development will be done on purpose, in the interests of
ish coffee cake, for example, is to receive an icing, this is
production efficiency. Although this speeds up the operat-
usually a rather thin icing that is drizzled over the top of
ing line, it produces the leathery crusts that are abandoned
the coffee cake in a random pattern, rather than applied
on dessert plates across the country.
in a solid layer (as on sweet rolls). A good Danish pastry is
Fillings for pies are usually either some kind of fruit in
one of the foundation stones of any small retail bakery to-
a starch-stabilized juice matrix or a custard. The formu-
day.
lation of a good pie filling deserves an entire article to itself
and will not be explored here. However, the stabilizing sys-
PIES tem should be such that during baking the filling will not
boil or foam excessively, to the point where it overflows the
The term pie (like biscuit) means something rather differ- side of the pie. If the pie crust at the filling/crust interface
ent in the United States than it does on the other side of does not bake rapidly enough, it will soak up moisture from
the Atlantic Ocean. In Europe a pie usually contains meat, the filling, and the final crust will be soggy. This may be
potatoes, and other vegetables and may have a crust of puff due to using a cold filling in the pie or having too low an
pastry, of mashed potatoes, or of a flour dumpling. It is oven temperature.
normally the main dish of a meal. In the United States, on One type of pie avoids this pitfall, by adding the filling
the other hand, a pie is for dessert, or is a sweet snack. It after the bottom crust is baked. An example is strawberry
need not be a baked food; for example, ice cream pies are pie; a single crust is baked in the pie pan, then the fruit is
now popular. In at least one instance (Boston cream pie), placed in the cooled crust and a strawberry-flavored starch
pie is more properly a filled, layered sponge cake. Having glaze is poured over the top. The pie is refrigerated until
said that, this section discusses pies primarily in terms of served.
the traditional one-crust or two-crust baked American des-
sert pie, and, briefly, the fried pie, a related, traditional
American dessert. Fried Pies
A pie crust is one of the simplest of baked doughs, com-
prising only flour, shortening, salt, and water. The ability These desserts are traditional in the southeastern part of
to combine these few ingredients properly to produce a the United States, although they are now produced com-
flaky, tender pie crust, however, is rare, as attested by the mercially and sold throughout the country. A pie crust with
number of leathery, soggy, nearly inedible pie crusts that a slightly developed gluten is used. A circle is rolled out,
are served to diners in U.S. restaurants every day. The first fruit filling is placed on one half the circle, the other half
step in making a pie crust is to cut the shortening into the of the crust is folded over, and the edges are sealed. This
flour; that is, mix the two using a fork or similar mixing is then fried in a half inch of hot fat, in a heavy skillet. In
tool, reducing the particle size of the shortening to small the commercial version, the shaped and filled piece is fried
lumps, perhaps one-quarter the size of a pea. Then a mea- in a deep fat (doughnut) fryer. A top conveyor belt keeps
sured amount of cold water (even ice water, in hot the pie submerged throughout its journey through the hot
weather), with the salt dissolved in it, is added, and the fat. The crust absorbs some of the frying fat, tenderizing it
so that it is not leathery as it would be if baked. The com-
mercial fried pie is given a sugar glaze before being cooled,
wrapped, and dispatched to the consumer. The traditional
fried pie, on the other hand, is usually eaten while still
warm, fresh from the kitchen, and any glaze or other top-
ping would be superfluous.
GENERAL REFERENCES
Technical Bulletins of the American Institute of Baking: Bagels,
8(11) 1986; 10(4), 1988; Croissants, 8(10), 1986; Donuts, 1(6,7)
1979; 2(7), 1980; 4(9), 1982; English Muffins, 1(1), 1979; Pizza
Dough, 1(11), 1979; 8(12), 1986; Chemically Leavened Pizza
Dough, 19(11), 1997.
A. Matz, Bakery Technology and Engineering, AVI Publishing,
Westport, Conn., 1972.
E. J. Pyler, Baking Science & Technology, 3rd ed., Sosland Pub-
lishing, Merriam, Kans. 1988.
W. J. Sultan, Practical Baking, 5th ed., Van Nostrand Reinhold,
New York, 1990.
BAMBOO SHOOTS
PRACTICAL DESCRIPTION
STORAGE
Spade
Second yr
bamboo
First yr bamboo
Cutting position of
first yr bamboo for Cutting of shoot
propagation
Mound
BIBLIOGRAPHY
FOOD USES
1. R. M. Ruberte, "Leaf and Miscellaneous Vegetables," in F. W.
In the preparation of shoots for use, the sheaths and tough Martin, ed., Handbook of Tropical Food Crops, CRC Press,
basal portions are removed, and the tender shoots are then Inc., Boca Raton, Fl., 1984.
sliced or cut lengthwise and boiled in water. The still crispy 2. M. Yamaguchi, "Bamboo Shoot," World Vegetables, AVI Pub-
slices can be used in many dishes. Upon tasting, if the lishing Co., Westport, Conn., 1983.
shoot is bitter, it is boiled again to remove the bitterness. 3. Department of Agriculture and Forestry, "Crop Production,"
Raw bamboo shoot is acrid, and boiling removes the acrid- in Taiwan Agricultural Yearbook, Taiwan Provincial Govern-
ity. The bitterness is from cyanogenic glucosides, which, ment, Taichun, Taiwan, 1990.
4. B. N. Lee, "Bamboo Shoot," Farmers Guide. Harvest Farm found in eastern Spain dating from around 7000 B.C. (2).
Magazine Ltd., Taipei, Taiwan, 1980 pp. 885-888. There, gatherers collected honey by robbing wild bee nests.
5. G. M. Leu, "Disappearing of Bamboos" Harvest 35, 16-17 Honey hunting is still widely practiced in Asia to obtain
(June 28, 1985). honey from A. dorsata and to a lesser extent from A. florea
6. G. A. C. Herklots, Vegetables in South-East Asia, George Allen nests. It can be postulated that an early stage in the de-
& Unwin Ltd., London, 1972. velopment of beekeeping involved the cutting of a log sec-
7. M. T. Chang, "Cultivation of Bamboo Shoot," Harvest 36, 42- tion enclosing a bee colony and transporting the log to the
45 (Aug. 1, 1986). dwelling of the gatherer. There the log and bees would pro-
8. M. L. Liao et al., "Respiration Measurement of Some Fruits vide a convenient source of honey and brood for periodic
and Vegetables of Taiwan," FIRDI Technical Report E-66, robbing by the new owner. The use of log sections as bee-
Hsinchu, Taiwan, 1982.
hives persists in some African regions. The first hives
9. T. R. Yen et al., "Quality Improvement of Canned Bamboo made by humans probably were composed of clay, straw,
Shoot," FIRDI Technical Report 237, Hsinchu, Taiwan, 1982.
or tree bark. In the Middle East, honey bees are still kept
10. R. Y. Chen et al., "Postharvest Handling and Storage of Bam- in clay pottery, mud, and straw hives. Some of these hive
boo Shoots," Acta Horticulture 258:309-316,1989.
materials were used some 6000 years ago.
11. R. Y. Chen et al., "Control of Postharvest Quality of Bamboo The advent of what is considered the "modern era" of
Shoot," FIRDI Technical Report 423, Hsinchu, Taiwan, 1986.
beekeeping came about with the discovery of movable-
12. G. T. Huang et al., "Improvement on the Quality of Dried Fer- frame beehives. The person generally credited with pub-
mented Bamboo Shoots," FIRDI Technical Report E-121,
Hsinchu, Taiwan, 1985.
licizing the significance of the "bee space" was Lorenzo L.
Langstroth who, in 1851, discovered that bees would re-
13. FIRDI, "Table of Taiwan Food Composition," FIRDI Technical
Report 24, Hsinchu, Taiwan, 1971.
frain from building wax connections between neighboring
combs, or combs and the side of the beehive, if the space
separating them was approximately 3/8 in. (3). This seem-
MING-SAI Liu ingly modest discovery led directly to the evolution of hives
Food Industry Research and Development Institute that had fully removable frames that enclose and support
Hsinchu, Taiwan the beeswax combs. These frames could be manipulated
easily by the beekeeper and removed for the purpose of
examining the brood or extracting honey. The latter part
BANANAS. See FRUITS, TROPICAL. of the nineteenth century saw the development of an amaz-
ing array of inventions based on this technology, including
machines for removing wax (uncapping) and extracting
BARLEY. See CEREALS SCIENCE AND TECHNOLOGY. honey from the new removable frames. Eventually, the
Langstroth hive became established as the standard-size
beehive that remains largely unchanged to the present
BEEKEEPING day.
Honey bees represent less than 12 of the thousands of bee
species that exist around the world. Honey bees are unique BIOLOGY OF HONEY BEES
in that they live in perennial social societies, and they pro-
duce a number of "hive products" that are used by humans All members of the genus Apis are eusocial, which means
in various ways. However, their greatest value to humans truly social. To entomologists this term indicates that there
is their role as pollinators of cultivated crops. Approxi- is cooperative care of the young by individuals of the same
mately one-third of the diet consumed by individuals living species, an overlap in generations, and production of a ster-
in advanced societies is the product of honey bee pollina- ile or nonreproducing worker caste. This type of social de-
tion. velopment is uncommon considering that there are over 1
million named insect species. Living as a colony, eusocial
HISTORY species like honey bees provide more food and protection
for themselves and their young than can any solitary in-
Honey bees (genus Apis) are believed to have originated in dividual. It is because honey bees store food for future
Southeast Asia (1). New species of Apis are still being de- needs that humans have been able to exploit them.
scribed from that region today. Four species that naturally Scientists subdivide the wide-ranging species A. melli-
inhabit large areas of the world include the Western honey fera and A. cerana into a number of races (4). These races
bee (Apis mellifera) from Europe and Africa, and the East- differ in behavioral and physical characteristics that are
ern honey bee (Apis cerana), the giant honey bee (Apis dor- the result of adaptations of the species over time, following
said], and the dwarf honey bee (Apis florea) from Southeast isolation in geographical regions. In fact, such races are
Asia. Only A. mellifera and A. cerana are cavity nesting sometimes called geographic races. In A. mellifera some
species and thus have been collected by humans and suc- races can be physically distinguished only through the use
cessfully transferred and managed in artificial domiciles of computer-assisted morphometric (body measurement)
or hives. analysis. To describe honey bee races, specialists use a tri-
It is likely that the first beekeepers were honey hunters nomial system of nomenclature as opposed to the tradi-
or honey gathers, as depicted in a Paleolithic rock painting tional binomial. For example, the Italian honey bee race's
4. B. N. Lee, "Bamboo Shoot," Farmers Guide. Harvest Farm found in eastern Spain dating from around 7000 B.C. (2).
Magazine Ltd., Taipei, Taiwan, 1980 pp. 885-888. There, gatherers collected honey by robbing wild bee nests.
5. G. M. Leu, "Disappearing of Bamboos" Harvest 35, 16-17 Honey hunting is still widely practiced in Asia to obtain
(June 28, 1985). honey from A. dorsata and to a lesser extent from A. florea
6. G. A. C. Herklots, Vegetables in South-East Asia, George Allen nests. It can be postulated that an early stage in the de-
& Unwin Ltd., London, 1972. velopment of beekeeping involved the cutting of a log sec-
7. M. T. Chang, "Cultivation of Bamboo Shoot," Harvest 36, 42- tion enclosing a bee colony and transporting the log to the
45 (Aug. 1, 1986). dwelling of the gatherer. There the log and bees would pro-
8. M. L. Liao et al., "Respiration Measurement of Some Fruits vide a convenient source of honey and brood for periodic
and Vegetables of Taiwan," FIRDI Technical Report E-66, robbing by the new owner. The use of log sections as bee-
Hsinchu, Taiwan, 1982.
hives persists in some African regions. The first hives
9. T. R. Yen et al., "Quality Improvement of Canned Bamboo made by humans probably were composed of clay, straw,
Shoot," FIRDI Technical Report 237, Hsinchu, Taiwan, 1982.
or tree bark. In the Middle East, honey bees are still kept
10. R. Y. Chen et al., "Postharvest Handling and Storage of Bam- in clay pottery, mud, and straw hives. Some of these hive
boo Shoots," Acta Horticulture 258:309-316,1989.
materials were used some 6000 years ago.
11. R. Y. Chen et al., "Control of Postharvest Quality of Bamboo The advent of what is considered the "modern era" of
Shoot," FIRDI Technical Report 423, Hsinchu, Taiwan, 1986.
beekeeping came about with the discovery of movable-
12. G. T. Huang et al., "Improvement on the Quality of Dried Fer- frame beehives. The person generally credited with pub-
mented Bamboo Shoots," FIRDI Technical Report E-121,
Hsinchu, Taiwan, 1985.
licizing the significance of the "bee space" was Lorenzo L.
Langstroth who, in 1851, discovered that bees would re-
13. FIRDI, "Table of Taiwan Food Composition," FIRDI Technical
Report 24, Hsinchu, Taiwan, 1971.
frain from building wax connections between neighboring
combs, or combs and the side of the beehive, if the space
separating them was approximately 3/8 in. (3). This seem-
MING-SAI Liu ingly modest discovery led directly to the evolution of hives
Food Industry Research and Development Institute that had fully removable frames that enclose and support
Hsinchu, Taiwan the beeswax combs. These frames could be manipulated
easily by the beekeeper and removed for the purpose of
examining the brood or extracting honey. The latter part
BANANAS. See FRUITS, TROPICAL. of the nineteenth century saw the development of an amaz-
ing array of inventions based on this technology, including
machines for removing wax (uncapping) and extracting
BARLEY. See CEREALS SCIENCE AND TECHNOLOGY. honey from the new removable frames. Eventually, the
Langstroth hive became established as the standard-size
beehive that remains largely unchanged to the present
BEEKEEPING day.
Honey bees represent less than 12 of the thousands of bee
species that exist around the world. Honey bees are unique BIOLOGY OF HONEY BEES
in that they live in perennial social societies, and they pro-
duce a number of "hive products" that are used by humans All members of the genus Apis are eusocial, which means
in various ways. However, their greatest value to humans truly social. To entomologists this term indicates that there
is their role as pollinators of cultivated crops. Approxi- is cooperative care of the young by individuals of the same
mately one-third of the diet consumed by individuals living species, an overlap in generations, and production of a ster-
in advanced societies is the product of honey bee pollina- ile or nonreproducing worker caste. This type of social de-
tion. velopment is uncommon considering that there are over 1
million named insect species. Living as a colony, eusocial
HISTORY species like honey bees provide more food and protection
for themselves and their young than can any solitary in-
Honey bees (genus Apis) are believed to have originated in dividual. It is because honey bees store food for future
Southeast Asia (1). New species of Apis are still being de- needs that humans have been able to exploit them.
scribed from that region today. Four species that naturally Scientists subdivide the wide-ranging species A. melli-
inhabit large areas of the world include the Western honey fera and A. cerana into a number of races (4). These races
bee (Apis mellifera) from Europe and Africa, and the East- differ in behavioral and physical characteristics that are
ern honey bee (Apis cerana), the giant honey bee (Apis dor- the result of adaptations of the species over time, following
said], and the dwarf honey bee (Apis florea) from Southeast isolation in geographical regions. In fact, such races are
Asia. Only A. mellifera and A. cerana are cavity nesting sometimes called geographic races. In A. mellifera some
species and thus have been collected by humans and suc- races can be physically distinguished only through the use
cessfully transferred and managed in artificial domiciles of computer-assisted morphometric (body measurement)
or hives. analysis. To describe honey bee races, specialists use a tri-
It is likely that the first beekeepers were honey hunters nomial system of nomenclature as opposed to the tradi-
or honey gathers, as depicted in a Paleolithic rock painting tional binomial. For example, the Italian honey bee race's
trinomial is A. mellifera ligustica. Other examples are A. ers feed the developing larva in such a way that a queen,
mellifera mellifera, a race from northern Europe and the rather than a worker, is produced.
first honey bee race known to have been introduced into
the New World, and A. mellifera carnica, the Carniolan
honey bee from southern Austria and Yugoslavia. DRONES
A colony of honey bees may contain more than 45,000
adult individuals during the summer when the population The drones are males and their primary function is to mate
peaks. Four life stages present in the colony are the eggs, with virgin queens. They are raised in specially con-
larvae, pupae, and adults. These stages can be further sub- structed cells that are larger than the worker cells. Genet-
divided by the two sexes, females and males (drones). The ically, drones are haploid, having a chromosome number of
females may be divided further into two castes, workers 16, in contrast to the diploid status of workers and queens,
and queens. which have a chromosome number of 32. In temperate
areas, drones are produced in large numbers, usually be-
ginning in March, and are maintained until the first killing
WORKERS frost. A typical colony in summer will have 1000 to 2000
drones. Populous colonies sometimes will keep their
Workers, as their name implies, do the work of the colony. drones into late November. Some scientists suspect that
The worker caste builds the combs used to house devel- drones have functions other than mating, but no evidence
oping eggs, larvae, and pupae (collectively called brood) has been forthcoming to support this viewpoint.
and to store honey and pollen. They forage outside the col-
ony for nectar (carbohydrate) and pollen (proteins, vita- MATING
mins, minerals, and fats) to provide food for the colony.
Workers also feed the brood, queen, and drones and defend In nature, mating of drones and queens occurs in flight.
the colony against intruders. When a worker bee stings, The queen mates only at one early period of her life, during
the barbed stinger usually pulls out of her abdomen and the so-called nuptial flight(s). About seven days after she
remains attached to her victim, where its odor attracts emerges from her cell as an adult, she is considered sexu-
more bees to sting. Bees that have stung die within a day. ally mature and will leave the hive to mate. A queen mates
Sexually, workers are females with 32 chromosomes with about 17 drones (5). Queens are believed to fly to a
and usually lack functional ovaries. However, in certain location known as a drone congregation area (DCA) to
situations, such as the absence of a queen, it is possible for mate. To this day, it is not possible to predict with certainty
workers to lay eggs. Laying workers are incapable of laying what geographical condition or other attributes are needed
fertile eggs since they do not mate with drones to obtain to establish a DCA. The results of recent work done with
sperm. Consequently, they lay eggs that only produce hap- radar suggest that DCAs may be busy intersections in a
loid drones. This leads to eventual death of the colony. In complex network of drone pathways. Drones injure them-
rare situations, laying workers can produce females im- selves mortally during mating, after which they fall to the
paternate (without fathers). This parthenogenic means of ground and die.
reproduction is found in the highest frequency in the race
A. mellifera capensis.
During the busy foraging season, the life span of a SWARMING
worker is about six weeks. Workers literally work them-
selves to death. However, workers reared late in the fall The process of swarming represents the natural method of
often live through the winter into the following spring. colony reproduction. Under certain conditions, often asso-
ciated with the seasonal growth cycle of the colony, workers
begin to raise additional queens in the colony. At some
QUEENS point before the virgin queens emerge from their cells, the
old queen will depart from the nest with approximately
Queens are also females. They have the capacity to mate half of the workers and drones and attempt to establish a
and lay fertilized eggs. Usually each colony has a single colony at a new home site. The propensity for swarming
queen. However, under certain conditions colonies may and the conditions leading up to this behavior vary within
have more than one queen. A few commercial beekeepers and among races of honey bees. Sometimes one or more of
intentionally manipulate beehives so they can maintain a the newly emerged virgin queens will also depart with a
two-queen colony that is sometimes more productive than group of workers and drones in an "after swarm," also at-
a single-queen colony. Queens live for as long as five years tempting to establish a new colony.
but most commercial beekeepers replace them every two
years. The queen is the egg-laying female of the colony. The DISEASES AND PESTS
maximum number of eggs a queen lays varies throughout
the season. It is estimated that a good queen can lay 1500
Larval Diseases
to 2000 eggs a day. A colony will produce new queens if its
queen becomes a drone layer (depletes her stored sperm) Like all living animals, the honey bee is subject to the rav-
or is injured or if the colony is about to swarm. New queens ages of diseases and pests. The diseases range from viral
have to be raised in specially constructed cells. The work- to fungal in origin. One troublesome brood disease is called
American foulbrood disease. This disease brought about emerged bees to infest. All castes of bees are susceptible,
the establishment of many state bee inspection programs and the mites tend to remain in drones and queens. Tra-
(6). American foulbrood disease is caused by Paenibacillus cheal mites feed by pushing their mouthparts through
larvae larvae (formerly Bacillus larvae). Only the spore membranous areas of the tracheal tubes and sucking he-
stage of this bacterium is infective and only in honey bee molymph (bee blood). Mite feeding causes hemolymph
larvae less than three days of age. Another important chemistry changes, destruction of flight muscles, darken-
brood disease is European foulbrood disease, caused by ing (healing?) of tracheal tubes, transmission of diseases,
Melissococcus pluton. In both cases, beekeepers sometimes and reduced life expectancy. Colony losses are common in
use an antibiotic (oxytetracycline) for disease prevention areas of colder climates, where new bees are not reared for
and treatment. Another bacterial disease of minor impor- months during the winter.
tance is powdery scale disease, which is caused by Paeni- Menthol fumigation inside the beehive currently is the
bacillus larvae pulvifaciens. only registered and legal means of reducing the mite popu-
All the known fungal diseases that affect the brood are lation. Treatments are temperature sensitive, with high
of minor significance except for chalkbrood disease, which heat driving bees from the boxes resulting in some queen
is caused by Ascosphaera apis. Until 1968, no chalkbrood losses. Once mite populations are reduced, they often can
disease had been found in the United States. Currently, be prohibited from increasing by placing thin patties, made
chalkbrood is reported present in most of the states, and of two parts sugar to one part vegetable shortening, in con-
many beekeepers report reductions in their honey crop due tact with the bees in the hive.
to this disease. There is no effective chemical control for The second important mite to be detected in the United
chalkbrood. States was the varroa mite, Varroa jacobsoni, found in
A number of viruses affect honey bees. Most virus dis- 1987 (10,11). Varroa is an ectoparasite that feeds through
eases of bees are considered of minor importance and no membranous portions of the exoskeleton of adult and lar-
treatment is necessary. Two brood diseases of viral origin val bees. Reproduction takes place only in capped cells con-
are sacbrood and filamentous virus disease (formerly be- taining worker or drone pupae. All developmental stages
lieved to be of rickettsial origin). of the mite feed on the pupa. Physiologically immature
male offspring mate with their sisters, delivering sperm
Adult Diseases that complete maturation in their sisters. When the bee
emerges from its cell, the mites are liberated.
Nosema disease is caused by the microsporidian Nosema
As with tracheal mites, Varroa feeding reduces protein
apis. This protozoan shortens the life span of adult bees
content in the host's hemolymph and reduces its life span.
and reduces their production of royal jelly. Consequently,
As mite populations increase, two or more Varroa infest
brood and honey production are reduced by 30 to 40%. The
the same cell. The host pupa is apt to shrink and have
subtle effects of this disease are difficult to recognize and
malformed wings and legs. Such individuals are carried
most beekeepers do not realize that their honey bees are
out of their cells by worker bees and discarded outside the
infected. Fumagillin is used by some beekeepers to treat
hive. Without replacement workers, the colony perishes.
this disease.
Varroa also are disease vectors. In 1995 and 1996 there
Chronic bee paralysis is a virus-induced disease that is
were so many Varroa in the country that we lost nearly
occasionally seen in honey bee colonies. This disease mim-
90% of our feral (unmanaged) colonies. Gardeners and
ics the effects of pesticide kills, and many beekeepers may
commercial growers realized these losses when they no-
misdiagnose the condition. Fortunately, the disease is not
ticed a total lack of honey bees on crops requiring polli-
serious. It is generally believed that requeening can abate
nation.
the disease.
Introduction of plastic strips containing a time-release
Other minor diseases affect the health of honey bees but
acaricide is the only currently registered, legal chemical
are of little economic significance. Noninfectious conditions
control for Varroa mites. The selective acaricide kills the
caused by pesticides and poisonous plants, such as Cali-
mites on contact without killing the bees. In a number of
fornia buckeye (Aesculus californica), cornlily (Veratrum
locations around the world, scientists are searching for
califonicum), death camas (Zygadenus venenosus), and
new and different chemistries to control the mite. Other
some locoweeds (Astragalus spp) can be serious problems
researchers are screening U.S. and foreign bee stocks for
in some years. A more detailed discussion of this subject
populations demonstrating tolerance or resistance to Var-
has been published (7).
roa and the tracheal mite. Results look much better for the
tracheal mite than for Varroa, which is an interspecific
Parasitic Mites
transplant from its original bee host, A. cerana (12).
The first of two problematic, then "exotic," parasitic mites
of honey bees was detected in the United States in 1984
(8,9). Acarapis woodi, the tracheal mite, lives and repro- AFRICANIZED HONEY BEES
duces in the thoracic tracheae (breathing tubes) of adult
honey bees. During warmer times of the year, mites remain An especially defensive, man-made, hybrid race of honey
in young worker hosts only during the three weeks that bees reached southern Texas in 1990. The result of inten-
they perform chores in the hive. When the workers begin tional crossing of European and African stocks of honey
to forage, the mites leave their original hosts at night, bees in Brazil, the Africanized honey bees (AHBs) ex-
when the bees are relatively motionless, and seek newly panded their population and the territory in which they
live at a phenomenal rate. The leading edge of the popu- Propolis
lation expansion progressed about 250 to 300 miles per
year as the bees moved from Brazil to Mexico. Fortunately Propolis or "bee glue" is a resinous material the bees collect
they slowed down considerably as they entered more tem- from plants. This material is used by honey bees to seal
perate climates. Population expansion to the east seems to small openings or cracks and for mummification of foreign
have stopped west of Houston, Texas, but is continuing to objects that are too large for the bees to remove from the
the west in New Mexico, Arizona, Nevada, and California. hive (such as a dead mouse). Because the bees also use
Various opinions exist, but it appears that AHBs may not propolis to cement together wooden parts of man-made
move, on their own, too much further north than their cur- beehives, most beekeepers consider propolis a nuisance
rent locations (13). and maintain bees that use less of the substance. Propolis
Away from their hives, AHBs forage similarly to Euro- has been shown to possess antimicrobial properties and is
pean honey bees (EHBs), can be used for pollinating crops, used in some European and Asian countries as the active
and produce good honey yields if managed carefully. How- ingredient in tinctures and throat lozenges. Propolis can
ever, their propensity to defend their nests extremely be scraped from wooden hive parts and can also be har-
quickly, with very large number of stinging bees, makes vested from a perforated plastic mat that is placed between
them inappropriate for the type of beekeeping that is prac- the supers (boxes that make up a beehive). After the bees
ticed in the United States. Fortunately, there is a segment deposit propolis on it, the mat is removed and frozen pre-
of the commercial beekeeping industry that produces new vious to breaking off the substance. Periodically, bee jour-
queens, mated outside of areas "colonized" by AHBs. These nals carry advertising for propolis, but the demand for this
new queens may be substituted for old queens or for material is quite limited.
queens of unsuitable stocks, but only after the old queen
has been found and removed from the colony. The worker Royal Jelly
bee population will be converted fully to offspring of the Royal jelly (bee milk) is fed to young honey bee larvae, and
new queen in about six weeks. it is this food that differentiates queens from workers. Only
female larvae selected to be queens are fed royal jelly vo-
luminously throughout their developmental period. Royal
POLLINATION jelly is used in some cosmetic products and food supple-
ments. In some countries it is believed that royal jelly pos-
The contribution of honey bees to agriculture far exceeds sesses medicinal properties. Collection of royal jelly is la-
the value of honey production. Whereas honey bees pro- bor intensive. In commercial production, larvae are grafted
duce an average of 200 million Ib of honey a year valued (moved into a queen cell cup) as if to produce queens. Nurse
at $150 million, the annual value of crops pollinated by bees are induced to feed the larvae liberal amounts of royal
honey bees exceeds $10 billion (14,15). jelly. Three days after grafting, the larvae are removed
from the cells and the royal jelly harvested.
Barley Malt
RAW MATERIALS OF BREWING
Malted barley is the principal ingredient of beer. It fur-
Water nishes almost all the required elements for making beer.
Malt provides starch and sugars, which will, partly or com-
Water is, only quantitatively, the major component of beer. pletely, become alcohol during fermentation; and protein
Its requirements for brewing are fairly simple. First, it and amino acids, which will supply nutrition for the yeast,
must meet local or international standards for potable wa- as well as color, foam, and flavor in the finished beer.
ter. The World Health Organization's standards for drink- Barley used to make malt is almost always selected
ing water are shown in Table 1. from special strains that have been developed and grown
The second requirement is that it not be too alkaline. A specifically for this purpose. There are two major types of
maximum alkalinity of 50 ppm (as calcium carbonate) is barley, distinguished by the number of rows on the stalk.
acceptable. Six-rowed barley is grown mainly in the midwest of the
A third requirement is that it be hard and contain cal- United States and Canada, but now also in Europe and
cium. The level of calcium considered most desirable is 100 Australia. Two-rowed barely is grown in the far west, and
ppm (as calcium), but lesser amounts may also be used. also in Europe and other barley growing regions. The two-
The water in Pilsner, Czechoslovakia, had these attributes, rowed barleys are considered by some to give a smoother
neutrality and hardness, and soon became the standard by beer. A drawing of a barley kernel is shown in Figure 5.
which all beer is made. The husk, which protects the seed and is composed of
All water supplies are either surface water or ground- the palea and lemma, is, in barley, alone among the cere-
water. Surface water is derived from rainfall or snow and als, fused to the testa and the pericarp. It is this fusion
may be quite pure. If it is collected in reservoirs near the that permits barley to be malted efficiently and to be the
source of rain or snow, it is usually soft and neutral. If it universal basis for making beer. Grains that lose their
is collected in rivers, its purity will depend on the distance husks at germination tend to become moldy when malted
between the collection and distribution points and the uses in bulk.
The malting of barley begins with steeping, in which the
barley, in tanks, is soaked in aerated water. The steeped
water is changed several times. The steeping is complete
when the barley reaches a moisture content of 45%. It is
then transferred to long, horizontal compartments,
through which moist air is blown. In 4-6 d, the barley
germinates and starts to grow as if it were to become a
barley plant. During this time the barley produces starch-
splitting enzymes, notably a-amylase and /?-amylase, and
also proteinases and cellulases. The amylases break down
some of the starch in the barley; the proteinases degrade
some of the proteins to amino acids, and the cellulases
soften the cell walls. All these enzymes are secreted by the
aleurone layer and migrate into the endosperm. These
Figure 4. Aging tanks assembled on site. Source: Courtesy of changes, which collectively are called modification, pre-
Paul Mueller Company. pare the barley for its use in brewing.
At the time when the modification is considered com-
plete, the malt is transferred to a kiln and dried. The tem-
perature at which the malt is dried determines the color
Table 1. World Health Organization Standards for and, partly, the flavor of the beer from which it will be
Drinking Water
made. Kilning stabilizes the malt and allows it to be
Maximum permissible shipped widely and to be stored for a year or more.
concentrations (mg/L) The analysis of a typical malt is shown in Table 2.
Chlorides 60
Sulfates 400 UNMALTED CEREALS (ADJUNCTS)
Calcium 200
Magnesium 150
Total dissolved solids 1,500 Cereals such as rice, corn, and sorghum are often used to
complement or attenuate the malt. These grains do not
Dorsal side
Table 2. Analysis of Barley Malt (%) both 1,4' and 1,6',the latter at the branch points. Sche-
Moisture 4.0 matic diagrams of amylose and amylopectin are shown in
Starch and dextrins 52.5 Figure 6 and 7, respectively.
Simple sugars 9.5
Total protein 13.0
Soluble protein 5.4 SPECIAL MALTS
Cellulose 6.0
Other fiber 10.0 Some malts are made with special properties, mainly dif-
Fats 2.5 fering in color and flavor. A caramel, or crystal, malt is
Minerals 2.5 made by heating a wet malt with steam under pressure.
The resulting malt is used with regular malt to produce
dark beers. A so-called chocolate malt is a variant of crystal
malt. These malts provide color and special flavor to the
contribute to flavor, color, or foam but serve only to supply beer. Malt may also be darkened by kilning at higher tem-
carbohydrates to the wort. Their use probably arose when peratures (20O0F or higher) or for longer times. Such malt
malt was in short supply. They are widely used throughout only imparts more color to the beer.
the world. Only in parts of Germany, in Switzerland, and Wheat may be malted, with difficulty, but it produces
in Greece is their use prohibited by law. This prohibition, an ordinary beer unless a yeast is used that by itself pro-
which dates to 1516 in Bavaria, as theReinheitsgebot, orig- duces a spicy flavor. This has found some favor in parts of
inally was intended as a means to police the taxation of Germany and Belgium.
beer because malt could only be made in a malthouse. The
prohibition on the use of other sources of carbohydrates
precluded the surreptitious increase in beer production. It HOPS
remains to this day as a vestigial reminder of days past
that has served to prevent the importation into those three Hops, Humulus lupulus, is a truly remarkable plant. Al-
countries of beers made with unmalted cereals. However, though it originally grew wild, and still does, it is inten-
the European Common Market has overruled this law and sively cultivated in a few countries for use only in beer.
such beers may now be imported into the all-malt coun- The major hop-growing countries are Germany, the United
tries. States, the Soviet Union, Czechoslovakia, Yugoslavia, and
The quantity of unmalted cereals may vary from 10 to the United Kingdom. Figure 8 shows hops growing in Ger-
50% of the total mash, depending on the beer to be pro- many. Hop picking by hand in Czechoslovakia is shown in
duced. Increased use gives a lighter, less bodied beer. If rice Figure 9.
or sorghum is used, it must be ground before mashing. If The use of hops in beer only goes back some 500 years.
corn is chosen, then a physically separated fraction of the Many plants had been used to flavor beer, until it was dis-
ground corn kernel that contains mainly starch and pro- covered that hops not only makes beer pleasantly flavored
tein and very little corn oil is used. but also controls the growth of spoilage bacteria. The use
Starch is the major component of both malt and the of hops is now universal in beer.
other cereals. It is a complex polysaccharide made up of Hops contain a group of compounds, humulones, which
about 35% of a straight-chain polymer of glucose known as are very insoluble in water, but which undergo a chemical
amylose and about 65% of a branched polymer, amylopec- rearrangement during the brewing process to form an
tin. The links in all of amylose are 1,4' bonds between isomeric group of compounds called isohumulones. The iso-
neighboring glucose units. The bonds in amylopectin are humulones are soluble in water and impart to beer a
Amylose Chain length
1300-2000
glucose units
Figure 6. Structure of the linear starch fraction. Each black circle represents a glucose unit, and
the aldehydic terminus of the chain is indicated by an asterisk. Interglucose bonding is a-1,4, as
shown in the inset, with carbon atoms in the glucose unit numbered in conventional fashion.
Figure 7. Structure of a small section of the branched starch fraction. Branching is effected
through an a-1,6 linkage, as shown in the inset.
palate-cleansing bitterness that provides beer with its un- In addition, hops contain a volatile oil containing many
usual property of drinkability. The isohumulones in beer odoriferous compounds, some of which survive into the fin-
can be readily analyzed, permitting a quantitative mea- ished beer. Some varieties of hops, such as Clusters and
sure of their presence and thus of the beer's bitterness. Not Galena, are used primarily for bitterness, whereas others,
many flavor compounds in other foods are so easily mea- such as Hallertau and Cascade, are used for their aroma.
sured. A diagram of humulone and its conversion product The essential oil of hops is, as in all plant materials, of
isohumulone is shown in Figure 10. The analogues of hu- terpenic origin. The major terpenes are myrcene (1), a di-
mulone (and isohumulone)cohumulone, adhumulone, terpene; humulene (2), and caryophyllene (3) sesquiter-
and prehumulonediffer only in the number of carbon penes (Fig. 11). Oxidation products of these hydrocarbons,
atoms in the side chains. such as humaladienone and caryophyllene epoxide have
Figure 8. Hops growing in Ger-
many. Source: Courtesy of S. S.
Steiner.
Figure 11. The terpenes (1) myrcene, (2) humulene, and (3)
caryophyllene.
Figure 10. Humulone and isohumulone.
been found and are probably more important to the flavor Hops is a perennial vine that grows to more than 20 ft
of beer. in one season. They are trained to high wires held by long
Also present in hop oil are alcohols, such as linalool and poles. The flowers are mechanically picked and dried in a
geraniol; ketones, such as undecanone-2; and esters, such kiln. Hops are used in several forms. The dried cones, com-
as geranyl butyrate. These survive into beer and are im- pressed into bales weighing 200 Ib, are used by many brew-
portant components of the hoppy aroma of some beers. ers. In this state, hops must be kept refrigerated. Alter-
natively, the hop cones can be milled to a powder and then Table 3. Hop varieties (In Order of Acreage Devoted to
recompressed into pellets. These are easier to use at a Each Variety)
brewery, but also need refrigeration. Lastly, the hops may United States Europe Australia
be extracted, with an organic solvent such as hexane or
alcohol, or with liquid carbon dioxide, and the extract used. Washington Perle (G) Pride of Ringwood
Hallertau Magnum (G)
These do not need refrigeration and are popular in tropical Galena
Hersbrucker (G)
countries. A cluster of Fuggle hops is shown in Figure 12. Nugget
Hallertau Tradition (G)
Some varieties of hops grown commercially are listed in Columbus
Spalter Select (G)
Table 3, with the country producing the major quantities Willamette
Hallertauer (G)
indicated. Cluster
Nugget (G)
Chinook
A typical analysis of hops is shown in Table 4. Cascade
Tettnanger (G)
Northern Brewer (UK & G)
Mt. Hood
Fuggle (UK)
YEAST Perle
Golding (UK & SU)
Tettnanger
Brewers Gold (UK & G)
Horizon
Yeast is a unicellular microscopic organism that is fairly Styrian (Y & SU)
Olympic
distinctive in being able to metabolize sugars either to car- Saaz (Cz)
Golding
Hallertau Tarus (G)
bon dioxide and water, in the presence of air; or to alcohol
Spalter (G)
and carbon dioxide, in the absence of air. It is this latter Idaho
Target (G)
trait that is used in all alcoholic fermentations. Galena Huller (G)
One genus of yeast, Saccharomyces is used in brewing. Cluster Orion (G)
But there are two species. One is S. cerevisiae, used in Chinook Record (G)
producing ales, and also for making bread, wine, and whis- Willamette Bullion (G)
key. It is a fairly hardy yeast and survives in the atmo- Nugget
sphere. Mt. Hood
The other is S. carlsbergensis (uvarum) used only for
lager beers and found no where else but in breweries. It is Oregon
Willamette
Nugget
Perle
Golding
Mt. Hood
Fuggle
Tettnanger
Note: G, Germany; Y, Yugoslavia; SU, Soviet Union; Cz, Czechoslovakia;
and UK, United Kingdom.
adding the contents of the boiling cooker. The combined In Germany, and its brewing followers, still a third
mash is allowed to rest at the temperature that results system, called decoction brewing, is common. Here too
from this mixing for a variable time, and then the tem- the mash tub cannot be heated, but a smaller decoction
perature is raised selectively until the final mashing off vessel can. The malt is transferred into the mash tub
temperature, usually 750C, is reached. at a low temperature. A small portion of this mash is
In the United Kingdom and its brewing satellites the pumped to the decoction vessel and boiled. The boiled
most common mashing system is a simple infusion mash is pumped back into the main mash vessel. This
method. In this system, the mashing process takes place serves to raise its temperature to a level that depends on
at a single temperature. This system developed with mash the relative volumes in both vessels. This transfer is re-
tubs that could not be heated. It is not nearly as versatile peated once or twice (double decoction or triple decoction),
as the double-mash system. Mashing, with or without corn leading to a series of rising temperatures in the mash
or rice, boiled separately in a small vessel, takes place at tub. This process is rather lengthy and has not found wide
about 650C. use.
of yeast and also to break down large, insoluble proteins
to simple soluble peptides for foam enhancement. Cytoly-
sis is required to reduce the viscosity of the barley gums
(soluble fiber) to accelerate the later filtration. After some
10 to 60 min, the temperature is raised by the addition of
the boiled cooker (or decoction vessel). The resulting tem-
perature may be held for 1060 min, and the temperature
raised again, finally ending at 750C. During these elevated
temperatures, two amylolytic enzymes, a-amylase and /?-
amylase, cooperate to hydrolyze most of the starch to fer-
mentable sugars. Beta-amylase, which operates best at
about 630C, attacks starch from its nonreducing end and
splits off the disaccharide, maltose. It cannot proceed past
a 1,6' linkage, and so depends on the concurrent action of
a-amylase. Alpha-amylase, which operates best at 7O0C,
splits any 1,4' linkage at random, and so provides a supply
of nonreducing ends for the /?-amylase to operate on. Co-
operatively, the action of these two enzymes can result in
the splitting of about 65-75% of the starch into mono-, di-,
and trisaccharides.
The mash temperature is raised to 75-770C when the
desired action of the amylolytic enzymes has been
achieved. This arrests any further enzymatic action and
prepares the mash for the next step, lautering.
(a) Phosphorylation
r
Dihydroxyacetone Glyceraldehyde
phosphate 3-phoshate
O
HC=O C-OPOH
Glyceraldehyde Il' I
H
3-phosphate O
1,3-Diphosphoglyeeric
acid
3-Phosphoglyceric 2-Phosphoglyceric
acid acid
perature, 0-30C. Much the same cleansing action occurs, mented beer to another tank, chilling it less, and treating
but the early transfer ensures the presence of sufficient it with a small quantity of beer that just started to ferment
yeast to cleanse the beer more efficiently. It takes 2-4 w. a day earlier. This subjects the fermented beer not just to
It has not found wide favor, probably because of the a specific quantity of yeast, but to very active yeast that
need to transfer the beer at times that could be inconven- very effectively cleanses the fermented beer. This process,
ient. called krauesening, is used by very fastidious brewers. It
A third, and most elegant way, is to transfer the fer- normally takes 3-5 w.
Alcohol
discovery that brown bottles filter the offending wave- Table 7. Analysis of American Beers
lengths of light. The aroma is caused by the action of light Standard beer All malt beer Light beer
on isohumulone, which splits off an unsaturated hydrocar-
bon, which in turn reacts with a trace of hydrogen sulfide Water 92 91 6
in the beer to give a mercaptan. Alcohol, wt% 3.8 3.9 3.3
Carbohydrates, % 3.4 3.8 <1.0
A third problem is that beer is a good medium for some Protein, % 0.3 0.6 0.2
nonpathogenic microbes and so must be sterile-filtered or Acids, as lactic, % 0.1 0.1 0.1
pasteurized. Either of these treatments effectively elimi- Ash, % 0.1 0.2 0.1
nate the problem. Isohumulones, ppm 15 25 15
Another shortcoming that has largely been eliminated
is the tendency for beer to become cloudy when it is chilled.
This haze is caused by a reversibly insoluble protein-
polyphenol complex. It is removed in one of several ways. Table 8. Vitamins in Beer
The protein may be solubilized by the enzyme papain, or
Vitamin content % Minimum daily
the polyphenols may be removed by absorption onto silica
of beer requirements
gel. These treatments are effective and widely used. Vitamin (mg/L) supplied by 1L
BLANCHING METHODS
Water Blanching
Water blanching is the most widely used method. There
are four basic designs of water blancher. Blanching time (min)
Figure 1. Typical example of relation between product output
1. The tubular blancher in which particulate vegetable and blanch time for various products blanched in various sizes of
matter is transported by pumped water through a system rotary water blancher. For a blancher diameter = 2 m, blancher
of tubes for the required residence time. Direct steam in- length is approximately a = 3.1 m, b = 4.5 m, c = 5.9 m, d = 7.4
jection is used to heat the water to blanch temperature, m, and e = 8.8 m.
Table 1. Multiply Graph Outputs by Blanching
Appropriate Factor for These Products
water Product
temperature
Product Factor Recycling
Potatoes preheating water
Temperature (0C)
whole 1.15
french fried 1.00
Carrots, whole 1.10
Beans, soaked 1.08
Peas
soaked 1.08
fresh 1.00 Recycling
Green beans cooling water
cross cut 0.70
whole 0.60 Preheating Blanching Cooling Cooling
counterflow and holding counterflow evaporative
Cauliflower, florets 0.50
Spinach, leaf 0.30 Heating zones Cool ing zones
Brussels sprouts 0.30
Cabbage, leaf 0.30 Figure 2. Representation of flow of water and temperatures in a
Cabinplant integrated blancher-cooler with heat exchanger.
Note: See Figure 1.
GENERAL REFERENCES TSEs disrupt the function of nerve cells. In TSEs there are
characteristic vacuolar degeneration of neurons in the
"Steaming into the Future," Potato Business World 6, 19-25 brain and spinal cord, giving the tissue a spongelike ap-
(1998). pearance (Fig, 1). TSEs evoke no immune response and are
S. Boyes et al., "Microwave and Water Blanching of Corn Kernels: inevitably fatal (2-5).
Control of Uniformity of Heating During Microwave Blanch- The incubation period (ie, the time between exposure
ing," Journal of Food Processing and Preservation 21, 461-484 and the onset of clinical signs) in cattle is very long, rang-
(1997).
J. I. Mate et al., "Effect of Blanching on Structural Quality of
Dried Potato Slices," J. Agric. Food Chem. 46, 676-681 (1998).
S. Meenakshi, B. Raghavan, and K. O. Abraham, "Processing of
Marjoram (Marjorana hortensis Moensch.} and Rosemary
(Rosmarinus officinalis L.). Effect of Blanching Methods on
Quality," Nahrung 40, 264-266 (1996).
G. Prestemo, C. Fuster, and M. C. Risueno, "Effects of Blanching
and Freezing on the Structure of Carrot Cells and Their Im-
plications for Food Processing," J. Sd. Food Agric. 77,223-229
(1998).
A. R. Quinero et al., "Optimization of Low Temperature Blanching
of Frozen Jalapeno Pepper (Capsicum annuum) Using Re-
sponse Surface Methodology," J. Food ScL 63, 519-522 (1998).
H. S. Raswamy and M. O. Fakhouri, "Microwave Blanching: Effect
on Peroxidase Activity, Texture and Quality of Frozen Vege-
tables," Journal of Food Science and Technology India 35,216
222 (1998).
U.S. Patents 752,431,730,717 (1998), D. R. Zittel.
JEREMY D. SELMAN
Campden Food & Drink Research Association
Campden, Gloucestershire
United Kingdom
BOVINE SPONGIFORM
Figure 1. Lesions in the gray matter of the brain of a sheep with
ENCEPHALOPATHY (BSE) scrapie: (A) typical spongiform change in neurons; (B) spongiform
change and astrocytic hypertrophy and hyperplasia. (a) Hematox-
Bovine spongiform encephalopathy (BSE, mad cow dis- ylin and eosin stain; (b), glial fibrillar acid protein (GFAP) stain.
ease), a progressive degenerative disorder of the central Magnification X 500. Source: Courtesy of Dr. Robert Higgins,
nervous system of cattle, was first recognized in the United School of Veterinary Medicine, University of California, Davis.
71. J. A. Luna, R. L. Garrote, and J. A. Bressan, "Thermo-kinetic Kingdom (UK) in November 1986 (1). Believed to be caused
Modeling of Peroxidase Inactivation during Blanching- by a newly classified proteinaceous infectious particle, a
Cooling of Corn on the Cob," Journal of Food Science 51,141-
145 (1986).
prion, BSE is one of several recognized fatal transmissible
spongiform encephalopathies (TSEs) found in various spe-
72. A. B. Newman, "The Drying of Porous Solids: Diffusion Cal-
culations," Transactions of the AlChE 27, 310 (1931).
cies. The epizootic of BSE in the UK affected more than
170,000 cattle, 70 domestic cats, and some zoo animals and
73. G. Hough, S. M. Alzamora, and J. Chirife, "Effect of Piece
Shape and Size on Leaching of Vitamin C during Water
is believed to have resulted in 40 human cases of variant
Blanching of Potato," Journal of Food Engineering 8,303-310 Creutzfeldt-Jakob disease (v-CJD, also known as new var-
(1988). iant or nv-CJD). The human cases resulted from the in-
74. P. Rice, J. D. Selman, and R. K. Abdul-Rezzak, "Nutrient Loss gestion of beef contaminated with the BSE agent.
in the Hot Water Blanching of Potatoes," International Jour-
nal of Food Science and Technology 25, 61-65 (1990). OVERVIEW
GENERAL REFERENCES TSEs disrupt the function of nerve cells. In TSEs there are
characteristic vacuolar degeneration of neurons in the
"Steaming into the Future," Potato Business World 6, 19-25 brain and spinal cord, giving the tissue a spongelike ap-
(1998). pearance (Fig, 1). TSEs evoke no immune response and are
S. Boyes et al., "Microwave and Water Blanching of Corn Kernels: inevitably fatal (2-5).
Control of Uniformity of Heating During Microwave Blanch- The incubation period (ie, the time between exposure
ing," Journal of Food Processing and Preservation 21, 461-484 and the onset of clinical signs) in cattle is very long, rang-
(1997).
J. I. Mate et al., "Effect of Blanching on Structural Quality of
Dried Potato Slices," J. Agric. Food Chem. 46, 676-681 (1998).
S. Meenakshi, B. Raghavan, and K. O. Abraham, "Processing of
Marjoram (Marjorana hortensis Moensch.} and Rosemary
(Rosmarinus officinalis L.). Effect of Blanching Methods on
Quality," Nahrung 40, 264-266 (1996).
G. Prestemo, C. Fuster, and M. C. Risueno, "Effects of Blanching
and Freezing on the Structure of Carrot Cells and Their Im-
plications for Food Processing," J. Sd. Food Agric. 77,223-229
(1998).
A. R. Quinero et al., "Optimization of Low Temperature Blanching
of Frozen Jalapeno Pepper (Capsicum annuum) Using Re-
sponse Surface Methodology," J. Food ScL 63, 519-522 (1998).
H. S. Raswamy and M. O. Fakhouri, "Microwave Blanching: Effect
on Peroxidase Activity, Texture and Quality of Frozen Vege-
tables," Journal of Food Science and Technology India 35,216
222 (1998).
U.S. Patents 752,431,730,717 (1998), D. R. Zittel.
JEREMY D. SELMAN
Campden Food & Drink Research Association
Campden, Gloucestershire
United Kingdom
BOVINE SPONGIFORM
Figure 1. Lesions in the gray matter of the brain of a sheep with
ENCEPHALOPATHY (BSE) scrapie: (A) typical spongiform change in neurons; (B) spongiform
change and astrocytic hypertrophy and hyperplasia. (a) Hematox-
Bovine spongiform encephalopathy (BSE, mad cow dis- ylin and eosin stain; (b), glial fibrillar acid protein (GFAP) stain.
ease), a progressive degenerative disorder of the central Magnification X 500. Source: Courtesy of Dr. Robert Higgins,
nervous system of cattle, was first recognized in the United School of Veterinary Medicine, University of California, Davis.
ing from two to eight years. Most animals show clinical most cattle over 30 months of age from use as human food,
signs between three and five years of age and demonstrate were enacted.
a slowly progressive disease with nonspecific neurological By-products from slaughtering cattle are used in hor-
signs, including incoordination, weakness, tremors, and ticultural applications, pet foods, cosmetics, and pharma-
anxiety. Once signs develop, animals usually die within ceuticals. Those tissues not meeting specified standards
two weeks to six months. are prohibited from use in manufacturing these products
Epidemiologically, BSE has been considered an "ex- and are now incinerated.
panded point source epizootic"; that is, it resulted from the
consumption of contaminated protein feed supplements
TRANSMISSIBLE SPONGIFORM ENCEPHALOPATHIES
(6). Meat and bone meal (MBM) produced from rendered
carcasses and offal from dead and butchered livestock has
TSEs are caused by similar, but not identical, agents and
been a common protein supplement used for decades in
produce specific and characteristic lesions in the brain of
livestock production. Changes in rendering practices in the
affected hosts. The apparent resistance/susceptibility fac-
late 1970s and early 1980s were considered a risk factor
tors in animals and humans are not yet fully understood,
in amplifying the disease through the resulting manufac-
and multiple "strains" have been identified in some TSEs,
ture of infectious MBM feed supplements (6-10).
including scrapie (2,3,13,14,17). All TSEs have long incu-
About 2000 cattle have been diagnosed with the disease
bation periods, evoke no immune response, and are inevi-
in other countries, some as the result of exportation from
tably fatal.
the UK of live cattle incubating the disease, and the ma-
TSEs in animals include cattle BSE, scrapie of sheep
jority from exportation of contaminated MBM subse-
and goats, transmissible mink encephalopathy, and
quently fed to native cattle (7-9).
chronic wasting disease of mule deer and elk (6,9,18). Con-
More than 170,000 cattle from more than 33,500 British
firmed cases in kudus, a gemsbok, an eland, a nyala, an
herds (67% of all dairy herds, 16% of all beef herds) have
oryx, an Ankole cow, cheetahs, pumas, a tiger, ocelots, and
been confirmed with the disease. The low average within-
more than 70 domestic cats are also believed to be BSE
herd incidence, with 35% of the farms experiencing only
caused by the feeding of contaminated protein supple-
one case, and 69% with four or fewer cases, is attributed
ments (19).
to uneven exposure to the agent in widely spaced batches
Human TSEs include kuru, Creutzfeldt-Jakob disease,
of feed (6).
Gerstmann-Straussler-Scheinker syndrome, and fatal fa-
In 1996 a possible link was made between BSE in cattle
milial insomnia. Human TSEs are heritable in about 15%
and 10 cases of Creutzfeldt-Jakob disease (CJD) in hu-
of the cases and are considered sporadic in about 85% of
mans (11). To date 29 humans have been confirmed with
the cases. Worldwide a few hundred cases have been as-
v-CJD (12), shown to share identical lesion patterns and
sociated with the use of tissues from infected donors (cor-
chemical characteristics with BSE (13-15). Evidence
neal transplants, cadaveric dura mater, and human pitu-
strongly supports the hypothesis that v-CJD in people and
itary extracts used to prepare growth and gonadotropin
BSE in cattle are the same disease, with transmission to
hormones), or contaminated intracranial electrodes and
people occurring through the ingestion of infected beef
neurosurgical instruments. Kuru, a TSE associated with
products (16,17).
the ritual handling and cannibalistic consumption of the
Perishable foods are especially vulnerable to acute cri-
brain of deceased tribal members in a region of New
ses in consumer confidence. Following the March 1996 an-
Guinea, with a known incubation period up to 30 years,
nouncement of the possible link between BSE and human
has all but disappeared due to changes in local customs
disease, British beef consumption fell for more than a
(2,3).
month to 25% of its preannouncement level, and the Eu-
ropean Union (EU) banned British beef imports. Global
markets, including those in countries without BSE, have BSE LINK TO HUMAN DISEASE
been impacted by this epizootic.
Beginning in July 1988 the UK responded to the cattle In 1990 the UK established the Spongiform Encephalop-
epizootic with a series of control measures. Mandatory pro- athy Advisory Committee to advise on the potential impli-
grams were enacted requiring euthanasia of affected cat- cations TSEs have on advised the government that it had
tle, prohibiting the use of affected cattle carcasses or spec- become concerned about 10 cases of Creutzfeldt-Jakob dis-
ified offal from sheep or cattle in feeds, and eventually ease with onset of symptoms in 1994 and 1995. These cases
banning MBM from all agricultural uses. A selective cull were unusual because they included patients younger than
program was instituted targeting herds that had BSE the expected (average age 27 vs 63 for sporadic CJD cases).
cases and removing nonaffected cattle that might have In addition, the neuropathology and clinical course in
been shared exposure to the agent. Current projections are these patients was distinguishable from that in other CJD
for BSE eradication between 2001 and 2005. patients. A review of medical histories, genetic analysis,
Measures to protect human health began in 1989 with and consideration of other possible causes of CJD "failed
the Specified Offal Ban (SBO), prohibiting the use of brain, to explain these cases adequately" (4,5,11).
spinal cord, tonsil, thymus, spleen, and intestinal tissues As many as 900,000 cattle might have been infected be-
of cattle origin in foods intended for human consumption. tween 1984 and 1995, with 450,000 entering the human
Additional measures, requiring meat from animals over 6 food chain prior to 1989 and 283,000 between 1989 and
months of age to be deboned prior to sale, and banning 1995 (6). Cattle are slaughtered at young ages and BSE's
long incubation period would preclude most infected ani- ence susceptibility/resistance, infectious dose, virulence,
mals from showing any clinical signs. Cattle in the earlier disease pattern, and incubation period (13,14,17).
stages of incubation are expected to have had much lower
accumulations of infectious agent in their brain and spinal Transmission
cord.
There have been no confirmed cases of v-CJD in people Variant CJD is believed to have been transmitted by con-
with occupations expected to have the highest risk of ex- suming infected beef products such as sausages, franks,
posure, including farmers, abattoir workers, butchers, and and hamburgers that contained portions of brain, spinal
veterinarians. The number of new cases of all types of CJD cord, dorsal root ganglia, retina, intestines, or bone mar-
in the UK remains stable, at about one new case per mil- row as components. A list of Specified Risk Materials
lion people per year. This rate is about the same in all (SRM) has been adopted by the European Union (EU) Sci-
countries, including Australia and New Zealand, where entific Steering Committee as a result of calf assay exper-
neither scrapie nor BSE have been identified. Currently 29 iments using various tissues from known infected animals
people, one in France and the remainder in the UK, are (Table 1; 22).
believed to have v-CJD (13). The proposed link between Prions are extremely resistant to heat, ultraviolet light,
BSE and v-CJD was eventually substantiated (13,14). ionizing radiation, and common disinfectants that nor-
There are no predictions of the number of human victims mally inactivate viruses and bacteria, and destroy nucleic
that might eventually result. acid (2,3,23-25). Contaminated surgical instruments have
been shown to retain infectivity following standard hospi-
tal sterilization techniques. Transplanted tissues from hu-
THE CAUSATIVE AGENT mans with CJD, including dura mater grafts, extracts from
pituitary glands, and corneas, have been demonstrated ve-
Prions and the "Protein Only" Hypothesis hicles of transmission. Strategies to protect the blood sup-
Prions, the name coined by Stanley Prusiner for protein- ply, including provisions to deplete blood products of leu-
aceous infectious particles, have changed our understand- kocytes because these white blood cells may play a role in
ing of infectious agents. All previously recognized patho- the transport of ingested abnormal prions to the nervous
genic agents use nucleic acid, either DNA or RNA, to system, are currently under consideration in the UK (26).
reproduce. Prions are abnormal structural variants of nor- Kuru was transmitted by ingestion and through open
mal cellular proteins found in the membranes of neurons cuts or abrasions. Scrapie in sheep has been transmitted
and other tissues (2,3). through open wounds and new infections have been asso-
Although scientific opinion generally supports Prusi- ciated with lambing of normal animals with infected ani-
ner's 1982 hypothesis that TSEs are caused by abnormal mals. Although the majority of cattle infections resulted
prion proteins, other research groups continue looking for from ingestion of contaminated protein feed supplements,
an unrecognized organism with nucleic acid (3), and one studies on potential maternal transmission report a small
group continues to promote Spiroplasma sp. as a potential risk of infection for calves born shortly before or after the
causative agent (20). onset of clinical signs of the disease in infected dams. Ex-
Prions are single molecules of about 250 amino acids perts indicate this rate is insufficient to perpetuate the ep-
and contain no nucleic acid. Abnormal prion protein is izootic in cattle but will delay the eradication effort (6,27).
formed within the host by genetic mutation (eg, familial
CJD), or by unknown means (eg, sporadic CJD), or enters
the body via oral or other routes (eg, BSE, kuru, scrapie,
Table 1. Levels of TSE Infectivity Associated with
etc), and proceeds to convert by contact normal protein into Various Ruminant Tissues
structurally aberrant forms. The conversion of normal cel-
lular prion protein to the distorted prion conformation is Category Organs
characterized by a structural change from predominantly High Bovine brain, eyes, spinal cord and dorsal root
alpha helices to beta sheets (alpha helixtbeta sheet 42:3 in infectivity ganglia; dura mater, pituitary, skull and bovine
normal prion protein, 30:43 in abnormal) (3,21). The dis- vertebral column, lungs
torted form has increased resistance to natural proteases ovine/caprine brain, eyes, and spinal cord, dorsal
and, as a result, accumulates in tissues, contributing to root ganglia and vertebral columns; ovine and
neuronal death and spongiform changes in the brain. Am- caprine spleens, lungs
Medium Total intestine from duodenum to rectum, tonsils
yloid plaques are formed from remnants of prion protein Bovine and caprine spleen, placenta, uterus,
infectivity
in some, but not all, forms of TSE disease. fetal tissue, adrenal, cerebrospinal fluid, lymph
TSEs such as scrapie have been shown to exist as dif- nodes
ferent "strains," evidenced by different incubation periods, Low Liver, pancreas, thymus, bone marrow, other
lesion patterns, and chemical characteristics. Historically, infectivity bones, nasal mucosa, peripheral nerves
strain differences in pathogenic organisms have always No detected Skeletal muscle, heart, kidney, colostrum, milk,
been associated with genetic differences represented by infectivity discrete adipose tissues, salivary gland, saliva,
varying nucleic acid sequences (3). Strain differences in thyroid, mammary gland, ovary, testis, seminal
prion diseases appear to be from conformational differ- testes, cartilaginous tissue, skin, hair, blood
ences of the same protein molecule. Functional behavior of clot, serum, urine, bile, feces
the molecule is linked to the conformation and may influ- Source: Ref. 22.
The persistence of chronic wasting disease of mule deer
and elk raises questions about possible methods of lateral
transmission between unrelated animals. There is a small
Number of cases
risk of transmission to uninfected lambs if they are born
in the immediate physical vicinity of infected ewes also
giving birth.
Susceptibility
The amino acid sequence in the prion protein of cattle dif-
fers from that of sheep at 7 positions, and that of humans
at 30 positions. It is thought that greater differences pro-
vide a more formidable "species barrier" to transmission.
Scrapie strains have not been shown to transmit to cattle;
however, BSE has been experimentally transmitted to Year
sheep and several other species. Prions from cattle and
humans, but not sheep, share specific amino acid se- Figure 2. Confirmed cases of BSE in UK cattle by year.
quences in two areas of the protein, possibly accounting for
the transmission in spite of the amino acid sequence dif-
ferences (2,3,21,28).
All cases of v-CJD have been recorded in people homo- Epidemiological studies suggest that UK cattle became
zygous for methionine at prion protein codon 129. This ge- infected through exposure to contaminated MBM feed sup-
notype is found in 38% of the UK population. Genotypes plements in 1981 to 1982 (6). Although the original source
that are heterozygous for methionine/valine (UK fre- of the contamination is unknown, the most accepted theory
quency 51%), or homozygous valine (UK frequency 11%), proposes that sheep scrapie prions completed a species
may have different incubation periods or increased resis- jump and induced normal cattle prion protein to become
tance to infection (15,29). distorted (6-9). This distorted cattle prion protein distorts
BSE has a characteristic pattern of lesions in all species others, eventually resulting in clinical disease. Affected
examined when changes are mapped by region of the brain. animals were slaughtered or died, rendered, and the re-
Also, protein digestion patterns of BSE prion are identical sulting MBM containing abnormal cattle prion protein was
between species and differ from other TSEs. Other TSEs, fed to other cattle. The UK sheep population has a high
however, demonstrate "strain" differences using these enzootic rate of scrapie, and a high ratio of sheep to cattle
tests and in clinical progression of the disease. Strain dif- (45 million to 12 million). This resulted in sheep repre-
ferences are believed to represent differing molecular con- senting 14% of rendered products, compared with 0.6% in
formations of identical proteins (13,14). the United States. The higher level of MBM supplements
fed to young calves in the UK (2-4% MBM in rations) may
Prevention and Treatment explain the high incidence of BSE as compared with other
EU countries (30).
Both normal and distorted prion proteins fail to stimulate A second theory suggests that cattle have always had a
any detectable host immune response, and no inflamma- low incidence of BSE, perhaps at a rate similar to the
tory reaction is associated with accumulations of abnormal l:l,000,000/year incidence of CJD found in humans, which
prion protein in neurons. The agent presents special chal- was unrecognized (31). Changes in rendering practices in
lenges to those attempting to develop effective drugs for the late 1970s and early 1980s no longer destroyed infec-
treatment and vaccines for prevention. tivity sufficiently to prevent accumulation of the necessary
A reliable antemortem test is an area of special need, infectious dose.
and a number of promising methods are under evaluation. A third hypothesis, offered in an effort to explain the
The long incubation period contributes to the difficulty of rapid appearance and spread of the epizootic, theorizes im-
validating the various tests being developed. Ultimately portation of the agent to the UK in MBM containing ab-
the determination of the risk from medical products incor- normal proteins from an unknown ruminant other than
porating organs, cells, sera, and bovine by-products, and cattle (32). The original source would have to be a country
that from various food products, depends on sensitive and or countries lacking the infrastructure necessary to iden-
specific antemortem testing methods. tify clinical cases and with rendering systems inadequate
to destroy the agent. The imported material would need to
THE BSE EPIZOOTIC be in sufficient quantity, or commingled with domestic
MBM, to result in the volumes of contaminated product
First recognized in November of 1986, with retrospective with infectious dose levels necessary to account for the
histological evidence of the first case dating from Novem- epizootic.
ber 1985, the BSE epizootic peaked in 1992 with more than Whatever the original source, changes in British ren-
1000 cattle cases confirmed per week (see Fig. 2). Reviews dering methods in the late 1970s and early 1980s are pro-
of archived tissue samples from cattle with undiagnosed posed to have played a role in the widespread amplification
disease have failed to identify any unrecognized cases prior of the disease (6-8). The solvent extraction step with steam
to 1985 (1,6). recovery was eliminated, and a liquid slurry process was
introduced (33). Both changes may have resulted in de- In 1997, the selective cull program was initiated, re-
creased exposure of materials to heat during rendering. quiring all cattle born on farms six months before and after
Critics note that TSEs such as scrapie have been demon- a confirmed case of BSE to be removed from the herd, eu-
strated to be resistant to solvents, and the temperatures thanized, and handled as if they are infected. No replace-
used (about 10O0C) are too low to inactivate the agent ments are allowed onto the farm until all such animals
(23,24,32). The impacts from these changes in the render- have been removed. Additional restrictions required all
ing system on the epizootic are unknown. The use of MBM meat from cattle more than 6 months of age to be deboned
in cattle rations as a source of supplemental protein had as a precaution to prevent any nervous tissue or bone mar-
been a common practice for decades prior to the emergence row from being consumed.
of BSE, and scrapie is known to have been endemic in the By-products from slaughtering cattle approved for use
UK for more than 250 years. as human food are considered "clean" and approved for use
BSE has been confirmed in native cattle in Ireland, in horticultural applications, pet food, cosmetics, and phar-
France, Portugal, the Netherlands, and Switzerland. Ex- maceuticals, or they can be buried in landfills. All other by-
ported British cattle have been found with the disease in products are considered "dirty" and are stained to prevent
Oman, the Falkland Islands, Germany, Denmark, Canada, accidental use, incinerated at 100O0C for sufficient time to
and Italy (1). The export of rendered animal feed products result in a protein-free ash, and then disposed of in land-
from the UK is considered the source of the disease out- fills. No rendered ruminant products can be used for ag-
breaks in native cattle in other countries. There are con- ricultural purposes.
cerns that the number of cattle, and the amount of feed, The number of new cases of BSE has fallen from its
exported should have resulted in significantly more dis- peak in 1992 of 900 to 1000 confirmed diagnoses per week,
ease than reported (30). There is confusion about whether to less than 200 per week in 1998. The UK expects to erad-
the expected cases failed to occur for unknown reasons, icate the disease between the years 2001 and 2005 (1,9,27).
went unrecognized within the surveillance systems in
place, or were unreported. In the European Union
On March 27,1996, the EU imposed a ban on exports from
ACTIVITIES TO PROTECT THE FOOD SUPPLY the UK of beef, live bovine animals, semen, embryos, and
bovine products (including MBM) that might enter the hu-
In the UK man or animal food chains or be used in Pharmaceuticals
or cosmetics. In December of 1996, the UK published the
In July 1988, with about 2000 cattle cases confirmed, and
Export Certified Herds Scheme (ECHS) to enable docu-
in response to a just completed epidemiological investiga-
mentation that an animal was from a BSE-free herd. In
tion implicating MBM (6), the UK made BSE a notifiable
March of 1998, EU farm ministers approved the ECHS,
disease. Euthanasia of affected cattle became mandatory,
permitting legal exports of beef from Northern Ireland
and their carcasses were banned from use in feed supple-
from June 1, 1998. The European Commission then pro-
ments. A few months later the carcass ban was expanded
posed to lift the export ban for the rest of the UK, as ap-
to include offal from sheep and cattle, although strict en-
plied to animals born after August 1, 1996 (the date the
forcement was not achieved. In 1989 the Specified Bovine
MBM ban became fully effective).
Offal (SBO) ban prohibited the use of brain, spinal cord,
tonsil, thymus, spleen, and intestinal tissues of cattle ori-
In the United States
gin in foods intended for human consumption and fertilizer
manufacturing. The United States has not imported processed beef, live
Beginning in 1991 controls on MBM went through a cattle, semen, embryos, MBM, or other beef products from
number of iterations, starting with prohibitions from use the UK since 1989. In 1990 the U.S. Department of Agri-
in ruminant feeds, and eventually resulting in a ban from culture (USDA) began tracing the 496 UK cattle imported
all agricultural use. In August 1996 mammalian MBM was to the United States between 1981 and 1989 and found no
made illegal to possess or use in any part of the food chain traces of BSE among those they were able to locate. A sur-
including on-farm, in transit, or at feed mills. A surveil- veillance program was begun that has examined thou-
lance system was imposed including statistical sampling sands of brain tissue samples from slaughtered animals
of protein supplements for the presence of ruminant and across 43 states without finding any evidence of BSE.
porcine proteins, and sheep and goat heads, spinal cords, In 1991 the USDA began enforcing stringent restric-
and spleens were banned from rendered use. tions on importations from other countries either known
Special programs for calf processing were initiated to to have had cases of BSE or considered to have inadequate
prevent male calves less than 20 days old from being used surveillance systems to detect the disease. The rendering
for human food. Data showing that cattle did not harbor of sheep for use in animal feed was discouraged, and risk
significant amounts of abnormal prion protein until later analysis activities were pursued. In 1993 the slaughter
in life led to the "Over Thirty Month scheme" (OTM, surveillance program was expanded to include "downer"
OTMS), which prohibited the slaughter of cattle over 30 cattle in response to reports suggesting disabled cattle,
months of age for human food. Beef cattle from BSE-free those that are unable to stand without assistance, repre-
herds, and reared on grass, are considered at very low risk sent unrecognized cases of BSE. Downer cattle cannot
of the disease and can be exempted and slaughtered for stand for many different reasons including metabolic dis-
human consumption up to 42 months of age. eases, injured musculoskeletal systems, or systemic illness
resulting in general weakness. BSE-affected cattle may be Species jump. A TSE of one species inducing disease
downers, but downers are not necessarily related to BSE. in another species.
On March 29, 1996, livestock and professional animal SRM. Specified risk material.
health organizations in the United States requested an SEAC. Spongiform Encephalopathy Advisory Commit-
American ban on the use of ruminant protein in ruminant tee.
feeds. In addition, these groups requested increased na-
tional surveillance, enhanced BSE educational activities, Transmissable mink encephalopathy. A TSE of
and expanded cooperative research efforts to provide extra mink.
measures to prevent the introduction of BSE into the TSE. Transmissible spongiform encephalopathy.
United States. Replacing animal origin proteins for feeds
in the United States will require about 3 million additional
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1995, pp. 205-223. Grape Nuts and Post Toasties.
25. D. Harlan, "Risk ReductionAn Ounce of Prevention," Inter- From humble beginnings, breakfast cereals became a
national Symposium on Spongiform Encephalopathies: Gen- large industry in the United States. In 1987 it was a $5.3
erating Rational Policy in the Face of Public Fears, The Ceres billion business, with 90% coming from the RTE segment
Forum, Georgetown University, December 12-13, 1996. and 10% from the hot cereal category. The per capita con-
26. World Health Organization, Report of an International Con- sumption of breakfast cereals in 1987 was 11.7 Ib for RTE
sultation of Experts Convened in Geneva from 24 to 26 March and 3.6 Ib for hot cereals (3).
1997 on the Issue of Human and Animal Spongiform Enceph-
alopathies and Medical Products, World Health Organization,
Geneva, Switzerland, 1997. READY-TO-EAT BREAKFAST CEREALS
27. D. J. Stekel et al., "Prediction of Future BSE Spread," Nature
381,119 (1996). Ready-to-eat breakfast cereals can be described by group-
28. D. C. Krakauer et al., "Phylogenesis of Prion Protein,"Nature ing them into a few basic cereal types: puffed, flaked,
380, 675 (1996). shredded, baked, and agglomerated.
29. R. C. Moore et al., "Mice With Gene Targeted Prion Protein
Alterations Show That Prnp, Sine and Prni Are Congruent," Puffed Cereals
Nature Genet 18, 118-125 (1998).
30. D. Butler, "Creutzfeldt-Jakob Researchers Seek Greater Ac- Puffed cereals are whole grains, grain parts, or a grain
cess to Data on Cases," Nature 381, 453 (1996). dough that has been formed into a specific shape and then
31. C. J. Gibbs, "Is BSE Endemic?" International Symposium on expanded by subjecting it to heat and pressure to produce
Spongiform Encephalopathies: Generating Rational Policy in a very light and airy grain product. The two types of pro-
the Face of Public Fears, The Ceres Forum, Georgetown Uni- cess that are normally used for puffed cereals are gun puff-
versity, December 12-13, 1996. ing and extrusion.
32. O. Hotz de Baar, "BSE: A Hypothetical Genesis," PROMED
communication, 12 December 1996. Gun Puffing. Gun puffing consists of a chamber (gun)
33. "Origins of BSE [comment]," Vet. Rec. 128, 310 (1991). that is charged with a quantity of grain material. The
chamber is subjected to high-pressure steam (100-250
psig) for 5-45 s. The pressure is then released very rapidly
DONALD KLINGBORG
giving a sound reminiscent of a gun. The shot of grain is
DEAN OLIVER
University of California propelled into an expansion vessel. The change from the
Davis, California high-pressure steam to atmospheric conditions causes the
grain piece to expand to about 3-10 times its original vol-
ume. The puff is then dried to a final moisture content of
BREAKFAST CEREALS 1-3% (4,5).
Breakfast cereals may be classified as hot cereals, requir- Extrusion. Extrusion employs either a single- or twin-
ing some preparation such as the addition of hot water, or screw extruder. A single flour or a mixture of grain flours
ready-to-eat (RTE) cereals, usually consumed with cold is fed into the extruder. These flours may have been pre-
milk. RTE cereals are so-called because they are pre- conditioned with water or steam before extrusion. Other
cooked using one of a number of processes. Corn, wheat, ingredients may be added to the extruder such as water or
rice, oats, or other grains may be puffed, flaked, shredded, sugar syrups. The design of the screw, barrel elements, and
or extruded; coated with sugars; enriched with micronu- die of the extruder impart desired characteristics to the
trients; or enhanced with fruits to provide a convenient, finished product. Heating or cooling is accomplished
nutritious, and readily digestible breakfast food. through mechanical energy from the screw (6) and through
The history of breakfast cereals parallels the growth of jacketing the extruder barrel. Pressures in the extruder
the Kellogg Company and the Postum Cereal Company, range from 500 to 2500 psig and temperatures range from
250 to 40O0F. As the material exists from the end of the Baked Cereals
extruder it expands to release steam from the product. The
Baked cereals are the nugget type or rotary mold type.
produce is then dried to 1-4% moisture.
They are normally made in a typical bakery process. The
Puffed cereals are often coated with a sugar solution
nugget type involves blending grain flours, yeast, salt, and
that may be flavored and dried to give a presweetened ce-
water together in a dough mixer, allowing the dough to
real. This coating is normally done in a rotating drum or
proof, forming the dough into loaves or sheets, baking in
screw auger where the puffed cereal is fed at a controlled
an oven, then breaking the baked grain material into
rate. Sugar syrup is sprayed onto the cereal in the desired
chunks, and drying to a final moisture of approximately
amount. The coated cereal is dried to remove excess mois-
2%. The chunks are ground into finished food size (8). The
ture.
rotary mold type utilizes a cookie baking line where the
ingredientsgrain, water, sugar, and shorteningare
Flaked Cereals
made into a dough. Pieces are formed by a cookie mold with
Flaked cereals are cooked whole grains, parts of grains, or a shape and size appropriate for RTE cereal. These are
flours that have been pelletized or agglomerated, flattened baked and dried in a typical baking oven.
into a flake, and dried or toasted. A normal process in-
volves blending the grain with a flavoring syrup that may Agglomerated Cereals
contain sugar, water, malt, or salt as well as other ingre-
Agglomerated cereals are blends of grain products such as
dients or combinations thereof. The blend is cooked in a
rolled oats, crisp rice, and toasted rolled wheat that have
steam atmosphere in a batch or continuous cooker. Cook-
been glued together using a sugar or maltodextrin syrup
ing conditions involve moistures between 25 and 40%, time
as a binding agent. Vegetable oil is added to prevent sugar
between 30 min and 3 h, and steam pressures of 15-40
absorption into the agglomerated piece and to improve
psig. The cooked material is dried (pelletized and sized if
crispness retention in milk. The process involves blending
required) to the desired flaking moisture, normally be-
the ingredients together in a ribbon blender or continu-
tween 12 and 22% moisture. The material is tempered for
ously in a mixer auger. The product is spread onto the belt
1-24 h to equilibrate moisture throughout the grain piece.
of a traveling screen dryer (4) and moisture is reduced to
After tempering, the pieces are fed through flaking rolls to
approximately 2-3%. The sheets of agglomerated grain are
get the desired flake thickness, normally between 0.010
sized off the dryer through the use of a grinder and then
and 0.035 in. After flaking, the wet flakes go to toasting
readied for packaging. Ingredient addition and sequencing
ovens where the product moistured is quickly brought
are important to insure good agglomeration of the product
down to 2-3%. At times, grain flakes (especially rice) are
without causing sugar lumps or bricking of the product in
oven puffed. This requires that the wet flakes be subjected
the package.
to a very high temperature (up to 60O0F) for a short period
of time, often 1 min or less (7). This is done effectively in
a fluidized bed dryer. HOT BREAKFAST CEREALS
Percent of calories
Hot wheat breakfast cereal is made with farina, which is
a fraction of middlings from hard wheat. Soft wheat is not
suitable because it produces a product that loses particle
integrity too rapidly during cooking. Particle size is critical
for quality. United States standards require that 100% of
the product pass through a 20-mesh sieve and not more
than 10% pass through a 45-mesh sieve. Farina must be
cooked in boiling water for several minutes to insure com-
plete starch gelatinization.
Instant farina cooks in about 1 min with boiling water.
Proteolytic enzymes are used to instantize farina by open- Protein Carbohydrate Fat
ing avenues for easier penetration of water into particles
to facilitate hydration during cooking (6). Figure 1. Percent calories in a cereal breakfast versus a bacon
and egg breakfast.
Corn
In the southern portion of the United States a breakfast Fortification
cereal made from corn called grits or hominy grits is pop-
ular. Grits are produced by dry milling white corn and are Cereal fortification has been practiced in the industry for
essentially small pieces of endosperm (6). decades and most RTE cereals today are fortified with vi-
tamins and minerals. In 1974 the Food and Drug Admin-
istration (FDA) proposed guidelines on cereal fortification
NUTRITIONAL CONSIDERATIONS that were later incorporated into a general fortification
regulation (14). This regulation, along with other guide-
lines (15), serves as the cornerstone for cereal fortification.
Breakfast Cereals and Dietary Recommendations
Cereal manufacturers today use the following guidelines
Dietary recommendations from the government and major for specific nutrient fortification.
health organizations suggest that the intake of dietary fat
and cholesterol should decrease and the caloric intake from
complex carbohydrates should increase (10). One way this 1. The intake of the nutrient is below the desirable
can be accomplished is to increase the amount of cereals level in the diets of a significant number of people.
and grains in the diet. A RTE breakfast cereal is right in 2. The food used to supply the nutrient is likely to be
line with these dietary recommendations. consumed in quantities that will make a significant
A recent General Foods study showed that adults who contribution to the diet of the population in need.
consumed breakfast, especially one that incorporated RTE 3. The addition of the nutrient is not likely to create an
cereal, had a better overall diet quality than those who imbalance of essential nutrients.
skipped breakfast. In addition, RTE cereal users usually
have lower daily intake of fat and cholesterol (11). 4. The nutrient added is stable under conditions of stor-
Another survey showed that 95% of the survey popu- age.
lation consumes some kind of food item in the morning. 5. The nutrient is physiologically available from the
Eighty-nine percent of these people eat breakfast. RTE ce- food.
reals were the second most frequently consumed meal, be- 6. There is reasonable assurance against excessive in-
hind a food group that included rolls, muffins, and toast take to a level of toxicity.
(12). A third survey showed that 88% of the survey popu-
lation consumed breakfast, and approximately 32% con-
sumed cereal, primarily RTE cereal (13). Other factors considered when fortifying include the esti-
Breakfast cereals are, therefore, an excellent vehicle for mated frequency of consumption of the food, the target con-
delivery of calories from complex carbohydrates and, at the sumer group, current health issues, and the dietary role of
same time, reduce fat calories. Figure 1 shows the distri- the product.
bution of calories in a complete cereal breakfast (1 oz ce- Breakfast cereals therefore make a significant contri-
real, 12 fl oz lowfat milk, two slices toast with spread, and bution to the overall diet quality of an individual through
6 fl oz orange juice) compared with a bacon and egg break- their ingredient and fortification profiles. They provide a
fast (one egg, two slices bacon, one slice toast with spread, logical way to translate dietary recommendations to in-
6 fl oz orange juice, and 8 fl oz lowfat milk). The cereal crease carbohydrate intake and decrease fat consumption;
breakfast is lower in fat and higher in carbohydrates than at the same time they provide a means for enhancement
the bacon and egg breakfast. of vitamins and minerals in the diet.
STABILITY OF BREAKFAST CEREALS Nutrient Stability
Breakfast cereals are usually fortified with vitamins and
Breakfast cereals should remain stable for up to one year minerals up to 25% of the U.S. recommended daily allow-
when stored under reasonably cool and dry conditions. ance or higher. These micronutrients, especially vitamins
RTE cereals should remain crisp without developing off- A, D, and C, are not stable during cereal processing. Hence,
flavors in storage. They should stay crisp in milk for at micronutrient fortification is done after processing, just be-
least 3-5 min. fore packaging (8,22). Properly maintained temperature
and humidity will protect micronutrients during storage.
Texture Stability
BREAKFAST CEREAL PACKAGING
Loss of crispness (staling) in RTE cereals is associated with
moisture pickup. Fresh RTE cereals have a moisture con- The forerunner of today's RTE cereal packaging was intro-
tent of 2-3% and are very crisp. A good indicator of sensory duced about 1900 by Nabisco in packaging the Uneeda Bis-
crispness is water activity (A11,), which is the ratio of the cuit. For the consumer, a folding carton with an internal
vapor pressure of water over the food material to the vapor liner became a convenient alternative to cracker-barrel-
pressure of pure water, both measured at the same tem- type bulk packaging. Although today's packaging resem-
perature. Fresh cereals generally have an Aw of about 0.20. bles that of the early 190Os, technological changes have
As the moisture content goes up, the Aw increases until it occurred in packaging materials and equipment as a result
reaches a critical value; for most cereals, this is around of more demanding product specifications, consumer
0.45 (16). Beyond the critical A^, the cereal becomes stele needs, distribution, merchandising, and regulatory and
and unacceptable. production requirements.
In the case of fruited cereals such as raisin bran, the The major functions of the RTE cereal package are con-
raisin, which contains up to 18% moisture, will transfer its tainment, preservation, identification, and integrity. Most
moisture during storage to the cereal, which has about 2- RTE cereal packaging systems comprise three compo-
3% moisture. As long as the critical Aw of the cereal is not nents: primary (liner), secondary (folding carton), and ter-
exceeded, the cereal will remain crisp. But the raisin could tiary (corrugated shipping container).
become unacceptably hard.
Some remedies to keep fruit soft while retaining cereal Primary Package
crispness include controlled addition of moisture to the ce-
The cereal liner's principal function is preservation. The
real to modulate moisture migration from the fruit. In
liner evolved over time from an uncoated, bleached sulfate
some cases this could make the cereal lose crispness. In-
paper to a more protective waxed glassine paper. Plastic
fusion of fruits with edible humectants such as glycerol will films were introduced in the mid-1970s. These coextruded
keep the fruits soft while preventing the cereal from be-
films provide superior product protection via improved
coming stale (16,17). Coating RTE cereals with hydropho-
moisture and grease barriers and seal integrity. In 1985
bic ingredients such as fats and oils, or incorporation of
films were made with bidirectional barrier properties to
ingredients like magnesium stearate in the formulation,
retain product aroma while preventing external contami-
can significantly improve the bowl life of the cereal (18,19).
nation (23). Cereal liners can be modified to preserve other
product attributes. Phenolic antioxidants can be incorpo-
Flavor Stability rated into both waxed paper liners and plastic film coex-
trusions to minimize oxidative rancidity, which may im-
Breakfast cereals can develop off-flavors during storage. part off-flavors to the product (21). Titanium dioxide is
Unsaturated fatty acids and other compounds containing generally added to plastic films to provide varying degrees
unsaturated linkages, such as vitamins, may undergo of opacity where transparency is not desired.
autooxidation, resulting in oxidative rancidity. Other re-
actions that can cause off-flavors are fat hydrolysis and Secondary Package
reversion (8,20). Susceptibility to oxidation depends on the
type of cereal grain used. Breakfast cereals made from oats The principal functions of the folding carton are liner con-
are more susceptible to oxidative rancidity because oats tainment and communication (graphics). Most cereal car-
contain higher levels of oil, about 7%. Other breakfast ce- tons are produced from a machine clay-coated newboard
reals, such as those made from rice, wheat, and corn, con- comprising multiple layers of recycled paper fiber and are
tain much less oil and thus are more stable in storage. printed by either offset lithography or rotogravure. A sec-
Antioxidants are used to retard autooxidation in break- ond method prints clay-coated sulfite paper before lami-
fast cereals. Butylated hydroxyanisole (BHA) and butyl- nation to an uncoated, special-bending newsboard using
ated hydroxytoluene (BHT) are the most common phenolic adhesives or waxes. Other less-economical, higher quality
antioxidants used. Federal regulations allow BHT and constructions using virgin fiberboard include coated, solid,
BHA to be added directly to breakfast cereals up to 50 ppm. bleached sulfate and coated, solid, unbleached sulfate.
The more common practice is to add antioxidants in the
wax liner of the cereal box. These phenolic antioxidants, Tertiary Package
volatile at room temperature, diffuse from the liner to the Maintenance of the integrity of the retail package through
product, thus providing protection from oxidation (21). the distribution cycle is the main function of the corru-
gated shipping case. Shipping cases are generally regular Foods," Journal of the American Medical Association 205,160
slotted containers able to withstand a burst test ranging (1968).
from 150-275 Ib. Top-to-bottom compression strength of 16. U.S. Pat. 4,256,772 (Mar. 17, 1981), A. Shanbhag and A.
the case is important to prevent crushing during handling Szczesniak (to General Foods Corp.).
and storage. Minimum standards for corrugated contain- 17. U.S. Pat. 4,103,035 (July 25, 1978), C. Fulger and T. Morfee
ers have been established for rail and truck shipments and (to Kellogg Co.).
are covered under specific uniform classification codes 18. U.S. Pat. 3,484,250 (Dec. 16, 1969), W. Vollink and M. Steeg
(24-26). (to General Foods Corp.).
19. U.S. Pat. 4,588,596 (May 13, 1986), D. Bone and co-workers
Cereal Packaging Line (to the Quaker Oats Co.).
20. R. B. Coulter, "Extending Shelf Life by Using Traditional Phe-
The bag-in-the-box (BNB) packaging system is replacing nolic Antioxidants," Cereal Foods World 33, 207-210 (1988).
the double package liner packing lines. BNB packaging 21. R. Sims and J. Fioriti, "Antioxidants as Stabilizers for Fats,
uses vertical form-fill-seal baggers coupled with horizon- Oils, and Lipid Containing Foods," in T. E. Furia, ed., CRC
tal cartoners. Product is deposited in the bag (liner) during Handbook of Food Additives, Vol. 11, 2nd ed., CRC Press, Inc.,
bag formation and is sealed prior to carton insertion. In Boca Raton, Fl., 1980, pp. 13-56.
contrast, traditional packing lines form a liner and carton 22. R. H. Anderson and co-workers, "Effects of Processing and
around a mandrel prior to product fill. BNB equipment is Storage on Micronutrients in Breakfast Cereals," Food Tech-
more efficient and flexible, operates with wider liner ma- nology 30, 110-114 (1976).
terial selection, and produces a higher quality cereal liner. 23. W. Drennan, "Barrier Resins Key New Package Develop-
ment," Plastics Packaging, 17-21 (July-Aug. 1988).
24. Uniform Freight Classification, Uniform Freight Classifica-
BIBLIOGRAPHY tion Committee, Chicago, 111., annual.
25. National Motor Freight Classification, American Trucking As-
1. G. Carson, The Cornflake Crusade, Rinehart & Co., New York, sociations, Washington, D.C., annual.
1957, pp. 147-175.
26. Coordinated Freight Classification, The New England Motor
2. J. Berry, Inside Battle Creek, rev. ed., Battle Creek Public Rate Bureau, Inc., Burlington, Mass., annual.
Schools, Brochure No. 6, Battle Creek, Michigan, 1989.
3. The Staff, "State of the Food Industry, Breakfast Cereals,"
Food Engineering 60, 86 (1988). GENERAL REFERENCES
4. R. Fast, "Breakfast Cereals: Processed Grains for Human
Consumption," Cereal Foode World 32, 241-244 (1987). A. Brody and K. Marsh, The Wiley Encyclopedia of Packaging
5. R. Daniels, Breakfast Cereal Technology, Noyes Data Corp., Technology, 2nd ed., John Wiley & Sons, Inc., New York, 1997.
Park Ridge, N.J., 1974. S. A. Matz, The Chemistry and Technology of Cereals as Food &
6. R. Hosney, Principles of Cereal Science and Technology, Amer- Feed, AVI Publishing Co., Westport, Conn., 1959.
ican Association of Cereal Chemists, St. Paul, Minn., 1986, S. A. Matz, Cereal Technology, AVI Publishing Co., Westport,
pp. 293-304. Conn., 1970.
7. D. Tressler and W. Sultan, Food Products Formulary, Vol. 2,
AVI Publishing Co., Westport, Conn., 1975. DICK FIZZELL
8. N. Kent, Technology of Cereals, Pergamon Press, Elmsford, G. COCCODRILLI
NY, 1983, pp. 144-153. CHARLES J. CANTE
9. F. H. Webster, "Oat Utilization: Past, Present, and Future," General Foods USA
in F. H. Webster, ed., Oats: Chemistry and Technology, Amer- White Plains, New York
ican Association of Cereal Chemists, Inc., St. Paul, Minn.,
1986, pp. 413-426.
10. Committee on Diet and Health, Diet & Health: Implications
for Reducing Chronic Disease Risk, National Academy Press,
BROWNING REACTION, ENZYMATIC
Washington, D.C., 1989.
11. K. Morgan, M. Zabik, and G. Stampley, "The Role of Breakfast The change in color following mechanical or physiological
in Diet Adequacy of the U.S. Adult Population," Journal of the injury of fruits and vegetables is due to oxidative reactions
American College of Nutrition 5, 551-563 (1986). of phenolic compounds by polyphenol oxidase (PPO) and
12. J. Markle, F. Vellucci, and G. Coccodrilli, Food Selection Pat- the reaction products, o-quinones, to various polymerized
terns of Individuals Who Consume a Food Item in the Morn- products. In food processing, such color change is common-
ing, Internal Research Report, General Foods USA, White place during preparation for canning, dehydration, freez-
Plains, N.Y., 1985. ing, or storage. Formation of the dark brown color causes
13. J. Heyback and F. Vellucci, Clustering Patterns of Food Intake the product to become unattractive and is accompanied by
at Breakfast, Internal Research Report, General Foods USA, undesirable changes in flavor and a reduction in nutritive
White Plains, N.Y., 1985. value. However, in some other cases such as the manufac-
14. 21 CFR Part 104, Federal Register 45, 6314-6324 (1980). ture of tea, coffee, or cocoa, this enzymatic browning re-
15. AMA Council on Foods and Nutrition and the Food and Nu- action is an essential part of the processing. Enzyme-
trition Board of the National Academy of ScienceNational catalyzed oxidative browning has been recognized since
Research Council "Improvement of Nutritive Quality of 1895, when the change in color of fresh apple cider was
gated shipping case. Shipping cases are generally regular Foods," Journal of the American Medical Association 205,160
slotted containers able to withstand a burst test ranging (1968).
from 150-275 Ib. Top-to-bottom compression strength of 16. U.S. Pat. 4,256,772 (Mar. 17, 1981), A. Shanbhag and A.
the case is important to prevent crushing during handling Szczesniak (to General Foods Corp.).
and storage. Minimum standards for corrugated contain- 17. U.S. Pat. 4,103,035 (July 25, 1978), C. Fulger and T. Morfee
ers have been established for rail and truck shipments and (to Kellogg Co.).
are covered under specific uniform classification codes 18. U.S. Pat. 3,484,250 (Dec. 16, 1969), W. Vollink and M. Steeg
(24-26). (to General Foods Corp.).
19. U.S. Pat. 4,588,596 (May 13, 1986), D. Bone and co-workers
Cereal Packaging Line (to the Quaker Oats Co.).
20. R. B. Coulter, "Extending Shelf Life by Using Traditional Phe-
The bag-in-the-box (BNB) packaging system is replacing nolic Antioxidants," Cereal Foods World 33, 207-210 (1988).
the double package liner packing lines. BNB packaging 21. R. Sims and J. Fioriti, "Antioxidants as Stabilizers for Fats,
uses vertical form-fill-seal baggers coupled with horizon- Oils, and Lipid Containing Foods," in T. E. Furia, ed., CRC
tal cartoners. Product is deposited in the bag (liner) during Handbook of Food Additives, Vol. 11, 2nd ed., CRC Press, Inc.,
bag formation and is sealed prior to carton insertion. In Boca Raton, Fl., 1980, pp. 13-56.
contrast, traditional packing lines form a liner and carton 22. R. H. Anderson and co-workers, "Effects of Processing and
around a mandrel prior to product fill. BNB equipment is Storage on Micronutrients in Breakfast Cereals," Food Tech-
more efficient and flexible, operates with wider liner ma- nology 30, 110-114 (1976).
terial selection, and produces a higher quality cereal liner. 23. W. Drennan, "Barrier Resins Key New Package Develop-
ment," Plastics Packaging, 17-21 (July-Aug. 1988).
24. Uniform Freight Classification, Uniform Freight Classifica-
BIBLIOGRAPHY tion Committee, Chicago, 111., annual.
25. National Motor Freight Classification, American Trucking As-
1. G. Carson, The Cornflake Crusade, Rinehart & Co., New York, sociations, Washington, D.C., annual.
1957, pp. 147-175.
26. Coordinated Freight Classification, The New England Motor
2. J. Berry, Inside Battle Creek, rev. ed., Battle Creek Public Rate Bureau, Inc., Burlington, Mass., annual.
Schools, Brochure No. 6, Battle Creek, Michigan, 1989.
3. The Staff, "State of the Food Industry, Breakfast Cereals,"
Food Engineering 60, 86 (1988). GENERAL REFERENCES
4. R. Fast, "Breakfast Cereals: Processed Grains for Human
Consumption," Cereal Foode World 32, 241-244 (1987). A. Brody and K. Marsh, The Wiley Encyclopedia of Packaging
5. R. Daniels, Breakfast Cereal Technology, Noyes Data Corp., Technology, 2nd ed., John Wiley & Sons, Inc., New York, 1997.
Park Ridge, N.J., 1974. S. A. Matz, The Chemistry and Technology of Cereals as Food &
6. R. Hosney, Principles of Cereal Science and Technology, Amer- Feed, AVI Publishing Co., Westport, Conn., 1959.
ican Association of Cereal Chemists, St. Paul, Minn., 1986, S. A. Matz, Cereal Technology, AVI Publishing Co., Westport,
pp. 293-304. Conn., 1970.
7. D. Tressler and W. Sultan, Food Products Formulary, Vol. 2,
AVI Publishing Co., Westport, Conn., 1975. DICK FIZZELL
8. N. Kent, Technology of Cereals, Pergamon Press, Elmsford, G. COCCODRILLI
NY, 1983, pp. 144-153. CHARLES J. CANTE
9. F. H. Webster, "Oat Utilization: Past, Present, and Future," General Foods USA
in F. H. Webster, ed., Oats: Chemistry and Technology, Amer- White Plains, New York
ican Association of Cereal Chemists, Inc., St. Paul, Minn.,
1986, pp. 413-426.
10. Committee on Diet and Health, Diet & Health: Implications
for Reducing Chronic Disease Risk, National Academy Press,
BROWNING REACTION, ENZYMATIC
Washington, D.C., 1989.
11. K. Morgan, M. Zabik, and G. Stampley, "The Role of Breakfast The change in color following mechanical or physiological
in Diet Adequacy of the U.S. Adult Population," Journal of the injury of fruits and vegetables is due to oxidative reactions
American College of Nutrition 5, 551-563 (1986). of phenolic compounds by polyphenol oxidase (PPO) and
12. J. Markle, F. Vellucci, and G. Coccodrilli, Food Selection Pat- the reaction products, o-quinones, to various polymerized
terns of Individuals Who Consume a Food Item in the Morn- products. In food processing, such color change is common-
ing, Internal Research Report, General Foods USA, White place during preparation for canning, dehydration, freez-
Plains, N.Y., 1985. ing, or storage. Formation of the dark brown color causes
13. J. Heyback and F. Vellucci, Clustering Patterns of Food Intake the product to become unattractive and is accompanied by
at Breakfast, Internal Research Report, General Foods USA, undesirable changes in flavor and a reduction in nutritive
White Plains, N.Y., 1985. value. However, in some other cases such as the manufac-
14. 21 CFR Part 104, Federal Register 45, 6314-6324 (1980). ture of tea, coffee, or cocoa, this enzymatic browning re-
15. AMA Council on Foods and Nutrition and the Food and Nu- action is an essential part of the processing. Enzyme-
trition Board of the National Academy of ScienceNational catalyzed oxidative browning has been recognized since
Research Council "Improvement of Nutritive Quality of 1895, when the change in color of fresh apple cider was
recognized first as a result of oxidation of tannin by the tinct reactions: (1) hydroxylation of monophenols to give o-
oxidase present in apple tissue (1). diphenols. This monophenol oxidase activity often requires
priming with reducing agents or trace amounts of o-
diphenol indicated as BH2,
POLYPHENOL OXIDASE
OH OH
PPO (phenolase or catechol oxidase) is a ubiquitous group
6
Monophenol Il OH
of copper metalloproteins and it is found in microorgan-
oxidase r ' ii ^ TT ^
isms (bacteria and fungi), plants, and animals, where it is + O2 + BH2 ^ I |j + B + H2O
involved in the biosynthesis of melanins and other poly-
phenolic compounds. PPO is of particular importance in
the processing and marketing of horticultural products be- and (2) the removal of hydrogens from o-diphenol to give
cause of the brown discoloration of bruised fruits and vege- o-quinone.
tables resulting from the action of this enzyme. Not only
does an undesirable color form, but browning is accompa-
nied by a loss of nutrient quality and the development of OH O
undesirable flavors. In some tropical fruits, the action of 1 OH Catechol Jl Q
PPO leads to major economic losses (up to 50%). Black (f^S oxidase ri^r'
2 11 I + O2 - l| J + 2 H2O
spots in shrimp are caused by PPO-catalyzed browning;
the browned shrimp are not acceptable to the consumer
and they are downgraded in quality. Millions of dollars are
spent each year on attempts to control PPO oxidation; to It was reported in 1944 that PPO preparations from
date none of the control methods are entirely successful. mushrooms had the ability to catalyze oxidation of mono-
On the other hand, browning by PPO is a desired reaction phenols in addition to catalyzing oxidation of polyphenols
in certain foods such as tea, coffee, cocoa, prunes, and (15). However, the ratio of rate of monophenol oxidation to
dates. that of polyphenol oxidation varied considerably from dif-
PPO was first discovered in mid 180Os in mushrooms ferent mushroom sources. Since then many reports have
(2). PPO is a generic term for the group of enzymes that shown a wide range of PPO activities in many different
catalyze the oxidation of phenolic compounds at the ex- fruits and vegetables in different ratios. Today, it is known
pense of oxygen to quinones. Quinones are highly reactive, that enzyme preparations from many other sources pos-
electrophilic molecules, which covalently modify and cross- sess these two activities in different ratios and that the
link a variety of cellular constituents including nucleo- ratios may change during isolation and purification. Most
philes of proteins such as sulfhydryl, amine, amide, indol, PPO preparations from potato, apple, mushroom, and bean
and imidazole substituents. These quinone adducts pro- possess both activities, whereas those from tea leaf, to-
duce brown or black color on cut surfaces of fruits and vege- bacco, mango, banana, pear, clingstone peach, and sweet
tables, and they are the major detrimental effect of the cherry have been reported not to act on monohydroxy phe-
enzyme in postharvest physiology and food processing. nols (16).
PPO is a copper-containing enzyme that belongs to a Laccase is less frequently encountered as a cause of
group of oxidoreductases. Although the function of PPO in browning in fruits and vegetables than is catechol oxidase.
plant metabolism is not well understood yet, the recent Laccase oxidizes o- and p-diphenols,
cloning of PPO presents opportunities to explore its func-
tion in plants as well as to explore the extent to which PPO OH O
expression can be manipulated. Various aspects of PPO
have been reviewed recently (3-8).
Depending on the substrate specificity, International
Enzyme Nomenclature has designated monophenol mono-
oxygenase or tyrosinase as EC 1.14.18.1, which hydroxyl-
OH ^^ . O
ates monophenols to o-diphenols; diphenol oxidase or cat- 17
echol oxidase or diphenol oxygen oxidoreductase as or 22 or + H2O
1.10.3.2, which dehydrogenates o-dihydroxyphenols to o- OH O
OH 0
quinones; and laccase orp-diphenol oxygen oxidoreductase
as 1.10.3.1. The first two enzymes, tyrosinase and catechol
oxidase, which many authors refer to as PPOs, occur in
A/ A^
practically all plants.
PPO was first described by G. Bertrand in 1895 who
demonstrated that the darkening of mushroom was due to In addition, it oxidizes various other p-diphenols, ra-
the enzymatic oxidation of tyrosine (9). In addition to its diphenols and p-phenylenediamine, but laccase does not
general occurrence in plants, PPO is also found in some oxidize tyrosine.
bacteria, fungi, algae, bryophytes, and gymnosperms (10- PPO appears in almost all tissues of plants; however,
13). Laccase was first observed by H. Yoshida in the latex significant differences in both the level of the activity and
of the Japanese lacquer tree (14). PPO catalyzes two dis- in the concentration of its substrates have been observed
among different cultivars of fruits and vegetables. The en- PPO LOCATION IN PLANT
zyme has been found in a variety of cell fractions, both in
organelles and in the soluble fraction of the cell (17,18). The vascular elements of many fruits and vegetables
The level of PPO often changes markedly during the de- darken rapidly when they are cut and exposed to air. The
velopment of the plant (19-21) and may be significantly relative PPO activity of different parts of apricots, apples,
affected by growing conditions. or potato plants vary. PPO is considered to be an intracel-
Recent emerging new scientific development in the field lular enzyme in plants except in a few cases where it is
of molecular biology offers not only the possibility of un- found in the cell wall fraction. The enzyme is located in a
derstanding the essential function of PPO in plants, which variety of cell fractions, both in organelles where it may be
has remained a puzzle for years, but it also promises to tightly bound to membranes and in the soluble fraction
control PPO and its substrates to prevent browning in (17,18). Histochemical studies using the electron micro-
foods. scope and the density gradient centrifugation support the
idea that PPO is bound within chloroplast lamellae and
PPO ANALYSIS grana and in mitochondria (34). Recent study suggested
more specifically that PPO is located in the grana lamellae
Qualitative and quantitative colorimetric tests and man- loosely associated with photosynthetic photo system II
ometric determinations have been used to detect and mea- (35). Many studies indicated that PPO is membrane-bound
sure enzyme activity. Because PPOs use molecular oxygen in plastides of nonsenescing tissues (3,5). It was suggested
to oxidize phenolic substrates, their activity can be deter- that PPO is located exclusively in plastids and is only
mined by measuring the rate of substrate disappearance released to the cytosol upon wounding, senescence, or de-
or the rate of product formation. When based on the rate terioration of the organelle (36). So far, no PPO genes en-
of substrate disappearance, oxygen absorption is usually coding a nonplastidic enzyme have been isolated (8). Con-
measured either manometrically in a Warburg respiro- version of particulate forms of the enzyme to soluble forms
meter or polarographically with an oxygen electrode. The occurs in fruits when they are exposed to stress conditions
most popular method of assay is to follow the initial rate or during ripening and storage. Browning reactions that
of formation of the quinone spectrophotometrically by mea- take place after the disruption of tissues rich in PPO may
suring the optical density. Care must be taken to restrict cause binding of soluble PPO to a particulate fraction. The
measurement to the initial phase of the oxidation, because microbial extracellular laccase has been studied exten-
the reaction soon slows down. Some researchers object to sively but the location of laccase in higher plants is not
the use of spectrophotometric analysis because it measures well known. Although it is believed that the enzyme is
the secondary reaction products of PPO, and the secondary found in a cytoplasmic soluble form, more information is
reactions are influenced by many factors difficult to con- needed on its location and distribution in plant tissues.
trol. Thus the presence of ascorbic acid creates a lag phase
and lowers the values obtained, whereas autooxidation
products of polyphenols may increase the levels of enzyme EXTRACTION AND PURIFICATION
activity. It is important to note that the reaction changes
with time and temperature and depends on the substrate Due to extremely low concentrations of PPO and laccase
type and concentration, on the pH of the reaction mixture, in plants and their instability, preparation and purification
and on the buffer used (22,23). A wide variety of substrates of PPO and laccase are not easy. PPO has been isolated
can be used with spectrophotometric methods: catechol from a variety of sources, but pigment contamination and
(24), pyrogallol (25), or chlorogenic acid (26). It has to be the occurrence of multiple forms have frequently ham-
taken into account that the reaction products formed from pered its characterization. Oxidation reactions taking
the oxidation of various phenols have absorption maxima place during the isolation of the enzyme, due to natural
at different wavelengths, that the substrate may undergo substrates within the plant, result in changes in enzyme
autooxidation, and that an excess of some substrates properties as well as in apparent multiplicity. Such reac-
causes strong inhibition of the enzyme (26). Other methods tions can be partially prevented by isolation under nitro-
for PPO activity are based on disappearance of ascorbic gen gas, by using reducing agents such as ascorbic acid or
acid, a reaction that is directly proportional to enzyme ac- cysteine, or by using phenol-adsorbing agents, such as
tivity (27) and spectrophotometric methods using Bes- poly(vinylpyrrolidone) or poly(ethylene glycol) (37,38). The
thorn's hydrazone (28), or 2-nitro-5-thiobenzoic acid (29). binding of PPO to membranes in many tissues further
It is important to differentiate between catechol oxidase complicates its isolation. Solubilization of acetone powder
and laccase on the one hand and peroxidase on the other. preparations or extracting with detergents also result in
Because peroxidative oxidation of phenols is often mis- modification in structure and properties of the enzyme. To
taken for PPO or laccase, peroxides should be removed minimize these changes, all extraction steps should be car-
from the reaction mixture by addition of catalase and al- ried out at temperature below O0C, preferably at -20 to
cohol to prevent any oxidation of phenols (30). For the de- -3O0C. Communition and homogenization are often car-
termination of laccase, syringaldehyde (31) and 2,6- ried out in liquid nitrogen or under a nitrogen atmosphere
dimethoxyphenol (32) have been used as substrates of (39). Acetone precipitation followed by buffer extraction is
laccase. The PPO and laccase activities can be differenti- one of the methods most often applied (16).
ated by the use of cinnamic acid derivatives to inhibit PPO For the purification of the enzyme, several methods
and cationic detergents to inhibit laccase (33). have been used that vary according to the enzyme source
and the degree of purity to be attained. Most often, pre- pH and Temperature Optima
cipitation with ammonium sulfate of different saturation,
The optimum pH for the activity of an enzyme preparation
gel chromatography on Sephadex columns, ion exchange
from any one source usually varies with different sub-
chromatography, DEAE-cellulose or DEAE-Sephadex are
strates and is characteristic of the substrate as well as the
applied. Recently, hydrophobic gel chromatography using
enzyme preparation. The optimum pH of PPO activity has
Phenyl-Sepharose CL-4B has been used effectively (40,41).
a relative wide range, pH 5.0 and 7.0. Some preparations
The separation of enzymes by electrophoresis is now a
were reported to be inactive below 4.0. The type of buffer
standard procedure. Sodium dodecylsulfate (SDS) tech-
and the purity of the enzyme affect the pH optimum; also,
niques and electroblotting of catechol oxidase also have
isoenzymes have different pH optima. Enzyme prepara-
been successfully used (42,43).
tions obtained from the same fruit or vegetable at various
stages of maturity have been reported to differ in optimum
PHYSIOCHEMICAL PROPERTIES
pH of activity as well. The pH optimum of laccase activity
Molecular Weight depends on the enzyme source and on the substrate. The
stability of the enzyme is reported to be dependent upon
Most reports on the molecular weight of PPO are based on
buffer and other factors in the medium. Optima between
estimates on partially purified preparations using gel ni-
pH 4.5 and 7.5 have been reported for enzymes from vari-
tration or acrylamide gel electrophoresis. Therefore, a wide
ous fungi and peaches (54).
range of values are reported. Often crude or partially pu-
The optimum temperature of PPO depends essentially
rified preparations show a multiplicity of forms, which may
on the same factors as the pH optimum. Generally, the
have resulted from association-dissociation reactions. De-
activity of PPO increases as the temperature rises from
pending on the source of the enzyme, the molecular
cold to temperatures of maximum activity (25-350C); ac-
weights vary between 29,000 and 200,000 with subunit
tivity declines rapidly at temperatures of 35 to 450C, de-
molecular weight from 29,000 to 67,000. Until recently, the
pending on the enzyme source and substrate (16). Like
enzyme from the bacterium Streptomyces glaucescens was
most enzymes, the application of heat (70-9O0C) to plant
found to have the smallest functional unit with one copper
tissues or enzyme solutions for a short period causes rapid
pair per polypeptide chain of 29,000 (44). The molecular
inactivation. Exposures to temperatures below zero may
weight of mushroom PPO has been reported to be between
also affect activity. Concentrated solutions of the enzyme
116,000 and 128,000 daltons (37). The enzyme consisted of
in dilute phosphate buffer at a pH near neutrality can be
four identical subunits of Mw ca 30,000, each containing
held without detectable loss of activity for several months
one copper atom (45). Two types of polypeptide chains,
at I0C or when frozen at -250C. However, the enzyme
heavy (Mw 43,000) and light (Mw 13,400) were reported in
slowly losses activity even in the frozen state. Thermo-
mushroom (46). Avocado, banana, tea leaf, and other
tolerance of PPO also depends on the source of the enzyme.
sources also showed multiple molecular weights in a wide
It is difficult to compare heat stability data of purified en-
range. The predominant form of PPO in grape had a mo-
zyme preparations with that of the enzyme when in tissues
lecular weight of 55,000 to 59,000 but upon storage it dis-
or juice. Different molecular forms of PPO from the same
sociated into 31,000-33,000 and 20,000-21,000 subunits
source may have different thermostabilities. Laccase is
(47). Based on recent knowledge regarding multiplicity of
usually more sensitive to inactivation by heat than is cat-
PPO, it is believed that many previous observations on
echol oxidase.
multiplicity were due to secondary reactions, such as tan-
ning, during enzyme preparation.
Activators and Inhibitors
With the advent of recombinant DNA technology in re-
cent years, numerous amino acid sequences have become The activation mechanism of PPO from different sources
available. These include PPO from the bacterium Strep- is not well understood, but it has been suggested that con-
tomyces glaucescens (48) and Streptomyces antibioticus formational changes of protein and perhaps protein asso-
(49), tomato (50,51), broad bean (52), and potato (53). All ciation or dissociation are involved in the process. Anionic
PPO molecules sequenced are single-chain proteins with detergents, such as sodium dodecyl sulfate, were found to
calculated Afw of 30,900 (273 amino acid residues) for S. reactivate PPO in crude and partially purified prepara-
glaucescens and S. antibioticus, 46,000 (407 amino acid tions from different avocado cultivars (55). Short expo-
residues) for Af. crassa, 68,000 (606 amino acid residues) sures to acid pH or urea also resulted in a severalfold re-
for the broad bean Vicia faba, and 66,300 (587 amino acid versible activation of grape and bean PPO.
residues) for tomato. Many compounds inhibit PPO activity but only a lim-
The molecular weight of laccase was also reported to ited number of PPO inhibitors are considered acceptable
vary according to their sources. Rhus vernicifera laccase on grounds of safety and expense for use to control enzy-
has been reported to vary between 101,000 and 140,000 matic browning during food processing. Practical aspects
depending on the species and variety. The Mw of the fungal of browning inhibition are discussed later. There are two
laccase varies between 56,000 and 390,000; peach laccase principal types of PPO inhibitor: compounds that interact
was reported to have a Mw of 73,500. These data suggest with the copper in the enzyme and compounds that
that laccases are a heterogeneous group of glycoproteins, affect the site for the phenolic substrate. The metal-
having a basic structural unit of between 50,000 and chelating agents such as cyanide, diethyldithiocarbamate,
70,000 Mw, which can undergo aggregation to give larger carbon monoxide, dimercaptopropanol, sodium azid, phen-
units. ylthiourea, and potassium methyl xanthate are all inhib-
itory. In general, there are five major types of PPO inhib- fense system is one of many theories of PPO function in
itors based on their chemical characters (56,57): plant. Enzymatic browning generated by PPO in a multi-
(1) reducing agents, such as ascorbic acid and sulfur diox- tude of plantpest interactions and its wound inducibility
ide; (2) copper-chelating agents, such as carbon monoxide, have led some scientists to the view that the primary role
tropolone, and diethyl dithiocarbamate; (3) quinone cou- of PPO is in plant defense (58). Therefore, the challenge
plers, such as cysteine and glutathione; (4) substrate here is to selectively modify PPO expression in specific tis-
analogues, such as cinnamic acid, p-coumaric acid, and sue to minimize its effects on browning of fruits and vege-
benzoic acid and some substituted cinnamic acids; and tables, while maximizing PPO expression in other parts of
(5) miscellaneous compounds, such as 4-hexylresorcinol the plant to maintain pathogen or herbivore resistance.
and poly(vinylpyrrolidone). Some other natural inhibitors Much progress has been made recent years. PPO genes
of PPO from various sources have been reported (57). The have been characterized from broad bean, tomato, potato,
activity of laccase is not inhibited by carbon monoxide or and grape, and all PPOs cloned have been found to encode
phenylhydrazine, both of which inhibit PPO. This response mature peptides of 57,000 to 62,000 Da with 8,000 to
permits an easy differentiation between laccase and PPO. 11,000 Da putative transit peptides, which posttransla-
tionally directs the protein to the chloroplast envelope
Substrate Specificity (7,35,51-53). The catalytic centers of the copper binding
regions for V. faba and tomato PPOs have been elucidated.
Whereas PPOs from animal tissues are relatively specific
The further characterization of PPO in various plants is
for tyrosine and dopa, those from fungi and higher plants
being made, and there is a great potential in near future
act on a wide range of monophenol and o-diphenols. There
to manipulate the levels of PPO in plant foods to overcome
are individual differences among PPOs from different
the adverse effects of PPO.
sources. The rate of oxidation of o-diphenols by PPO in-
creases with increasing electron withdrawing power of
substituents in the para position. o-Diphenol substitution Mechanism of Oxidation
(-CH3) at one of the positions adjacent to the -OH groups
In spite of extensive studies on PPOs, its reaction mecha-
prevents oxidation. These positions should remain free for
nism is still unclear. One of the reasons is that the mech-
oxidation to take place. As mentioned earlier, some PPO
anism of PPOs on phenolic compounds is complicated. As
preparations from some plants lack cresolase activity,
stated earlier, the cresolase reaction apparently involves a
which may be due to changes in the structure of the protein
hydroxylation reaction, which differs from the oxidation of
during preparation. Some arguments regarding the physi-
the o-diphenols by the catecholase reaction. For a long time
cal relationships between the cresolase and catechol oxi-
there was a difference of opinions as to whether hydroxy-
dase functions suggested that both functions are catalyzed
lation of monophenols and oxidation of o-dihydroxy phe-
by a single site, whereas others imply the participation of
nols were catalyzed by the same enzyme. The oxidation
two sites, either on the same enzyme molecule or different
mechanism of PPO from N. crassa has been extensively
ones. Although PPO could oxidize a wide range of pheno-
investigated (44), and a plausible theory of its catalytic ac-
lics, the individual enzymes tend to prefer a particular sub-
tivation is shown in Figure 1.
strate or certain type of phenolic substrates. The affinity
The proposed mechanisms for hydroxylation and de-
of plant PPOs of the phenolic substrates is relatively low.
hydrogenation reactions with phenols probably occur by
The Km is high, usually around 1 mM, which is higher than
separate pathways but are linked by a common deoxy PPO
most of fungi and bacteria, 0.1 mM. The affinity to oxygen
intermediate (middle in Fig. 1). In dehydrogenation of cat-
is also relatively low, ranging from 0.1 to 0.5 mM. Mono-
echol oxidase (cycle A in Fig. 1), oxygen is bound first to
phenols and o-diphenols have been considered as the ex-
the Cu(I) groups of deoxy PPO to give oxy PPO in which a
clusive substrates of PPO for a long time, but a recent
Cu-Cu distance of the two Cu(II) groups is about 3.4 to 3.6
study showed that aromatic amines and o-aminophenols
A. This would allow two Cu(II) groups of oxy PPO to bind
also undergo the same catalytic reactions (ortho hydroxy-
to the oxygen atom of the two hydroxyl groups of catechol
lation and oxidation), as documented by product analysis
(an efficient 2e-transfer from catechol to the binuclear site)
and kinetic studies (44).
and from the O2-PPO-catechol complex (at about the 1
o'clock position on the A cycle of Fig. 1). The catechol is
Cloning of PPO Genes
then oxidized to o-benzoquinone (at about 11 o'clock posi-
Scientific interest in molecular biology of PPO is that the tion), and the enzyme is reduced to met PPO. Another mol-
molecular weight and the form of PPO have long been a ecule of catechol binds to met PPO, is oxidized to o-
matter of speculation because of the various forms of the benzoquinone (and water) and the enzyme reduced to
PPO as described earlier. Identification of PPO genes offers deoxy PPO, completing the A cycle.
a great potential to produce transgenic plants having reg- The mechanism of o-hydroxylation of a monophenol by
ulated levels of PPO. Because PPO is responsible for sig- PPO is shown in B cycle in Figure 1. In vitro, the reaction
nificant decreases in postharvest quality of many crops due begins with met PPO of A cycle. Met PPO must be reduced
to enzymatic browning associated with injury or senes- by a reducing compound BH2 (shown previously) if a lag
cence, downregulation of PPO using antisense could sig- period is to be avoided, to give deoxy PPO. Deoxy PPO binds
nificantly increase quality attributes of most fruits and O2 to give oxy PPO, the monophenol is bound to one of the
vegetables. However, overexpression of PPO may poten- Cu(II) groups via the oxygen atom of the hydroxyl group
tially minimize pest damage to crop plants. This plant de- to give the O2-PPO-monophenol complex (at about 5 o'clock
Met
Deoxy
Figure 1. Proposed mechanisms of oxidation of o-diphenol (cycle A, for catechol) and monophenol
(cycle B) for Neurospora crassa PPO. Source: Adapted from Refs. 2 and 44.
on the B cycle). Subsequently, the o-position of the mono- 4 Cu2 +(enzyme) + 2 catechol -> 4 Cu+(enzyme)
phenol is hydroxylated by an oxygen atom of the O2 of the + 2 o-quinone + 4 H
O2-PPO-monophenol complex to give catechol, which then
dissociates to give deoxy PPO, to complete the cycle. Only 4 Cu+(enzyme) + 4 H + + O 2 - > 4 Cu2+ (enzyme) + 2 H2O
the first cycle of hydroxylation on a monophenol requires
starting at the met PPO; all subsequent cycles begin with Recent understanding of the complete amino acid se-
deoxy PPO (2). quence of fungal PPO and the site of interaction with the
Because copper is the prosthetic group, the catalytic ac- phenolic substrate made it possible to create models that
tivity of PPOs is based on the cupric-cuprous valency include a binuclear center. Histidine residues appear to
change. On isolation of the enzyme in its natural state, the lignand at least one of the two active sites of the copper
copper is in the cuprous form, but in the presence of o- atoms. Monophenols bind to one of the Cu2+ atoms,
dihydroxy phenols, the copper would be oxidized to cupric whereas diphenols bind to both of them, as shown in Fig-
form. The substrate is oxidized by losing two electrons and ure 1 (59,60). Catechol oxidase can undergo conformational
two protons. The two electrons are taken up by the copper changes induced by the substrate O2 and by pH. The
of the enzyme, which then passes into the cuprous state. changes in conformation are accompanied by changes in
The cuprous enzyme rapidly transfers the two electrons to the Km of the enzyme for both its substrates, oxygen and
oxygen, which immediately forms water with the two pro- diphenol.
tons that were liberated, and the enzyme returns to the A two-step reaction mechanism by laccase has been re-
cupric state. This two-state reaction can be represented by ported (61). The first step in the oxidation of quinol by lac-
case was the formation of the semiquinone, with transfer CONTROL OF BROWNING IN FOODS
of an electron from substrate to the copper in the enzyme.
The second step was a nonenzymatic disproportionation Extensive studies have been carried out to control enzy-
reaction between two semiquinone molecules to give one matic browning ever since Lindet (1) recognized in 1895
molecule of quinone and one of quinol. The function of cop- that the change in color occurring in freshly pressed cider
per and electron transfer in the reaction mechanism has was enzymatic. The practical control of enzymatic brown-
been studied by using inorganic ions, electron paramag- ing in foods has been carried out by several methods. The
netic resonance, and spectrophotometric methods (3,62). method of choice is dependent upon the food product and
the intended use. The enzymatic browning in fruits and
The Brown Pigment vegetables can be controlled at the beginning by selecting
Although the mechanism of pigment formation from phe- cultivars that are least susceptible to discoloration either
nolic substrates is not understood completely, the general because of the absence of the certain phenolic substrate or
course of pigmentation is known to involve enzymatic ox- because the substrate or enzyme is present at low concen-
idation, nonenzymatic oxidation, nonoxidative transfor- tration. It is also possible to select fruits and vegetables at
mations, and polymerizations. The o-quinones formed stages of maturity where discoloration is at minimum.
from phenolic compounds by PPOs are the precursors of Other methods include the removal of oxygen from fruit
the brown color. The o-quinones themselves possess little and vegetable tissues as well as from the atmosphere sur-
color, but they are among the most reactive intermediates rounding the food; the addition of acids to reduce the pH
occurring in plants. They take part in a secondary reaction, and thus reduce PPO activity; the addition of antioxidants
bringing about the formation of more intensely colored sec- or reducing substances; the addition or treatment with
ondary products. The most important secondary reactions permissible inhibitors; and heat inactivation of the en-
are coupled oxidation of substrates oxidized, complexing zyme. The use of antioxidants during processing and heat
with amino compounds and proteins, and condensation inactivation of the enzyme are widely used practices that
and polymerization. The principal reaction of o-quinones have been moderately successful.
in browning reaction is the one leading to the formation All fruits susceptible to browning should be processed
of the unstable hydroxyquinones. The hydroxyquinones as quickly as possible. Heating destroys the enzymes re-
polymerize readily and are easily further oxidized non- sponsible for the reaction; thus when fruit is canned or
enzymatically to a dark brown pigment. made into jams or jellies, browning stops as soon as the
As a typical oxidation reaction, tyrosine is oxidized to fruit is heated sufficiently to denature the enzyme. The
dihydroxyphenylalanine (dopa) quinone by PPO and then exact temperature necessary varies with enzyme, rate of
proceeds to melanin (Scheme 1). Tyrosine is first converted heating, pH, and other factors such as size of the fruits.
into dopa, which is then oxidized to the corresponding dopa Unfortunately some undesirable effects on quality often
quinone. The dopa quinone, on intramolecular rearrange- result from an adequate heat process. In general, cherry,
ment, is converted into 5,6-dihydroxy indole-2-carboxylic peach, and apricot take 2 to 3 minutes in boiling water and
acid, which on further oxidation is converted into red 5,6- apple, pear, and plum take 4 to 5 minutes to inactivate
quinone indole carboxylic acid; then finally the black mel- enzymes responsible for browning on surface. Vegetables
anins are formed. Quinones also react readily with simple such as beans and peas also take 3 to 5 minutes. The op-
amines, such as timum blanching conditions for strawberry, black currant,
sour cherry, and prune range from 1.5 to 3 minutes at 850C.
o-Benzoquinone + glycine - 4-A^gIyCyI-O-benzoquinone In the preparation of fruit for freezing, sugars and sugar
solution have been used to sweeten and to exclude direct
This reaction product is the intermediate responsible for contact of the fruit tissue with molecular oxygen. The
the deamination of glycine with the concomitant formation sugar solutions inhibit discoloration by reducing the con-
of deeply colored pigments. o-Quinones also react with pro- centration of dissolved oxygen and by retarding the rate of
teins, sulfhydryl compounds, such as cysteine, and produce diffusion of the oxygen from the air into the fruit tissues.
dark-colored, insoluble products. Concentrated sugar solutions also exert an inhibiting ef-
Dimerization or polymerization of o-quinones that lead fect on fruit PPO. The pH also affects the rate of the brown-
to the colored products is common. The formation of dimers ing reaction: acid dips are sometimes used to lower the pH
or oligomers of o-quinone by condensation of a hydroxy qui- and by this method delay or retard browning. The effect of
none with a quinone was recently demonstrated. The en- many salts and compounds such as sulfur dioxide, hydro-
zymatically generated caffeoyl tartaric acid o-quinones gen sulfide, hydrocyanic acid, and thiourea on PPO has
were shown to oxidize other phenols, such as 2-S- been studied extensively.
glutathionyl caffeoyl tartaric acid and flavans, by coupled In the home preparation of fruits, pineapple juice and
oxidation mechanisms, with reduction of the cafeoyl tar- lemon juice have long been used to prevent browning. Pine-
taric acid quinones back to caffeoyl tartaric acid (63). The apple juice has a relatively high concentration of sulfhy-
o-quinones formed by enzymatic or coupled oxidation can dryl compounds, which are active antioxidants, whereas
also react with a hydroquinones to yield a condensation lemon juice contains relatively high amounts of both citric
product (64-66). It is possible to regenerate the original acid and ascorbic acid.
phenolic from an intermediate by reduction provided that Heat treatments and the application of sulfur dioxide
oxidation and subsequent transformation had not gone too or sulfites are common commercial methods for inactivat-
far. In later stages the browning is no longer reversible. ing PPO. PPO activity can be inhibited by the addition of
Tyrosinase
a CH2
/
NH2
Tyrosine
+Q
Slow
wnx^\/CH2
CHCOOH -- H0f |[
HO1^^ NH2
^
Dopa
^CHCOOH
/
+ O ^,^.X^s^^CEk
=-*
Fast
] ^f
(^^
U
^CHCOOH
'
NH2
Dopa quinone
Fast
HOr^V'A
I ^ + CO2
^JxX^r^\COOH --^-
+0 HO-^^V^ACOOH
Slow Fast
HO^^X^NH 0^\^^NH HO^^/^-NH
5,6-Dihydroxyindole Dopachrome Leuco compound
Fast
NH J ^ - O
O >x\ \\
+Protein
1 7 \ - rV^O . Melanin-Protein
^^^^^ ivrw Relatively I I
O' ^^ NH glow <^\/A
Indole I I /
5,6-Quinone n^^V^^NH
Melanin
Scheme 1.
sufficient amounts of acidulants, such as citric, malic, or the time required for inactivation. To minimize the
phosphoric acids to yield a pH of 3 or lower. Oxygen can be undesirable changes due to excess heating, optimum
eliminated by vacuum or by immersing the plant tissues temperature-time requirements for PPO must be estab-
in a brine or syrup. Phenolic substrates can be protected lished. Rapid cooling after enzyme inactivation is also
from oxidation by reaction with borate salts, but these are necessity for best quality retention.
not approved for food use. Sulfur dioxide is a very effective inhibitor of PPO and
For products such as vegetables, which ultimately end has been used for many years. It readily reacts with com-
up cooked, heat inactivation by steam or hot water blanch- pounds such as aldehyde and other carbonyl-containing
ing is the most practical method of inactivating PPOs. molecules. These reaction products are ineffective against
Overblanching should be avoided due to loss of firmness PPO, and therefore, a sufficient amount of free SO2 must
and nutrients. Most commercial blanching of vegetables be maintained. In order to be effective in preventing PPO
has been based on the residual activity of the peroxidase activity, SO2 must penetrate throughout the tissues. SuI-
because peroxidase is one of the most stable enzymes in furous acid penetrates better than the bisulfite form. The
plants. It has been generally accepted that if peroxidase is use of excess SO2 produces both undesirable flavors and
destroyed it is quite unlikely that other enzymes including an excessively soft product. In recent years the safety of
PPOs will have survived. There are, however, problems as- sulfites in foods has been questioned because of their haz-
sociated with the use of peroxidase as an indicator of an ard to certain asthmatics. Since August 9, 1986, the U.S.
adequate blanch in that several enzymes other than per- FDA has banned the use of sulfur dioxide in fresh fruits
oxidase have been shown to be largely responsible for qual- and vegetables and has required a label declaration on
ity deterioration during frozen storage of different vege- those food products (such as dehydrated fruits, frozen po-
tables (67,68). Therefore, optimization of blanching of tato products, wine) containing more than 10 ppm of sul-
individual products has to be established in order to tailor fiting agent. Because of these restrictions, food processors
the process to each type of raw material and product de- have turned to a number of sulfite alternatives, mostly for-
sired. Heat inactivation of PPO in fruit products has been mulations effective against enzymatic browning, with
applied to fruit juices and purees and to fruit intended for varying success. The demand for more effective browning
such products. Because the enzyme is very labile to heat inhibitors has stimulated considerable research activity in
at 850C and above, the higher the temperature, the shorter this area during the last decade.
Ascorbic acid and its isomer, erythorbic acid, and deriv- better understanding of the mechanism of action of PPO
atives such as ascorbic acid-2-phosphate, ascorbic acid- and its essential metabolic roles in plants, it is expected
triphosphate, ascorbic acid-6-fatty acid esters are reported that genetic engineering techniques will be the most im-
to control browning. Ascorbic acid is a very effective re- portant tools in preventing unwanted enzymatic browning.
ducing agent, as it reduces the o-quinones formed by PPO A molecular biology approach will provide a more precise
to the original o-dihydroxy phenolic compounds. Ascorbic method of decreasing PPO expression, while retaining the
acid alone or in combination with citric acid have been used desirable genetic traits of plants.
widely by the food industry. Its prevention of browning
lasts as long as any residual ascorbic acid remains, and,
therefore, stabilized forms of ascorbic acid should be effec- BIBLIOGRAPHY
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33. J. R. L. Walker and R. F. McCallion, "The Selective Inhibition 53. M. D. Hunt et al., "cDNA Cloning and Expression of Potato
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Phytochemistry 18, 193-215 (1979). 55. V. Kahn, "Latency Properties of Polyphenol Oxidase in Two
35. A. R. Lax and J. W. Gary, "Biology and Molecular Biology of Avocado Cultivars Differing in Their Rate of Browning," J.
Polyphenol Oxidase," in C. Y. Lee and J. R. Whitaker, eds., ScL FoodAgric. 28, 233-239 (1977).
Enzymatic Browning and Its Prevention, ACS Symposium Se- 56. J. R. L. Walker, "Enzymatic Browning in Fruits," in C. Y. Lee
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The Chloroplast Oxidase With No Established Function," 8-22.
Physiology Plantarum 72, 659-665 (1988). 57. C. Y. Lee and J. R. Whitaker, Enzymatic Browning and Its
37. D. Kertesz and R. Zito, "Mushroom Polyphenol Oxidase. I. Prevention, ACS Symposium Series 600, Washington, D.C.,
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96, 447-462 (1965). 58. S. Duffy and G. Felton, "Enzymatic Antinutritive Defenses of
38. W. D. Loomis and J. Battaile, "Plant Phenolic Compounds and the Tomato Plant Against Insects," in P. Hedin, ed., Naturally
the Isolation of Plant Enzymes," Phytochemistry 5, 423-438 Occurring Pest Bioregulators, American Chemical Society,
(1966). Washington, D.C., 1991, pp. 166-197.
59. M. E. Winkler, K. Lerch, and E. I. Solomon, "Competitive In- domestication of animals constituted the earliest begin-
hibitor Binding to the Binuclear Copper Active Site in Tyros- nings of human civilization and culture. There is good rea-
inase," J. Am. Chem. Soc. 103, 7001-7003 (1981).
son to believe, therefore, that the milking of animals and
60. J. R. Whitaker, Principles of Enzymology for the Food Sci- the origin of butter making aforedate the beginning of or-
ences, 2nd ed., Marcel Dekker, New York, 1994.
ganized and permanent recording of human activities.
61. T. Nakamura, "On the Process of Enzymatic Oxidation of Hy- The evolution of the art of butter making has been in-
droquinone," Biochem. Biophys. Res. Commun. 2, 111-113
timately associated with the development and use of
(1960).
equipment. With the close of the eighteenth century the
62. R. A. Holwerda, S. Wherland, and H. B. Gray, "Electron construction and use of creaming and butter-making
Transfer Reactions of Copper Protein," Ann. Rev. Biophys.
Bioeng. 5, 363-396 (1976). equipment, other than that made of wood, began to receive
consideration, and the barrel churn made its appearance.
63. V. Cheynier, C. Osse, and J. Rigaud, "Oxidation of Grape Juice
Compounds in Model Solutions," J. Food ScL 53, 1729-1732
By the middle of the nineteenth century attention was
(1988). given to improvement in methods of creaming. These ef-
64. V. L. Singleton, "Oxygen with Phenols and Related Reactions forts gave birth to the deep-setting system. Up to that
in Musts, Wines, and Model Systems: Observations and Prac- time, creaming was done by a method called shallow pan.
tical Implications," Am. J. Enology Viticulture 38, 69-77 The deep-setting system shortened the time for creaming
(1987). and produced a better-quality cream. An inventive Bavar-
65. V. Chenyier, N. Basire, and J. Rigaud, "Mechanism of trans- ian brewer in 1864 conceived the idea of adapting the prin-
Caffeoyltartaric acid and Catechin Oxidation in Model Solu- ciple of the laboratory centrifuge. In 1877 a German en-
tions Containing Grape Polyphenoloxidase," J. Agric. Food gineer succeeded in designing a machine that, although
Chem. 37, 1069-1071 (1989). primitive, was usable as a batch-type apparatus. In 1879
66. J. Oszmianski and C. Y. Lee, "Enzymatic Oxidation Reaction engineers in Sweden, Denmark, and Germany succeeded
of Catechin and Chlorogenic Acid in a Model System," J. in the construction of cream separators for fully continuous
Agric. Food Chem. 38, 1202-1204 (1990). operation (1).
67. M. H. Lim et al., "Enzyme Indicators of Adequate Blanching," In 1870, the last year before introduction of factory but-
in Proceedings International Conference on Technical Inno- ter making, butter production in the United States was
vations in Freezing and Refrigeration of Fruits and Vegetables, 514 million Ib, practically all farm made. Authentic records
University of California-Davis, Calif., July 9-12, 1989, pp. concerning the beginning of factory butter making are
67-72. meager. It appears that the first butter factory was built
68. C. Y. Lee, N. L. Smith, and D. E. Hawbecker, "An Improved in Iowa in 1871. This beginning also introduced the pooling
Blanching Technique for Frozen Sweet Corn-on-the-cob," in system of creamery operation (1).
Proceedings International Conference on Technical Innova- Other inventions that assisted the development of the
tions in Freezing and Refrigeration of Fruits and Vegetables,
University of California-Davis, Calif., July 9-12, 1989, pp.
butter industry included the Babcock test (1890), which
85-90. accurately determines the percentage of fat in milk and
69. T. P. Labuza, J. H. Lillemo, and P. S. Taoukis, "Inhibition of
cream, the use of pasteurization to maintain milk and
Polyphenoloxidases by Proteolytic Enzymes," Flussiges Obst. cream quality; and the use of pure cultures of lactic acid
59, 15-20 (1992). bacteria and refrigeration to help preserve cream quality.
70. J. Oszmianski and C. Y. Lee, "Inhibition of Polyphenol Oxi-
dase Activity and Browning by Honey," J. Agric. Food Chem. BUTTER CONSUMPTION
38, 1892-1895 (1990).
71. G. M. Sapers and F. W. Douglas, "Measurement of Enzymatic
Browning in Cut Surfaces and in Juice of Raw Apple and Pear
Butter production and consumption has recently increased
Fruits," J. Food Sd. 52, 1258-1262 (1987). from a long decline Table 1-4. A dramatic shift occurred,
starting in 1985, to the table spreads category of products
(less than 80% fat) from full-fat butter, margarine, and
CHANG Y. LEE blends (2, Land O'Lakes, unpublished data, 1985). The
Cornell University spreads category encompasses all non-Standard-of-
Geneva, New York Identity table spreads (ie, from O to 79.9% fat). Major mar-
ket forces have changed this production consumption turn-
around. As noted in a 1984 survey, the most important
BULKING AGENTS. See SUGAR: SUBSTITUTES, BULK,
REDUCED CALORIE.
Table 4. Per Capita Consumption of Butter Standards for butter in the United States were established
for the Years 1950 to 1995 by an Act of Congress and are supported by the USDA
Year Pounds per capita standards for grades of butter. In the revised standards the
1950 10.7
following definitions apply. Butter refers to the food prod-
1960 7.7 uct usually known as butter, which is made exclusively
1970 5.4 from milk, cream, or both, with or without common salt;
1980 4.5 and with or without additional coloring matter. The milk
1990 4.0 fat content of butter is not less than 80% by weight, allow-
1995 4.5 ing for all tolerances. Cream refers to the cream separated
Source: Refs. 3, 4, and Land O'Lakes unpublished data, from milk produced by healthy cows. Cream is pasteurized
1996. at a temperature of not less than 73.90C for not less than
30 min; or it can be pasteurized at a temperature of not
less than 890C for not less than 15s. Other approved meth-
ods of pasteurization give equivalent results (5).
barriers to increased butter sales were listed in the follow- The cream may be cultured by the addition of harmless
ing order (2): lactic acid bacteria to enhance flavor, natural flavors ob-
tained by distilling a fermented milk, or cream may be
1. Price (opinion of an overwhelming majority when added to the finished butter. In addition, color, derived
butter is compared to margarine) from a Food and Drug Administration (FDA) approved
2. Health (negative consumer attitudes toward choles- source, may be used.
terol and saturated fats are increasing) There are three U.S. grades of butter: AA, A, and B.
3. Poor spreadability Butter is graded by first classifying its flavor organolepti-
cally. In addition to the overall quality of the butter flavor
4. Inadequate promotional spending
itself, the standards list 17 flavor defects and the degree
5. Product innovation in margarine and spreads to which they may be present for each grade. If more than
6. Legislation and regulatory restrictions one off-flavor is noted, assignment is made on the basis of
the flavor resulting in the lowest grade. This grade is then
The forces that have had a positive impact on butter are lowered by defects in the workmanship and the degree to
as follows: which they are apparent. Disratings are characterized by
negative body, flavor, or salt attributes, which are fully de- the bovine mammary gland in assembling a complex array
scribed in the standards. Butter that does not meet the of fatty acids into triglycerides. This is not an arcane study;
requirements for U.S. Grade B is not graded. To bear the it is necessary if processes such as fractionation are to yield
USDA seal, the finished product must fall within the fol- products with consistent qualities throughout the year. In
lowing microbiological specifications: proteolytic count not effect, the detailed structure of milk fat is not yet under-
more than 100 per gram, yeast and mold not more than 20 stood. Perhaps this is not surprising if we consider only the
per gram, and coliform not more than 10 per gram. Butter 15 major fatty acids; there are 153 (3375) possible triglyc-
should be stored at 4.40C or lower or at less than - 17.80C, eride structures using a purely random model.
if it is to be held for more than 30 days (6). The concentration of milk fat results in a dairy product
Legal requirements for butter vary considerably in dif- called butter. The concentration is a two-stage process with
ferent countries. For example, in Europe butter must con- the first stage being effected in a mechanical separator,
tain 82% fat and in France it may contain a maximum of which causes a 10-fold concentration of the fat into an in-
16% moisture (6). In some tropical parts of the world, milk termediate product, cream. The second stage is the churn-
fat is used in nearly anhydrous form because it is less sus- ing process, which results in a further twofold concentra-
ceptible to bacterial spoilage. This product is known as tion of the fat.
ghee. In the Middle East and India ghee is prepared from In butter manufacture, the preparation of the cream is
heated cow or buffalo milk. effected quite independently of the butter-manufacturing
stage. Today most butter plants receive their cream from
other operations rather than directly from the farm, as was
COMPOSITION
the case in the past. Because of general improvement in
sanitation practices, the receipt of fresher milk and cream,
The composition of milk fat is somewhat complex. Al- and advances in the knowledge and understanding of del-
though dominated by triglycerides, which constitute some eterious handling conditions, the quality of cream is con-
98% of milk fat (with small amounts of diglycerides, mono- stantly improving.
glycerides, and free fatty acids), various other lipid classes The composition of milk fat is the most important factor
are also present in measurable amounts. It is estimated affecting the firmness of butter and, therefore, its spread-
that about 500 separate fatty acids have been detected in ability. The composition of milk fat changes primarily ac-
milk lipids; it is probable that additional fatty acids remain cording to the feed; therefore, the entire problem is con-
to be identified. Of these, about 20 are major components; nected to the animal's diet. Today, the fatty acid
the remainder are minor and occur in small or trace quan- composition of milk fat produced in various countries is
tities (7,8). The other components include phospholipids,
rather accurately known, along with its seasonal varia-
cerebrosides, and sterols (cholesterol and cholesterol es-
tions. In Europe the amount of saturated fatty acids is gen-
ters). Small amounts of fat-soluble vitamins (mainly A, D,
erally highest in winter and lowest in summer or fall (Table
and E), antioxidants (tocopherol), pigments (carotene), and
flavor components (lactones, aldehydes, and ketones) are 5) (11). Green fodder decreases the amount of saturated
also present. fatty acids and correspondingly increases the amount of
The composition of the lipids of whole bovine milk is unsaturated fatty acids (12). The differences between the
given in Table 2 (7,8). The structure and composition of the maximum and minimum values can be fairly large. For
typical milk fat globule is exceeding complex^ The globule palmitic and oleic acids, the quantitatively most important
is probably 2 to 3 // in diameter with a 90-A-thick mem- fatty acids, a difference of more than 10% between the
brane surrounding a 98 to 99% triglyceride core. The com- maximum and minimum values was found in some cases.
position of the milk fat membrane is quite different from This makes it understandable that there are also signifi-
milk fat itself in that approximately 60% triglycerides are cant differences in the physical characteristics of the but-
present, much less than in the parent milk fat (Table 3) ter. The structure of the triglycerides in the milk fat, along
(9,10). with the fatty acid composition, is important in determin-
It has been generally recognized that butterfat consists ing the physical characteristics of the fat, because the soft-
of about 15 major fatty acids with perhaps 12 or so minor ening point of fat has been found to rise as the result of
(trace quantity) acids. Triglycerides are normally defined interesterification (13).
with respect to their carbon number (CN), that is, the num- Protected oils are hydrolyzed in the abomasum, and the
ber of fatty acid carbon atoms present in the molecule; the fatty acids are absorbed in the small intestine, thereby
three carbon atoms of the glycerol moiety are ignored. Be- avoiding hydrogenation. The 18:2 content in the milk fat
cause the fatty acid spectrum of milk fat is dominated by was increased about fivefold, and the 14:0, 16:0, and 18:0
acids containing an even number of carbon atoms, so is the were decreased accordingly. Plasma and depot fats were
triglyceride spectrum. However, the proportion of triglyc- also increased in 18:2 content by this program (14).
erides with an odd carbon number is about three times Results at the USDA are similar: cow's milk can be in-
greater than the proportion of odd-numbered fatty acids. creased in 18:2 acid from 3 to 35% by feeding protected
Although obvious correlations exist between fatty acid safflower oil (15,16). However, at high 18:2 levels, milk de-
composition and triglyceride distribution, detailed infor- velops an oxidized off-flavor, usually after about 24 h, and
mation is lacking that would enable the triglyceride dis- creams require a longer aging time for satisfactory churn-
tribution to be predicted from the fatty acid composition. ing. As expected, butter that contains more than 16% lin-
Much more needs to be understood of the strategy used in oleic acid is soft and sticky (8).
Table 5. Compositional Characteristics of Summer and Winter Milk Fat, 1970
Fatty acids
Samples investigated (N = 140) Volatile Saturated Monounsaturated Polyunsaturated Iodine number
Total 10.98 56.50 29.81 2.50 32.2
Summer 9.49 58.82 33.53 3.14 36.8
Winter 12.45 59.15 26.15 1.86 27.7
Source: Ref. 11.
There are also differences in the butter fat of different butter has a higher solids content than does a tub mar-
cows on identical rations, and the age of the animal and garine. Hence the latter product is more easily spread (18).
duration of lactation have some influence on butter fat As crystallization proceeds, the growing crystals im-
composition. Much of the dairy literature provides infor- pinge to form aggregates. A network results, in which both
mation relating dairy animal species and the composition the solid and liquid phases may be regarded as continuous.
of the butter fat from them. Formation of the network greatly increases the firmness
Textural characteristics of butter are significantly de- of the fat.
pendent on milk fat composition and method of manufac- As a liquid fat is cooled, crystallization begins. There
ture. It is possible, therefore, knowing the chemical com- are two parts to the crystallization: (1) nucleation and
position of milk fat, to select the appropriate technological (2) growth. In a bulk fat, nucleation occurs at the surfaces
parameters of butter making to improve the texture. To of impurities, a phenomenon described as heterogeneous
obtain butter with constant rheological characteristics and nucleation. A considerable degree of supercooling is nec-
to control the parameters of the butter-making process it essary to initiate nucleation. Subsequent growth of the nu-
is necessary to consider the difference in the chemical com- clei tends to be slow in natural fats because of competitive
positions and the properties of the milk fat in various sea- inhibition. In materials of low molecular weight, impuri-
sons. ties are rejected at the face of growing crystal. In fats, how-
From the standpoint of nutritional value, the vitamin A ever, the various triglyceride species are so closely related
content of butter is important. Because the source of vi- that the term impurity tends to lose its meaning (19).
tamin A in butter is ^-carotene or other carotenoid pig-
ments in the feed of the cows, the content of this vitamin Hydrogenation
varies considerably, being highest in the summer when the
dairy herds are in pasture and lowest in winter when there Hydrogenation of various fats and oils is used extensively
are no green feedstuffs in the rations. A portion of the car- in industry but is not generally applied to butter fat (the
otene in the feed that is transferred by the cow into the high cost of the raw material argues against its use as a
butter fat varies with the feeding regimen parallel to var- feedstock). The process reduces the degree of unsaturation
iations in the production of vitamin A, so that the intensity of the fat and increases its melting point.
of the yellow color of butter to some extent serves to indi- Given the criticism directed at milk fat because of its
cate its vitamin A content. saturated nature, there appears to be little future in in-
The vitamin A potency of butter is in part due to vitamin creasing the degree of saturation by means of hydrogena-
A as such and in part to carotene, which is partially con- tion. The reverse procedure, desaturation or dehydroge-
verted to the vitamin in the human body. The vitamin A nation, offers more attractive prospects.
content of butter is usually within the range of 6 to 12
mg/g, and the carotene content is in the range of 2 to 10 Cream Quality
mg/g (17); 1IU of vitamin A is defined as the amount pos- Raw cream should be processed without delay to minimize
sessing the biological activity of 0.6 jug of pure ^-carotene. deterioration of quality. If the cream is to be held for more
The vitamin D content of butter is much less significant than two hours between separation and processing, it
than that of vitamin A, but it is nevertheless appreciable. should be cooled below 50C. For holding periods exceeding
It varies from about 0.1 to 1.0 ITJ/g, being highest in the one day it may be advantageous to heat, treat, or pasteur-
summer and lowest in the winter (17). ize the cream.
To make high-quality butter, the cream must be of high
MODIFICATION OF MILK FAT quality. The flavor of butter is the most important organ-
oleptic property, and it depends in no small part on the
Melting and Crystallization of Milk Fat Triglycerides
flavor quality of the cream from which it is made. There is
no real alternative to tasting in assessing flavor and this
The complex fatty acid composition of milk fat is reflected simple but important procedure should be conducted rou-
in its melting behavior. Melting begins at - 3O0C and is tinely as part of the overall quality-control program.
complete only at 370C. At any intermediate temperature, The application of hazard analysis of critical control
milk fat is a mixture of solid and liquid. To a large extent, points (HACCP) to butter production is one of the newer
the solid: liquid ration determines the rheological proper- techniques to ensure improved butter safety and quality
ties of the fat. For example, at refrigeration temperature, (20).
Fat Content ration of fats and a major factor in determining the shelf
life of fat-containing foods (23). Unsaturated fatty acid es-
The percentage of fat in the cream must be known and ters react with oxygen to form peroxides. Although flavor-
controlled. It influences fat losses in churning. Knowledge less themselves, peroxides are unstable and readily decom-
of the fat content assists in yield estimations for opera- pose to yield flavorful carbonyl compounds. The latter are
tional conditions in continuous manufacture. A number of the source of the characteristic oxidized flavors that are
satisfactory procedures are available, with the Babcock detectable at low concentrations. The rate of oxidation de-
test being the most common. pends on the concentration of dissolved oxygen, the tem-
The chemical composition of the triglycerides, which perature, the presence of prooxidants such as copper and
comprise milk fat, varies throughout the year depending iron, the degree of unsaturation of the fat, and the presence
on the stage of lactation and the cow's diet. This causes a of antioxidants that may retard the onset of oxidation.
cyclic change in the melting properties of the fat. In the Compared with many fats, milk fat has a good oxidative
control of the butter-making process and the physical prop- stability, because it is high in total saturates, low in poly-
erties of the finished butter this factor must be monitored. unsaturates, and contains natural antioxidants, princi-
The term melting property is used rather than softness or pally a-tocopherol.
hardness because these more correctly refer to an alto- The development of oxidative rancidity in milk fat is the
gether different attribute of solids. A number of procedures major determinant of the stability of the fat on storage.
have been used to follow the seasonal change in the melt- Dissolved air in the milk fat can give dissolved oxygen lev-
ing properties. The iodine number, refractive index and dif- els of up to 40 ppm at 3O0C. In practice, the dissolved ox-
ferential scanning calorimetry, or pulsed nmr spectroscopy ygen level in the freshly processed milk fat would be about
can be used to prepare a melting curve. However, the ex- 5 ppm at 450C, a level sufficient to permit the development
pense and complexity of these melting curve techniques of oxidative rancidity, but if the milk fat were allowed to
precludes the approach in most quality-control situations equilibrate with the air, then this level could increase to
(21). The traditional chemical determinations for fat, sa- 33 ppm with a consequent increase in the rate of devel-
ponification value and Polenske value, are of limited value. opment of oxidative rancidity.
They are scarcely relevant for quality control, and the in- The oxygen level in the milk fat may be limited by either
formation they represent can be more usefully quantified active or passive actions. For passive control, processing
by the determination of the fatty acid profile using gas procedures and plant design are established to minimize
chromatography. oxygen (air) exposure. Deaeration devices (24), the use of
Today the use of stainless steel has essentially elimi- antioxidants, effective destruction of lipases, and nitrogen
nated the exposure of the fat to copper and iron. The pres- spanning of container headspace are examples of active
ence of copper and, to a lesser extent, iron can catalyze control of product quality.
oxidative deterioration of butter during storage, particu-
larly in the presence of salt and a low pH. Consistency
Many procedures have been used or proposed to assess
the microbiological quality of the milk or cream. Generally, Consistency has been defined as "that property of the ma-
microbiological tests are performed to determine the hy- terial by which it resists permanent change of shape and
giene of production and storage conditions or for safety rea- is defined by the complete force flow relation" (8). This im-
sons. Tests include total counts and counts for specific plies that the concept of consistency includes many aspects
classes of microorganisms such as yeasts and molds, coli- and cannot be expressed by one parameter. Today more
forms, psychotrophs, and pathogens such as Salmonella. importance is attached to spreadability than anything else
Rapid-screening tests based on dye reduction or direct ob- in the evaluation of the consistency of butter. The general
servation using a microscope or automatic total counters consensus is that butter should be spreadable at refriger-
are also in use. ator temperatures. There is no suitable method available
to measure such a subjective criteria as the spreadability
Lipase Activity of butter. For this reason, the firmness of butter, which
should correlate well with spreadability, was selected as
Lipolysis in butter after manufacturing caused by ther- the parameter to be measured. It was recommended that
moresistant lipase enzymes created in milk or cream by the use of the cone penetrometer, along with other meth-
psychotrophic bacteria is an increasing problem. Based on ods, could give good results (25).
a termination of the lipase activity in cream, the keeping
quality of manufactured butter in regard to lipolysis can Flavor
be predicted with reasonable accuracy. A similar prediction
for sweet cream butter can be based on activity determi- One of the most important consumer attributes of butter
nation in the serum phase (22). is the pleasing flavor. Butter flavor is made up of many
volatile and nonvolatile compounds. Researchers have
Oxidation identified more than 40 neutral volatiles, of which the most
prominent are lactones, ethyl esters, ketones, aldehydes,
The flavor of dairy products is largely determined by the and free fatty acids (26). The nonvolatiles, of which salt
fat component. Consequently, it is particularly important (sodium chloride) is the most prominent, contribute to a
to restrict the development of oxidized off-flavors in the fat balanced flavor profile. Diacetyl and dimethyl sulfide also
source before use. Oxidation is the chief mode of deterio- contribute, especially in cultured butter flavor (27).
Ripened or cultured creams use lactic acid bacterial cul- serum. Whether separation is accomplished by gravity or
tures selected for their ability to produce volatile acid and centrifugal methods, the result depends on this difference
diactyl flavors. The NIZO (Dutch Research Institute for (28).
Dairy) process was developed to incorporate concentrated
lactic starters or to directly inject starter distillates to pro- Crystallization
duce the flavor and characteristics of cultured butter (25).
In the United Kingdom, Canada, Ireland, and the United The crystal structure of fat and the resulting physical prop-
States, sweet cream, salted butter is primarily used, but erties of butter made by both conventional and alternative
in France, Federal Republic of Germany, and Scandinavia, processes have received considerable study. When conven-
the taste of cultured butter is preferred (6). tionally churned or Fritz butter is made, most of the milk
fat is contained within the fat globule in cream during the
Body and Texture cooling and crystallization process. The fat globule pro-
vides a natural limit to the growth of fat crystals. Cooling
The physical properties of butter that are noted by the and holding of cream is normally carried out overnight,
senses are described by butter graders by means of appro- and thus sufficient time exists for the crystallization pro-
priate qualifications of the terms body and texture. The cess to approach equilibrium (29).
exact meaning of these terms has not been clearly defined. The principles of crystallization of plastic fats in the
Frequently they are used as if they had the same meaning. type of equipment used for margarine manufacture have
Certain properties such as hardness and softness refer to been described (30). It is important to develop small fat
the body of butter, whereas properties such as openness crystals that remain substantially discrete and do not form
refer to texture. But some of the properties, such as leak- a strong interlocking structure. Small crystals (eg, 5-//m
iness or crumbliness, lead to confusion. Usually, most body diameter) have a greater total surface area than large crys-
and texture terms are used to describe a defect such as tals and will bind water and free liquid fat by absorption
gritty, gummy, sticky, and the like. more effectively (29). Large crystals impart a gritty texture
Good butter should be of fine and close texture; have a to the product. When fats are cooled rapidly in a scraped
firm, waxy body; and be sufficiently plastic to be spread- surface heat exchanger, fat crystallization commences, but
able at cold temperatures. the fat is substantially supercooled on exiting. If crystal-
lization is then permitted to continue under quiescent con-
Color ditions, crystals will grow together and form a lattice struc-
The color of butter may vary from a light creamy white to ture. The product will thus be hard and brittle and may
a dark creamy yellow or orange yellow. Differences in but- tend to leak moisture. If, however, crystallization is per-
ter color are due to variations in the color of the butter fat, mitted to occur under agitated conditions (eg, for 1-3 min
which is affected by the cows' feed and season of the year; in a pin worker), the formation of small, independent crys-
variations in the size of the fat globule; presence or absence tals will be favored and the product will have a fine, smooth
of salt; conditions of working the butter; and the type and texture. If crystallization under agitated conditions is per-
amount of natural coloring added. mitted to continue for too long, the product will be too soft
Butter colorings are oil soluble and most often are nat- for most patting or bulk filling operations, and it is likely
ural annatto, an extraction of the seeds of the tropical tree to be too soft and greasy at warm room temperatures.
Bixa orellana, or natural carotenes, extractions from vari-
ous carotene-rich plants. Because they are oil soluble, col- Neutralization
orings are added to the cream to obtain the most uniform When lactic acid has developed in the raw, unpasteurized
dispersion. cream by microbial activity to a degree considered exces-
sive, neutralizer may be added to return the cream acidity
PROCESSING to a desirable level. Sodium carbonates have been found
suitable in practice for batch neutralization. For continu-
Milk and Cream Separation ous neutralization by pH control, sodium hydroxide is
more suitable. These chemicals should be of food grade.
The most basic and oldest processing method is cream sep-
aration. Ancient people are known to have used milk freely. Fractionation
It is probable that they used the cream that rose to the top
of milk that had been held for some time in containers, Fractionation by thermal crystallization, steam stripping,
although there is little in ancient literature to suggest that short-path distillation, supercritical fluid extraction, or
such use was common. It is well established that in early crystallization using solvents can achieve fat alterations of
times butter was produced by churning milk. significance to the dairy industry. Milk fat is a mixture
The principal questions concerning separation in a of triglycerides with a range of molecular weights, degrees
butter-manufacturing facility are the choice of cream fat of unsaturation, melting points, and other physical prop-
content and the choice of the separation technique, milk erties. Milk fat is an important component of most dairy
separation before or after pasteurization, temperature of products, but it has been consumed traditionally for the
separation, and regulation of the fat content. Separation most part as butter.
of cream from milk is possible because of a difference in Fractionation of butter fat for the selective removal of
specific gravity between the fat and the liquid portion, or cholesterol has been recently reported using supercritical
fluid extraction (31), steam stripping or deodorization (32), ing, is now the predominant process for butter manufac-
short-path molecular distillation (33), and absorption pro- ture in most butter-producing countries. In the churning
cesses (28). Various enzymatic investigations are under process crystallization of milk fat is carried out in the
way to isolate cholesterol reductase (34) and to insert the cream, with phase inversion and milk fat concentration
gene for cholesterol reductase into lactic and acid bacteria taking place during the churning and draining steps. How-
biogenetically (35), resulting in the reduction of the dairy ever, because of the discovery that cream could be concen-
fat cholesterol to its major by-product, coprostanol. trated to a fat content equal to or greater than that of
butter, methods have been sought for converting the con-
Heat Treatment centrated or plastic cream directly into butter. Such meth-
ods would carry out the principal butter-making steps es-
The heat treatment of cream plays a decisive role in the sentially in reverse order, with concentration of cream in
butter-manufacturing process and the eventual quality of a centrifugal separator, followed by a phase inversion, cool-
the butter. It is important that milk and cream be handled ing, and crystallizing of the milk fat (37).
in the gentlest possible way to avoid mechanical damage Increased demands on the keeping qualities of butter
to the fat, a serious problem in continuous manufacture require that, in addition to careful construction, operation,
(Fritz process) of butter (36). Cream is pasteurized or heat and cleaning of the milk and cream processing equipment,
treated for the following reasons: to destroy pathogenic mi- research to develop machines that will ensure butter pro-
croorganisms and reduce the number of bacteria; to deac- duction and packing under conditions eliminating contam-
tivate enzymes, to liquefy the fat for subsequent control of ination and air admixture must be carried out. It has been
crystallization, and to provide partial elimination of un- demonstrated that butter produced under closed condi-
desirable volatile flavors. tions has a better keeping quality than butter produced in
open systems (38).
Batch Butter Manufacture There are two classes of continuous processes in use:
Today batch processing is not used to any extent for the one using 40% cream, such as the Fritz process, and the
production of large quantities of butter. Batch systems are other using 80% cream, such as the Cherry-Burrell Gold'n
still encountered in small butter plants, primarily in less Flow. As much as 85% of the butter in France is made by
industrially developed countries. Continuous systems are the Fritz process. In this process 40% fat cream is churned
more efficient and cost effective for large outputs; batch as it passes through a cylindrical beater in a matter of
systems have low capital intensity. seconds. The butter granules are fed through an auger
The processing of cream by a batch churn requires fill- where the buttermilk is drained and the product is squeeze
ing to approximately 30 to 50% capacity at a cream tem- dried to a low moisture content. It then passes through a
perature of 4.4 to 12.80C. Cream temperature will vary second working stage where brine and water are injected
depending on seasonably of the cream, the butter charac- to standardize the moisture and salt contents. As a result
teristics desired, and the desired rate of fat inversion. of the efficient draining of the buttermilk, this process is
Churning is accomplished by rotation of the churn at ap- suitable for the addition of lactic acid bacteria cultures at
proximately 35 rpm until small butter granules appear. this point. The process then becomes known as the NIZO
The process usually requires about 45 min for coalescence method when the lactic starter is injected (Land O'Lakes,
of the fat globules and clean separation of the buttermilk unpublished data, 1985). Advantages of the NIZO method
so that it can be drained (37). The granules may be washed over traditional culturing are improved flavor develop-
with cold water to remove surface buttermilk. Salt is then ment; acid values as a result of lower pH; more flexible
added with water if the fat content standardization is re- temperature treatment of the cream, because culturing
quired. The butter is worked to ensure uniformity and de- and tempering often are accomplished concurrently; and,
sirable body and texture characteristics. most important, sweet cream buttermilk is produced.
The latest in developments in butter making have been
Continuous Butter Manufacture outlined in the European Dairy Magazine (39), with the
article centering on dosing systems, and for the addition of
Between 1930 and 1960 a number of continuous processes salt and culture. In addition, a number of patents have
were developed. In the Alfa, Alfa-Laval, New Way, and been issued for improved butter-making processes (40),
Meleshin processes phase inversion takes place by cooling making butter directly from milk (41), and for flexible in-
and mechanical treatment of the concentrated cream. In tegration of added ingredients, and molding and demold-
the Cherry-Burrel Gold'n Flow and Creamery Package ing (42).
processes, phase inversion takes place during or immedi- The Cherry-Burrell Gold'n Flow process is similar to
ately after concentration, producing a liquid identical to margarine manufacture (43). The process starts with
melted butter, prior to cooling and working. The Alfa, Alfa- 18.30C cream that is pumped through a high-speed desta-
Laval, and New Way processes were unsuccessful com- bilizing unit and then to a cream separator from which a
mercially. The Meleshin process, however, was adopted 90% fat plastic cream is discharged. It is then vacuum pas-
successfully in the Republic of Russia. The Cherry-Burrel teurized and held in agitated tanks to which color, flavor,
Gold'n Flow process appears to have been the more suc- salt, and milk are added. Then this 80% fat-water emul-
cessful of the two American processes (29). sion, which is maintained at 48.90C, is cooled by use of
The Fritz continuous butter-making process, which is scraped surface heat exchangers to 4.40C. It then passes
based on the same principles as traditional batch churn- through a crystallizing tube, followed by a perforated plate
that works the butter. Prior to chilling, 5% nitrogen gas is oped the IBC method (45). The main principles of the IBC
injected into the emulsion. method are as follows. After sweet cream churning and
Although the Meleshin process continues to be in wide- buttermilk drainage, a starter culture mixture is worked
spread use in the former USSR, the use of alternative con- into the butter, which produces both the required lowering
tinuous butter-making processes based on high-fat cream of butter pH and, because of the diacetyl content of the
has declined in Western countries during the past 20 years starter culture mixture, the required aroma. The starter
(29). The principal reasons for this decline appear to be the mixture consists of two types of starter culture. (1) Lacto-
economics and butter quality, particularly when compared coccus lactis and (2) L. cremoris and L. lactis ssp. diacety-
with the Fritz process. A Fritz manufacturing process can lactis. With respect to production costs, the experience
be installed in existing batch churn factories with almost with this method shows that for the manufacture of mildly
no modification to cream-handling or butter-packing cultured butter, the direct costs are only about one-third of
equipment. The churns could be retained in case the Fritz the costs of other methods (45).
breaks down. However, very little batch plant equipment
could be reused in the alternative systems (ie, Gold'n Butter-Vegetable Oil Blends
Flow). When a completely new plant is being bought, the
alternative systems still tend to be more expensive, and In the early 1980s blends of butter and vegetable oil prod-
operational advantages over the Fritz are not significant. ucts appeared in the U.S. market. These blends generally
Butter from the Fritz process is nearly identical in its were 40% butter and 60% vegetable oil for a total fat con-
physical and flavor characteristics to batch-churned but- tent of 80%, within the margarine Standard of Identity and
ter, whereas butter produced by the alternative processes designation. With the increasing popularity of reduced-fat
tends to be different. These differences may be perceived (less than 80%), spreads, starting in the mid-1980s, other
as defects by the consumer, and manufacturers have been blends with butter fat contents of 2 to 25% were intro-
reluctant to alter a traditional product. duced. As noted in Table 1, the full 80% fat blends have
The alternative systems have a number of advantages declined in preference to the lower-fat spreads; the blend
compared with a modern Fritz line: (1) The most attractive spreads have taken a portion of this market share (Land
advantage is the flexibility to produce a wide range of prod- O'Lakes, unpublished data, 1996).
ucts with fat contents ranging from 30 to 95% butter- A number of processes were developed using continuous
vegetable oil blends and the incorporation of fractionated churns (46) and alternative systems similar to the Cherry-
fats; (2) these processes also present the possibility of a Burrell Gold'n Flow process (47). The major disadvantage
number of operational advantages by use of an efficient to churning, either batch or continuous, was that the re-
centrifuge during the cream concentration stage; fat losses sultant buttermilk would be adulterated with some vege-
in the buttermilk can be substantially reduced; and (3) the table fat and would be less valuable than standard butter-
composition of the butter can be more accurately con- milk. An advantage of alternative processing systems is
trolled, either by including a batch standardization step or their ability to easily accommodate the manufacture of
by the use of accurate continuous metering systems. reduced-fat spread blends.
With the popularity of blends in the United States, sev-
Reworking Butter
eral products were introduced in Europe and Australia and
Since significant amounts of butter are made during high have subsequently expanded the market for butter fat us-
milk production periods of the year (spring) and highest age (Land O'Lakes, unpublished data, 1996). An even ear-
consumption tends to be during the late fall, butter by ne- lier entry into the blend category was Swedish Bregott in
cessity needs to be stored under conditions to ensure con- Europe.
tinuing quality. These conditions are usually in bulk frozen
form. Thawing and the subsequent reworking have re- Whipped Butter
sulted in development of new and superior processes and
equipment. The equipment is in a closed system with Whipped butter is a product produced to improve spread-
clean-in-place, and the process includes butter blocks at ability; air or nitrogen is incorporated. With the incorpo-
temperatures > - 50C that are transported to a shredder, ration of gas, the butter's volume increases by approxi-
from which the butter chips pass via large-diameter screw mately 33%. Generally, whipped butter is sold in tub
conveyors to the silo; from here they are pumped through rather than stick form.
the reworker where optimal moisture distribution is
achieved by two counterrotating kneading rollers, and re- Spreadable Butter
worked butter emerges at 6 to 140C. Equipment for re-
working of butter blocks that have a temperature of In 1937 a process known as the Alnarp method was devel-
> - 250C incorporates a butter tempering system after the oped to increase the spreadability of butter made from win-
shredder, and temperature of the emerging butter can be ter milk fat. The apparent reason for its effectiveness is
regulated (44). that it increases the liquid fat content of the milk fat (Fig.
D (48).
BUTTER PRODUCTS The consistency of butter is determined by the percent-
age of solid fat present, which is directly influenced by the
Cultured Butter Manufacture fat composition, the thermal treatment given to cream
There are several ways of making cultured butter from prior to churning, the mechanical treatment given to but-
sweet cream. Pasilac-Danish Turnkey Dairies, Ltd. devel- ter after manufacture, and the temperature at which the
Two industrial processes in practice for the fractiona-
tion of milk fat are the Tirtiaux system, and the DeSmet,
which is a semicontinuous bulk crystallization process.
They are dry fractionation processes enabling one- or two-
Yield value (k Nrrr2)
CACAO BEAN. See CHOCOLATE AND COCOA. nonaqueous solvents is a crystalline solid that melts at 235
to 2370C. At atmospheric pressure it begins to sublime
CAFFEINE without decomposition at 12O0C and at 8O0C under high
vacuum. Its crystals are hexagonal and form parallel
Caffeine (1,3,7-trimethylxanthine) was isolated from coffee plates. When crystallized from water, the monohydrate
in 1820 (1). Thein was isolated from tea in 1827 and later forms long, silky, white needles. It becomes anhydrous at
shown to be identical with the coffee isolate. It was sub- 8O0C. Caffeine is soluble to the extent of 0.6% in water at
sequently identified in cocoa, mate, kola nuts, and other O0C, 2.13% at 250C and 66.7% at 10O0C. The pH of dilute
plants; structure was determined in 1875. Caffeine is one solutions is 6.9. In aqueous solution, caffeine forms dimers
of several methylxanthines that occur naturally, primarily and higher polymers by base stacking (3). It is fairly stable
in plant matter that is used to prepare beverages. Other in dilute bases and acids, forming salts with the latter.
methylxanthines that usually accompany it include theo- Caffeine is considerably more soluble in chlorinated sol-
bromine and theophylline. The methylxanthines, as dio- vents: 8.67% in methylene chloride and 12.20% in chloro-
xypurines, are related to two nucleic acids: adenine and form at 250C. Its ultraviolet absorption spectrum shows a
guanine. This is relevant to their biosynthesis and physi- maximum at 274 nm with no variation over the pH range
ological effects. Their relationship to uric acids accounts 2 to 14.
for their metabolic fate. The structures of caffeine and re-
lated compounds are shown in Figure 1. Chemical Properties
Total synthesis was first achieved in 1895 starting with
dimethylurea. Dimethyluric acid, chlorotheophylline, and Complexation occurs with many acid radicals, notably
chlorocaffeine were intermediates (2). chlorogenate, salicylate, citrate, benzoate, and cinnamate.
Chlorogenic acid forms a tightly bound 1:1 complex. It is
PROPERTIES soluble in chloroform and can be recrystallized from aque-
ous alcohol, attesting to its stability. In plant matter much
Physical Properties of the caffeine exists in this form (4). Complexes with phe-
Caffeine is a white, odorless powder with a slightly bitter nolic molecules are only stable below pH 6. Caffeine is a
taste. The anhydrous form obtained by crystallization from weak base; its acid salts hydrolyze readily. It is converted
Guanine Adenine
2-Aminohypoxanthine 6-Aminopurine 1,3,7-Trimethyluric acid
Concern with the physiological effects of caffeine has stim- Natural Products
ulated research on its analysis in food and biological sys-
tems. High-performance liquid chromatographic (hplc) A high proportion of the human population has consumed
analysis of caffeine in food products requires only the fil- caffeine-containing beverages for many centuries. Authen-
tration of aqueous extracts and injection onto a suitable ticated usage of tea in China dates from A.D. 350. The bev-
column. Detection is frequently based on the measurement erage reached Europe in 1600. Coffee came into use as a
of juv absorption at 280 nm (7). Determination of caffeine beverage in Arabia around A.D. 1000 and was brought to
at the low concentrations present in body fluids is accom- Europe in the seventeenth century. Cocoa was consumed
plished by direct injection onto reversed-phase hplc col- by the Aztecs in Mexico. In many parts of South America
umns (8). Gas chromatographic determination of caffeine mate has been a source of substantial caffeine intake. Caf-
in beverages using a flame ionization detector has also feine content of several contemporary food products is
been described (9). Capillary electrophoresis has also been shown in Table 1.
used for caffeine determination (10). Variations in caffeine content in specific plant species
result from varietal diversity, climatic changes in the grow-
ing areas, and horticultural techniques. In tea, youngest
OCCURRENCE leaf has the highest concentration (17). Processing condi-
tions also affect caffeine content. High coffee roasting tem-
Caffeine is present in various tissues of about 60 plant spe- peratures result in caffeine loss by sublimation (18). There
cies, several of which are used to prepare beverages (11). is a higher level of caffeine in tea than in coffee beans, but
The most important are the following: 200 cups of tea beverage are obtained per pound of tea
leaves, whereas only about 40 to 60 cups of coffee are usu-
Coffee beans (Coffea arabica and Coffea canephora var. ally prepared per pound of coffee beans.
robusta) By far, the greatest sources of dietary caffeine are coffee
Tea leaves (Camellia sinensis vars. assamica and sinen- and tea, but cola beverages provide an increasing portion
sis) of the intake. The total per capita intake of caffeine by
Cocoa beans (Theobroma cacao) adults in the United States is about 3 mg/kg of body weight
Mate stems and leaves (Ilex paraguariensis) with about 2 mg/kg coming from coffee and most of the rest
from tea. For caffeine users, average intake is approxi-
Guarana seeds (Paullinia cupana) mately 4 mg/kg (19). The consumption by heavy users is
Kola nuts (CoZa acuminata and Cola verticillata) of interest because of concern with possible health effects.
Mean daily intake (mg/kg body weight) in the United
BIOGENESIS States by consumers in the 90th to 100th percentiles of
consumption varies with age level as follows:
The biogenesis of caffeine is probably similar in all plants,
1-5 yr 4.7 12-17 yr 2.9
but with differences in the rates of various steps. It has its 6-11 yr 3.2 18 yr+ 7.0
origin in the cell purine pool. Precursors include 7-
methylxanthosine, 7-methylxanthine, and theobromine. Tea and soft drinks are the major caffeine sources for users
Synthesis of caffeine from adenine occurs readily in young under the age of 18. Coffee becomes the major source for
tea leaf. 7-Methylguanilic acid and 7-methylguanasine are those over that age (20).
also on the biosynthetic path. A 7-methyl-7V-nucleoside hy-
drolase mediates the removal of ribose from 7-methylxan- Caffeine as a Food Additive
thosine. S-adenosylmethionine is the methyl donor for the
methylation of the xanthines in reactions catalyzed by N- In addition to its natural occurrence in plants, caffeine is
methyltransferase (12,13). A possible reaction path is added to the very widely consumed cola drinks and other
Table 1. Caffeine in Food Products few soft drinks have a higher level. No-caffeine colas have
Caffeine content Caffeine per become widely consumed.
(%) serving" (mg)
Prescriptions and Over-the-Counter Medications
Food product Range Mean Range Mean
In the United States prescriptions and over-the-counter
Coffee, arabica 0.58-1.7 1.2 35-80 60
(OTC) medications use a total of about 50 metric tons of
Coffee, robusta 1.2-3.3 2.2 60-140 120
Coffee, instant 2.2-5.0 3.3 45-105 65 caffeine annually. Caffeine-containing medications are
Coffee, decaf. 0.03-0.09 0.06 2-6 3 used for certain types of pain relief, treatment of infant
Tea, black 1.2-4.6 3.0 20-48 35 apnea, alertness increase, and weight loss.
Tea, green 1.0-2.4 1.9 17-40 24
Tea, instant 4.0-5.0 4.8 20-30 22 CAFFEINE PRODUCTION
Cocoa, powder 0.08-0.35 0.2 1-8 4
Chocolate milk 0.01-0.025 0.02 2-7 5
Milk chocolate 0.005-0.04 0.02 2-14 6
Approximately 450 tons of caffeine are required annually
Dark chocolate 0.02-0.10 0.08 6-28 23 in the United States for addition to beverages and for phar-
Mate 0.9-2.2 2.0 36-42 40 maceutical use. This need is partially met by the decaf-
Guarana paste 3.9-5.8 4.7 feination of coffee (21). The methylation of theobromine
Kola nut 0.8-2.2 1.5 obtained by extraction of cocoa hulls provides part of the
Cola drinks 0.08-0.16 0.09 20-30 28 remainder of the requirements. Dimethyl sulfate, diazo-
"Serving size is assumed to be 6 oz for hot beverages, 8 oz for cold beverages, methane, and methyl iodide can be used to prepare caf-
and 1 oz for chocolate products. feine from xanthine or any of the related monomethyl- or
dimethylxanthines (22). Patented synthetic processes are
also based on classical organochemical ring closure tech-
niques and do not require the availability of xanthines as
soda products. This usage is based on its stimulatory prop- starting materials.
erties and the slight degree of bitterness that it imparts. In 1995 the United States imported about 1000 tons of
In 1978 the U.S. Select Committee on GRAS Substances caffeine. About 500 tons came from China. Domestic syn-
reaffirmed the safety of caffeine as a beverage additive at thetic caffeine was list-priced at $7.25/lb. The product from
levels current at that time 10 to 12 mg/100 mL). A very China was approximately $4.50/lb (23).
METABOLISM OF CAFFEINE PHARMACOLOGY
!
O H
O CH3 Hv U ' O CH3
H
H. N X AX I I > ^ N -VN
? T CHO O^N^N y |T \CHO
O^ N ^ NH2 I o^ N ^ NH2
I CH3 ,
CH3 3-Methylxanthine CH3
6-Amino-5-(JV-methylformylamino)- f \ 6-Amino-5-(N-methylformylamino)-
1-methyluracil / \ 1,3-dimethyluracil
\ / O CH3 \ /
Y^VV1* OHX /
O CH3 O CH3 \ T JL^ / O H O H
CH
? T ^H
H N
%M /H3^N\-^
J T /^OH ^iVTN>
O^ N N CT^ N N
\
\ ?
3
\ 1,3,7-Trimethyluricacid/
/ 7 T /> -*^N^-N
O^ N N
O^'^N N
O H ? O > O CH,
H
'%YA"<3 - A") - H C
' -N\^CHO
X
O^^-OHO O^ N o^A^
H H H
5-Acetylamino-6-formylamino-3-methyluracil Paraxanthine 6-Amino-5-(AT-methylformylamino)-
1,7-dimethylxanthine 3-methyluracil
I I
TT O O CH3
O HjI H3Cx I '
1180 1 CHs
^N-V * 1 I VOH
1 I O^N^N
O^N^NH 2 I
I il
H
5-acetylamino-6-amino-3-methyluracil 1,7-dimethyluric acid
dependent. It is markedly subject to the development of to caffeine also becomes explicable by this mechanism
tolerance. since caffeine is known to induce the formation of addi-
The arousal model as an explanation for the foregoing tional adenosine receptors in the rat (40).
effects has been suggested (37). Positive response to the
arousal effect of caffeine plus those of any other biological Physical Dependence
and background impacts, increases with an increase in
stimuli but is reversed as the total arousal level exceeds Addiction to caffeine may develop even from short-term
the tolerance level. (seven days) administration of high dosages. Headache
and fatigue are the most common withdrawal symptoms
Other Effects but depression, irritability, anxiety, and vomiting may also
occur. Severity of symptoms that may last for up to one
Caffeine has been reported to increase work output and week range from mild to incapacitating. Many caffeine con-
endurance in long-term exercise regimens. Ergogenic prop- sumers exhibit no withdrawal symptoms. The physiology
erties of caffeine have been observed in many studies of of caffeine withdrawal is not well understood (41).
athletic performance but are subject to confounding fac-
tors: nature of activity, degree of training of athletes, level Toxicity
of caffeine tolerance, and habitual caffeine usage. There
are also many "no effect" reports. An interesting interpre- The physiological effects of caffeine become greatly inten-
tation of these varying results is that the mood-elevating sified at high dosages. Caffeine affects the cortex, the me-
properties of caffeine may be responsible for some of the dulla, and eventually the spinal cord as dosages are in-
positive effects reported (38). creased (28). The LD50 of caffeine is similar for many
Caffeine produces a mild diuresis in humans and in- mammalsabout 200 mg/kg (42). This would suggest an
creases the excretion of sodium, potassium, and chloride LD50 of about 3.5 g for humans based on normal metabolic
ions (28). The thermogenic properties of caffeine cause an weight corrections. It is more generally accepted that the
increase in the resting metabolic rate. Consideration has lethal oral dose is about 1Og. Lethal plasma concentration
been given to its use in managing obesity (39). Respiratory is in the range of 0.5 to 1.0 mM. To achieve this concentra-
rate is increased by caffeine at a plasma level of 5 mg/L. tion would require the consumption of about 75 cups of
The mechanisms for this stimulation are complex and in- coffee over a very short period of time (40). Lethality re-
volve many separate effects. They include increased pul- sulting from beverage consumption is most unlikely. The
monary blood flow through vasodilation, increased sensi- few recorded cases of death from caffeine consumption
tivity of the respiratory centers to carbon dioxide, and have involved the pure substance or medications contain-
improved skeletal muscle contraction (28). This multiple ing it.
response is utilized in the treatment of infantile apnea.
Caffeine as a Drug
Mechanism of Physiological Activities
The primary uses of caffeine as a drug are based on its
The effects of caffeine on the cardiovascular, neurological, effects on the respiratory, cardiovascular, and central ner-
and renal systems and on lipolysis are primarily triggered vous systems. Premature infants, for example, are subject
by the blockage of adenosine receptors through competitive to apnea, a transient but potentially dangerous cessation
antagonism (40). The structural relationship between caf- of breathing. Caffeine has been used to control this syn-
feine and adenine (and therefore adenosine) was shown drome. It decreases apneic episodes and regularizes
previously. Other suggested mechanisms such as the in- breathing patterns (28). It is also used for the treatment
hibition of phosphodiesterases and modification of calcium of bronchiospastic disease in asthmatic patients. Caffeine
metabolism may also be operative but are inadequate to is used widely in drug mixtures designed for relief from
explain these effects at reasonable caffeine concentrations. migraine-type headaches because of its vasoconstrictor ef-
Adenosine and caffeine show contrasting effects on blood fects on the cerebral circulation. Many OTC preparations
pressure, activity of the central nervous system, urine out- of this type are available. They contain 30 to 200 mg of
put, and lipolysis. The well-known induction of tolerance caffeine per tablet. A common application of caffeine's
stimulatory effects on the central nervous system is the of increased cancer risk. An extensive survey of human
use of 100- to 200-mg tablets to prevent drowsiness when studies, based primarily on coffee and tea consumption,
driving or whenever this condition is undesirable. There show little correlation between consumption of the bever-
are about 2000 nonprescription and about 1000 prescrip- ages and cancer incidence (50).
tion drugs containing caffeine. Theoretical considerations suggest a lack of carcino-
genic potential of caffeine based on the facts that it does
not alkylate or combine covalently with DNA, it does not
MUTAGENICITY undergo metabolic activation, and it lacks some of the
structural features of known purine carcinogens (47).
Caffeine attains the same concentration in gonadal tissue Determination of the effect of caffeine on fibrocystic dis-
as in the circulating plasma and may thus reach levels of ease of the breast has also been pursued. Results of the
up to 0.05 mM for very heavy consumers (43). In vitro mu- studies are mixed. There may be some correlation between
tagenicity studies in which positive results are obtained caffeine consumption (based on dietary coffee) and fibro-
generally involve concentrations at least 100 times greater cystic breast disease (51).
and are therefore at or above the lethal concentration for
humans. At these high concentrations, DNA repair is in-
hibited, an effect attributable to its purine analog struc- DECAFFEINATION
ture. Caffeine may thus be considered a weak mutagen
with no significance for humans. Concern with the physiological effects of coffee prompted
early consideration of ways to decaffeinate the product.
The first commercial plant was established by the firm
TERATOGENICITY Kaffee HAG in Germany in 1906 and in the United States
a few years later. The U.S. plant was expropriated by the
Caffeine is teratogenic to rodents at high dosage levels government during World War I, terminating production
(44). Effects such as cleft palates and ectrodactyly result of decaffeinated coffee in the United States until 1932.
from administration of lOOmg/kg/d or more, but only when Only one brand was available until the mid-1950s and
given in a single dose by gavage or injection. Increased solely as the instant product. Consumption later increased
fetal absorption and decreased fetal weight also occur at rapidly and in 1997 accounted for 35% of the instant prod-
these levels, which approach lethality. True teratogenic re- uct and 12 to 14% of ground roasted coffee. Decaffeinated
sponses have usually been associated with dosages that tea appeared on the market in 1978. In 1997 it accounted
result in maternal toxicity. Delayed bone ossification is ob- for approximately 15% of leaf tea consumed in the United
served at much lower levels, but this effect is rapidly com- States and 20% of pure instant tea.
pensated postnatally.
The role of caffeine in the outcome of human pregnancy Coffee
is generally determined by retrospective questioning.
Studies have been based on beverage consumption recall Chlorinated compounds were the first caffeine extractants
and are therefore inexact with regard to the amount of used with coffee. To expedite removal of caffeine, coffee
caffeine ingested or the effects of other beverage compo- beans are steam treated to bring about swelling for greater
nents. There is no clear evidence of teratogenic effects due solvent permeability and to break down caffeine com-
to caffeine (45). Conflicting data exist concerning the re- plexes. In all extraction processes it is necessary to wet the
lationship between maternal caffeine consumption and in- coffee for efficient caffeine removal. Green beans are de-
fant birth weight (46). Since caffeine crosses the placental caffeinated to prevent extraction and loss of the aromatic
barrier, it is possible for high concentrations to occur in the components that are generated only during roasting. After
neonate (47). Most medical advice cautions against high solvent removal by steam distillation, the beans are
caffeine intake during pregnancy. roasted.
Trichlorethylene was commonly used as the solvent un-
til it was eliminated in 1977 because of its suspected car-
CARCINOGENICITY cinogenicity. Methylene chloride then became the decaf-
feinating solvent of choice (36). A residue level of 10 ppm
The carcinogenetic potential of caffeine has been studied is approved by the U.S. Food and Drug Administration. An
intensively in rodents (48). The results of about a dozen unofficial standard providing for the removal of 97% of the
well-controlled studies indicate no carcinogenic effects at- original caffeine has come into use for decaffeinated coffee.
tributable to caffeine. Epidemiological studies regarding The beverage therefore contains 2 to 4 mg of caffeine per
the risk of cancers of the bladder, colon, rectum, pancreas, cup. To eliminate residues of chlorinated compounds, other
breast, ovaries, and liver to human coffee drinkers have decaffeinating solvents are now used. Ethyl acetate is ap-
been carried out in different parts of the world (49). Con- proved in the United States. The process has some dis-
flicting results have been obtained. In almost all instances, advantages: 5 to 6% solids loss and more difficult de-
dose-response relationships have not been observed, cast- solventization.
ing doubt on any causal relationships between the effect Decaffeination using water as the only solvent to con-
and the consumption of coffee. The fact that tea consump- tact the coffee is also carried out. A concentrated coffee
tion often produces different effects, sometimes converse, extract freed of caffeine contacts the green beans. Noncaf-
makes it unlikely that caffeine itself is a causative agent feine solids are not removed under these conditions. The
extract is then regenerated for use by adsorbing the caf- 11. B. A. Kihlman, in Caffeine and Chromosomes, Elsevier, Am-
feine on activated carbon (52). Coffee oil expressed from sterdam, 1977, pp. 11-13.
beans is used as a decaffeinating solvent along with other 12. E. Looser, T. W. Bauman, and H. Warner, "The Biosynthesis
vegetable oils in another operating process. Caffeine is re- of Caffeine in the Coffee Plant," Phytochemistry 13, 2515-
moved from the oils by a liquid-liquid extraction system 2517 (1974).
with water as the second solvent (53). 13. P. Mazzafera et al., "S-Adenosyl-L-MethioninerTheobromme
Supercritical CO2 extraction is now widely used for de- I-Af-Methyltransferase, an Enzyme Catalyzing the Synthesis
caffeination (54). The process is carried out at 300 bars and of Caffeine in Coffee," Phytochemistry 37, 1577-1584 (1994).
at 60 to 9O0C. Caffeine solubility increases as temperature 14. T. Suzuki, H. Ashihara, and G. R. Wallace, "Purine and Purine
and pressure are raised. The extracted caffeine may be re- Alkaloid Metabolism in Camellia and Coffea Plants," Phyto-
moved from the supercritical fluid by reducing the pres- chemistry 31, 2575-2582 (1992).
sure, thereby decreasing its solubility or by passing the 15. H. Ashihara and H. Kubota, "Biosynthesis of Purine Alkaloids
mixture over activated carbon. Techniques that avoid the in Camellia Plants," Plant Cell Physiol. 28, 535-539 (1987).
necessity for repressurizing the gas are preferable. Super- 16. O. Negishi, T. Ozzawa, and H. Imagawa, "Biosynthesis of Caf-
critical processes are capital intensive but result in prod- feine from Purine Nucleotides in Tea Plant," Biosci. Biotech-
nol. Biochem. 56, 499-503 (1992).
ucts of superior quality with no solvent residues. In 1997
supercritical extraction was used to prepare about 50% of 17. M. A. Bokuchava and N. I. Skobeleva, "The Biochemistry and
Technology of Tea Manufacture," CHt. Rev. Food Sd. Nutr. 12,
the decaffeinated coffee in the United States.
348 (1980).
Tea 18. M. Dong et al., "The Occurrence of Caffeine in the Air of New
York City," Atmos. Environ. 11, 651-653 (1977).
The commercial procedures for the decaffeination of tea 19. J. J. Barone and H. R. Roberts, "Caffeine Consumption,"Food
are, in principle, similar to those used for coffee. For prac- Chem. Toxicol. 34, 119-129 (1996).
tical reasons it is necessary to utilize manufactured black 20. H. R. Roberts and J. J. Barone, "Biological Effects of Caffeine;
tea rather than fresh green leaf. Conservation of aroma History and Use," Food Technol. 37, 32-39 (1983).
during processing is desirable. Decaffeinated tea appeared 21. U.S. Pat. 4,818,552 (Apr. 4, 1989), L. Kaper (to Douwe Eg-
on the market in 1978. Similar process evolution took place berts).
as with coffee. Decaffeination with supercritical CO2 be- 22. U.S. Pat. 2,534,331 (Dec. 19, 1950), D. W Woodward (to E.I.
came a commercial process in 1984 (55). Aroma may be du Pont de Nemours & Co.)
previously stripped with dry supercritical CO2 or with the 23. Anonymous communication, Chemical Marketing Reporter
moist gas at atmospheric pressure for later addition to the 247, no. 8 Feb. 20 (1995).
product (56). 24. R. W. Von Borstel, "Biological Effects of Caffeine; Metabo-
lism," Food Technol. 37, 40-45 (1983).
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112, 359-365 (1993).
in several stages, namely, initiation, promotion, and pro-
37. B. Smith, "Effects of Acute and Habitual Caffeine Ingestion
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in Physiology and Behavior; Tests of a Biobehavioral Arousal
Theory," Pharmopsychoecologia 7, 151-167 (1994).
begins with attack of a cancer-inducing agent on a target
site in the DNA of the cell. In this process a normal cell is
38. R. J. Lamarine, "Caffeine as an Ergogenic Aid," in G. A.
Spiller, ed., Caffeine, CRC Press, New York, 1998, pp. 244- converted into a cancer cell. The transformation is irre-
245. versible. During the promotion stage the transformed cell
39. A. G. Dulloo et al., "Normal Caffeine Consumption: Influence may grow into a tumor; not all cells do. Progression is the
on Thermogenesis and Daily Energy Expenditure in Lean and stage wherein a benign tumor may become malignant.
Postobese Human Volunteers," Am. J. Clin. Nutr. 49, 44-50 Nutritional studies of the influence of diet on cancer risk
(1989). can be carried out in animals by direct experimentation
40. R. Von Borstel and R. J. Wurtman, "Caffeine and the Cardio- and in humans by using epidemiological methods. Both
vascular Effects of Physiological Levels of Adenosine," in P. B. methods provide useful data that can then be examined
Dews, ed., Caffeine, Springer-Verlag, Berlin, 1984, pp. 142- further to determine influences of diet on causation and,
150. possibly, inhibition of tumor growth.
41. R. R. Griffiths and P. P. Woodson, "Caffeine Physical Depen- Animal studies are relatively easy to carry out. The ani-
dence: A Review of Human and Laboratory Animal Studies," mal of choice (almost always a mouse or rat) is subject to
Psychopharmacology (Berlin) 94, 437-451 (1988). treatment with a carcinogenic agent and observed for a
42. B. Stavric, "Toxicity to Humans. 2. Caffeine," Food Chem. Tox- specified length of time before being subjected to necropsy.
icol 26, 645-662 (1988). The advantages of this system are an experimental con-
43. R. H. Haynes and J. D. B. Collins, "The Mutagenic Potential sistency and total control over diet and life span. But even
of Caffeine" in P. B. Dews, ed., Caffeine, Springer-Verlag, Ber- here different strains of mice or rats do not always give the
lin, 1984, pp. 231-238. same result. Additionally, the experimental animal is
44. J. G. Wilson and W. J. Scott, Jr., "The Teratogenic Potential caged, which may produce a certain amount of stress; a
of Caffeine in Laboratory Animals," in P. B. Dews, ed., Caf- lifetime effect of treatment is never seen; and there are
feine, Springer-Verlag, Berlin, 1984, pp. 165-187.
virtually no studies in which the diet is varied. Still, ani-
45. A. Berger, "Effects of Caffeine Consumption on Pregnancy mal studies provide useful data concerning mechanisms of
Outcome," J. Reproduct. Med. 33, 945-956 (1988).
carcinogenesis and of effects of dietary and drug treat-
46. J. Nash and T. V. N. Persaud, "Reproductive and Teratological ment. The results of animal studies are not directly appli-
Risks of Caffeine," Anatomischer Anzeiger 167, 265-270
(1988). cable to humans.
Epidemiological studies of cancer in humans use varied
47. W. D. Parsons and A. H. Niems. "Prolonged Half-Life of Caf-
feine in Healthy Term Newborn Infants," J. Pediatrics 98, approaches. Ecological or correlation studies are studies in
640-641(1981). which differences between populations are examined.
48. H. C. Grice, "The Carcinogenic Potential of Caffeine," in P. B. These may be examinations of specific nutrients or of pat-
Dews, ed., Caffeine, Springer-Verlag, Berlin, 1984, pp. 153- terns of food intake. Generally investigation of food dis-
164. appearance data is not as useful as studies of individual
49. Committee on Diet and Health, National Research Council, dietary components. Studies in humans may include mi-
Diet and Health, National Academy Press, Washington, D.C., grant studies (cancer incidence in the new location vs can-
1989. cer incidence in the old location); case-control studies, in
50. G. A. Spiller and B. Bruce, "Coffee, Tea, Methyl Xanthines, which cases are compared with age-matched controls; and
Human Cancer, and Fibrocystic Breast Disease," in G.A. follow-up studies, in which appearance of cancer is com-
Spiller, ed., Cancer, CRC Press, New York, 1998, pp. 326-336. pared between exposed or unexposed individuals. Studies
51. U.S. Pat. 3,671,263 (June 20, 1972), J. M. Patel and A. B. involving assessment of past dietary intake are subject to
Wolfson (to Proctor and Gamble Co.). errors in recall. Many foods are important sources of more
52. Anonymous, "Coffex Avails Swift Water Process to N. Amer- than one nutrientmeat, for instance, is a source of both
ica," Tea and Coffee Trade Journal 160, 45-47 (1988). protein and fatwhich adds to the complexity of diet as-
53. U.S. Pat. 4,837,038 (June 6, 1989), J. C. Proudley (to Nestea sessment.
SA). A good example of the complexity of epidemiological
54. U.S. Pat. 4,820,537 (Apr. 11, 1989), S. N. Katz (to General studies may be found in two studies of diet effects on colon
Foods Corp.). cancer carried out in Australian cities that are about 400
55. W. Ger. Pat. 3,515,740 (May 2, 1985), H. Klima, E. Schiitz, miles apart. In Adelaide, Potter and McMichael (1) found
and H. Vollbrecht (to SKW Trostberg AG). colon cancer risk to be associated with protein and energy
56. Eur. Pat. 269,970 (June 8, 1988), E. Schiitz and H. Vollbrecht intake, but fiber intake was, if anything, a risk for colon
(to SKW Trostberg AG). cancer. Kune et al. (2) in Melbourne found dietary fiber to
be protective.
HAROLD GRAHAM Armstrong and Doll (3) reviewed the effects of diet on
Consultant cancer worldwide and suggested that the correlations
New York, New York found in their survey be regarded as guides to further re-
search rather than as evidence of causation. In 1987 a re- of simple sugars as did Hems (11), but an inverse corre-
view by Doll and Peto (4) raised interest in diet and cancer lation was seen with starch intake (12). Longtime feeding
to a new level. They suggested that 30 to 70% of cancer in of sucrose to rats (13) or mice (14) did not result in in-
the United States might be related to diet and stated that creased tumorigenesis. The available evidence is scanty,
this value was "highly speculative and chiefly refers to and it is not possible to form any conclusion except for the
dietary factors which are not yet reliably identified." safe one; namely, more research is needed. Most dietary
In 1982 a committee of the National Academy of Sci- fiber is carbohydrate in nature, but that represents a spe-
ences (U.S.) (5) reviewed influences of diet on cancer. Their cial case that is discussed later.
conclusions were (in part):
+ sulfate
Glucosinolates
well as a crop rotation with cereals; wheat or barley follow- cereal grains (15%). The maximum moisture content for
ing canola is the preferred sequence. Most fields are not storage of clean canola seeds in a cool environment (< 150C)
cropped with canola more than once every four years. This is 10% (24); others sources (22,25) even suggest lower op-
practice permits a break in disease and insect pest cycles, timum levels of moisture (8-9%) for storage over periods
while preserving the soil structure. Canola is susceptible of several months. Above this level, the seeds must be air
to several fungal diseases such as blackleg (Leptosphaeria dried; air temperatures must be kept below 380C to pre-
maculans), stem rot (Sclerotinia sclerotiorum), damping- vent heat damage. Aeration during storage, although at
off (Fusarium spp.), root rot (Rhizoctonia spp.), and black much lower airflow rates than drying, is also required to
spot or leaf spot (Alternaria spp.); disease severity varies prevent moisture gradients and to cool the stored grain.
with year and location (19). A number of different insects Figure 2 shows how storage is affected by both tempera-
can also cause serious damage to canola (eg, flea beetle) ture and moisture content. Canola is particularly prone to
(20). Crop rotation is effective in controlling fungi and in- microbial spoilage, with severe losses in seed and oil qual-
sects. Several herbicides are also available for a variety of ity. The rate of spoilage rapidly increases if nonuniform
weed species (12,21). distributions of moisture and temperature exist in the
stored grain. An important consideration regarding mois-
Harvest and Storage Practices ture content of canola is that before solvent extraction of
the oil, the seed must be cooked rapidly at temperatures
The date and method of canola harvesting are important
between 80 and 10O0C and at water contents between 6
determinants of yield and seed quality (12,18,22). Imma-
and 10% to inactivate myrosinase; above 10% moisture,
ture seeds have higher chlorophyll and free fatty acids con-
hydrolysis of glucosinolates would occur; below 6%, heat
tents. On the other hand, if the harvest is delayed, canola
inactivation of the enzyme is difficult.
is susceptible to shattering of the pods, particularly in
Chlorophyll is another important quality parameter of
windy areas. To avoid this, swathing (leaving cut plants to
canola. Besides imparting an undesirable color to the oil,
dry in the field) is applied when the majority of the seeds
chlorophyll promotes oxidative rancidity in salad oils. Sev-
are at a firm doughlike stage (moisture content 35-40%).
eral environmental factors and agronomic practices, in-
Swathing facilitates uniform maturation and yields seeds
cluding length of growing season, temperature during seed
of good color and high in oil and protein. Premature swath-
ing (seed moisture >45%) results in reduced yields,
whereas late swathing (moisture <20%) increases shatter-
ing losses and the possibility of frost damage. Canola is
ready to combine when the moisture content is below 15%. Spoilage
Freshly harvested seeds normally require up to six weeks will occur
Grain temperature (0C)
ACP ACP
CoASH CoASH
^
C4:0
i
i
I Lauroyl - ACP
I thioesterase
C12 : O - C12 : O - ACP
i
I Palmitoyl - ACP
' thioesterase
C16 : O C16 : O - ACP
I
CIS : O
Stearoyl - ACP
thioesterase
CIS : O - ACP
p-IQ . O*
~ lb * 6
/ Lmoleoyl
/ desaturase
p-io . o*
Stearoyl-ACP in i
desaturase /, 0^1
,. / desaturase
CIS : 1 - ACP /
i /
CIS : 1 CIS: I- CoA
\ Fatty acid
\ elongase
C20 : 1 - CoA
\ Fatty acid
^ elongase
C22 : 1 - CoA
Figure 3. A simplified scheme for the synthesis of fatty acids in plants seeds. Abbr.: ACPacyl
carrier protein; CoASHcoenzyme A. * The oleoyl and linoleoyl desaturases act on C 18:1 and C 18:2
moieties of phosphatidylcholine to produce C 18:2 and C 18:3, respectively.
(possess cytoplasm that allows normal production of pol- The Brassica oilseeds have responded to genetic manip-
len), and (3) a restorer or male parent line that carries ulation better than any other crop. The rapidly growing
nuclear genes that will restore normal fertility to the hy- interest for crop improvement and modification by noncon-
brid cultivars. The expected level of heterosis (up to 40% ventional breeding approaches as a result of advances in
seed yield increase) is sufficient to offset the cost associated molecular biology and tissue culture techniques is cur-
with the development of an effective cytoplasmic male- rently focused on several areas of research (39,45,46).
sterile, genetic restorer system (10,31). Although SI hy-
brids have been released in Canada, a limitation of the self- 1. Production of haploids by culture of reproductive or-
incompatibility system for field crops, even though it is gans to reduce the time required for new cultivar de-
used for vegetable crops, is the relatively high cost. velopment.
Table 1. Fatty Acid Composition of Normal and Modified and versatile Brassica oilseeds in the future. Specialty oils
Rapeseed Oil Resulting from Selection and by-products for both food and industrial uses, which
Fatty acid are within reach of today's breeders, are expected to influ-
ence the production and marketing of rapeseed/canola in
Oil Type 16:0 16:1 18:0 18:1 18:2 18:3 20:1 22:1
the years ahead.
High erucic
Normal 3 <11 11 13 8 8 50 COMPARISON OF CANOLA WITH OTHER OILSEEDS
Selected 2 <1 1 11 12 9 9 57
The reduction of erucic acid in rapeseed oil resulted in a
Canola marked increase in oleic acid along with smaller increases
Low erucic 4 <1 1.5 61 27 9.5 21 <1 in linoleic and linolenic acids. Canola oil has a fatty acid
High-oleic 3.5 <1 2.5 77 8 2.5 1.5 <1 composition similar to peanut and olive oil with the excep-
Low-linolenic 4 <11 61 27 2 1 <1 tion of the lower palmitic and higher linolenic acid con-
High-laurica 3 <1 1.5 33 11 6.5 1 <1 tents. Canola oil contains the lowest level of saturated
a
C12:0, 39%; C14:0, 4%.
fatty acids (mainly palmitic and stearic acids) and the
Source: Refs. 41 and 42. highest content of unsaturated fat (mainly monounsatu-
rated) of the common edible vegetable oil sources (Fig. 4).
The total quantity of polyunsaturated fatty acids
(C18:2n-6 and C18:3n-3) in canola oil is intermediate
among the vegetable oils, although it contains an excellent
2. Protoplast fusion to transfer desirable genetic traits,
balance between linoleic acid and linolenic acid compared
particularly those carried by cytoplasmic organelles
with other widely used vegetable oils. The relatively high
(chloroplast, mitochondria). Transfer of cytoplasmic
linolenic acid content of regular canola oil (10%) makes it
traits such as male sterility and herbicide resistance
susceptible to oxidative rancidity. This problem has been
was made possible via protoplast fusion and microin-
alleviated in the newly developed low linolenic acid culti-
jection techniques (39).
vars (35,36), although the presence of lipoxygenase in ca-
3. Selection of cell variants with desirable agronomic nola seeds has been reported (48). In most respects, there
characteristics (eg, herbicide resistance, drought tol- is no obvious physical property distinguishing canola oil
erance, winter hardiness) after treatment with mu- from other common vegetable oils. Rapeseed oils (both high
tagenic agents and selection pressure of treated and low erucic acid), however, contain a C2s brassicasterol,
cells. which is not found in other edible vegetable oils (49); bras-
4. Gene transfer using suitable vectors (Agrobacterium sicasterol is thus a suitable marker to identify Brassica oils
tumefaciens) or by microinjection techniques. in vegetable oil blends.
The protein content of canola meal varies with the va-
Consideration is primarily given to genes responsible for riety from which it is produced; it ranges between 36 and
herbicide and fungal disease resistance, osmotolerance, 42%. Canola meal is higher in fiber than soybean meal
manipulation of triglyceride composition, and production (Table 2). The amino acid composition compares well with
of novel high value chemicals (eg, jojoba-type waxes having that of soybean meal (50,51). Although the latter has a
as precursors eicosenoic and erucic acids). greater lysine content, canola meal contains more of the
Most prevalent among the novel-trait canola cultivars sulfur-containing amino acids (methionine and cystine).
are herbicide-tolerant cultivars. Several B. napus varieties Consequently, the two meals tend to complement each
that are tolerant to the herbicides glyphosate (Round-up other when used as feedstuffs in rations for livestock and
Ready), glufosinolate-ammonium (Liberty Link), and imi- poultry. Canola meal is a richer source of minerals than
dozolonone (Smart) are presently being grown in Canada. soybean meal (50,51) (Table 3). However, the presence of
In fact, herbicide-tolerant varieties were estimated to ac- higher amounts of phytic acid and fiber in canola meal re-
count for 55 to 60% of the total acreage devoted to canola duces the availability of calcium, magnesium, manganese,
production in 1998 (47). By contrast, it was estimated that phosphorus, zinc, and copper for nonruminant animals
only 25 to 30% of the total acreage was devoted to trans- (viz., poultry and swine) (51,52). Nevertheless, canola meal
genie herbicide-tolerant varieties in 1997. In addition to is a better source of available calcium, iron, manganese,
the development and testing of B. napus lines, several lines phosphorus, selenium, and most vitamins than is soybean
of herbicide-tolerant B. rapa also have been developed and meal. Canola meal has been shown to have less metaboliz-
are being tested for agronomic properties. The rapid de- able energy than soybean meal (50); on a nutrient content
velopment of transgenic canola varieties in Canada has basis alone, canola meal is equivalent to 70 to 75% of 44%
been the result of effective collaboration among industry, protein-content soybean meal for feeding poultry and to
government, and university researchers and the fact that about 75 to 80% of the same for feeding swine and rumi-
canola breeding in Canada is conducted primarily by pri- nants. A reduction in fiber content of the meal would im-
vate industry, companies such as Pioneer Hi-Bred, Zeneca prove the metabolizable energy value. Seeds with yellow
Seeds, Plant Genetic Systems (Canada) Lyd., Saskatche- color have a lower hull content and, in turn, fiber content
wan Wheat Pool, AgrEvo, Limagrain Canada, and Svalof than dark seeds, and the hull is more digestible (50). None-
AB (48). The impact of genetic engineering and conven- theless, the available energy in canola meal is a critical
tional breeding is expected to result in even more valuable factor in its use in animal feeds.
Comparison of Dietary Fats
DIETARYFAT Fatty acid content normalized to 100 per cent
Canola oil
Safflower oil
Sunflower oil
Corn oil
Olive oil
Soybean oil
Peanut oil
Cottonseed oil
Lard*
Beef tallow*
Palm oil
Butterfat*
Coconut
*Cholesterol content (mg/tbsp): lard 12; beef tallow 14; butterfat 33. No cholesterol in any vegetable-based oil.
Source for data: POS Pilot Plant Corporation, Saskatoon, Saskatchewan, Canada June 1994.
Saturated f a t L i n o l e i c acid
Alpha-linolenic a c i d M o n o u n s a t u r a t e d f a t
9an Omega-3 fatty acid
Figure 4. Fatty acid composition of common dietary fats. Source: Canola Council of Canada.
PROCESSING
High Erucic Acid Oil Alkyl esters of brassylic acid are excellent plasticizers.
Erucic acid, a long chain fatty acid (C22:1) containing a sin- The corresponding allyl and vinyl esters form polymers
gle double bond, exhibits high fire and smoke points and copolymers that may be used in molding compounds,
(2710C). These properties allow erucic acid to withstand reinforced plastics, laminates, sealants, and coatings (85-
high temperatures and still remain a liquid at room tem- 88).
perature (79). Consequently, oils containing high levels of
erucic acid are used as lubricants or in lubricant formula- STANDARDS AND SAFETY
tions (80). Because of their lubricant properties, HEAR oils
have found applications as spinning lubricants in the tex- The standards for crude and refined, bleached, deodorized
tile, steel, and shipping industries, as drilling oils, and as canola oil, as outlined in Table 6, were established in 1987
marine lubricants (81). High erucic acid oil has also been by the Canadian General Standard Board (CGSB). Such
used for the clinical treatment of adrenoleukodistrophy, a standards are used in purchasing, consumer protection,
rare children's disease. Hydrogenated HEAR oils have in- health and safety, international trade, and regulatory ref-
dustrial applications by producing hard, glossy waxes (82). erence (90). In addition, there is also the Canada Agricul-
tural Products Standard Act, which defines the quality of
Erucic Acid Derivatives
products, including canola oil (Table 4), for regulating the
Erucic acid and its hydrogenated derivative, behenic acid, grading, packing, and marketing of processed canola oil in
and erucyl and behenyl alcohols as well as other deriva- Canada. These come under the jurisdiction of Agriculture
tives including esters, amides, amines, and their salts are Canada (90).
used extensively in industry as slip, softening, antifoam- Canola oil has been approved by Health and Welfare
ing, and release agents; emulsifiers; processing aids; con- Canada under the Food and Drugs Act and Regulations as
ditioners; antistatic agents; stabilizers; and corrosion in- safe for human consumption (91). The Canadian legisla-
hibitors (80). tion favors consumption of canola oil over that of rapeseed
oil by limiting the amount of C22 monoenoic fatty acids
CH3(CH2)7CH = CH(CH2)nCOOH such as erucic acid (C22:1) permitted in dietary fats. The
erucic acid three sections of this act, outlined in Table 7, refer to this
CH3(CH2)7CH2CH2(CH2)11COOH particular restriction. For example, Section B.09.022 re-
behenic acid fers to a restriction of less than 5% C22 monoenoic fatty
acids in fats and oils, in shortenings, salad and cooking
Erucamide, the amide derivative of erucic acid, has oils, as well as table spreads. A similar restriction is cited
been used for many years as a processing aid and antiblock in Section B.07.043 for salad dressings, while Section
Table 6. Canadian General Standards Board Requirements for Canola Oil
A. Crude canola oil
Characteristics Super degummed Degummed
Free fatty acids (as oleic acid), % by mass, maximum 1.0 1.0
Moisture and impurities, combined % by mass, maximum 0.3 0.3
Phosphorus, ppm, maximum 50 200
Chlorophyll, ppm, maximum 30 30
Sulfur, ppm, maximum 10 10
Refined, bleached color, Lovibond (133.4 mm cell), maximum 1.5 red 1.5 red
Erucic acid, % by mass, maximum 2.0 2.0
Table 7. Regulations in Canada's Food and Drugs Act B.25.054(a)(iii) limits C22 monoenoic acids in infant for-
Relating to Canola and Rapeseed Oils mula to a maximum of 1% of the calories. In Canada, only
2% erucic acid is now permitted in canola oil, which is
B.09.001 (S) Vegetable fats and oils shall be fats and oils much lower than the 5% indicated in the Codex standard
obtained entirely from the botanical source for low erucic acid oils by Codex Alimentarious Commis-
after which they are named, shall be dry and
sweet in flavour and odour and, with the
sion FAOAVHO 1982 (89). Erucic acid oil with a maximum
exception of olive oil, may contain Class IV of 2% was subsequently granted GRAS (generally regarded
preservatives, an antifoaming agent, and /?- as safe) status in the United States (1985) by the FDA (92).
carotene in a quantity sufficient to replace This oil, now identified as canola oil, has since been rec-
that lost during processing, if such addition is ognized by the American Health Foundation as a healthful
shown on the label. product in the consumer market. A comprehensive review
B09.022 No person shall sell cooking oil, margarine, on the safety and health aspects of canola oil (93) con-
salad oil, simulated dairy products, shortening cluded that, because of its fatty acid composition, canola
or food that resembles margarine or oil can be a good substitute for saturated fat in diets in-
shortening, if the product contains more than tended to reduce the risk of hypercholesterolemic and cor-
5 percent. C22 Monoenoic Fatty Acids
calculated as a proportion of the total fatty
onary heart disease. Current nutritional recommendations
acids contained in the product. by many health organizations suggest a reduction of the
B07.043 No person shall sell a dressing that contains calories derived from fat in the diet to about 30% and no
more than 5 percent C22 Monoenoic Fatty more than 10% of the caloric intake as saturated fat.
Acids calculated as a proportion of the total
fatty acids contained in the dressing.
FUTURE OF CANOLA
B25.054 (1) Except as otherwise provided in this Division,
no person shall sell or advertise for sale of
human milk substitute unless it contains, The discovery of cytoplasmic male sterility (CMS) in Bras-
when prepared according to directions for use. sica spp. a decade ago led to considerable research in de-
(a) per 100 available kilocalories veloping new hybrids. Because B. napus spp. of canola are
(i) not less than 3.3 and not more than 6.0 mainly self-pollinated, the development of hybrids re-
grams of fat. quires cross-pollination. The CMS system has been per-
(ii) not less than 500 milligrams of linoleic fected and is now used for the production of commercial
acid in the form of a glyceride. hybrids. Future research should result in improved hy-
(iii) not more than 1 kilocalories from C22 brids for commercial production. The application of bio-
Monoenoic Fatty Acids. technology (and genetic engineering) will assist in the de-
Source: Ref. 92. velopment of improved canola lines that mature early, are
frost resistant, are resistant to pesticides, are blackleg tol- 14. G. R. Fenwick, R. K. Heaney, and W. J. Mullin, "Glucosino-
erant, as well as higher yielding. B. napus varieties require lates and Their Breakdown Products in Food and Food
long days to flower, so future research will develop lines Plants," Crit. Rev. Food Sd. Nutr. 18, 123-201 (1983).
that mature earlier without any loss in yield 15. B. Uppstrom, "Seed Chemistry," in D. S. Kimber and D. I.
(8,31,35,94,95). New high protein lines will also be devel- McGregor, eds., Brassica Oilseeds: Production and Utiliza-
oped for B. napus varieties, whereas higher yields and oil tion, CAB International, Wallingford, UK, 1995, pp. 217-242.
content and modified fatty acid composition are the long- 16. D. S. Hutcheson, "Development of Improved B. campestris
term goals for B. rapa breeding research programs. Bio- Cultivars Essentially Free from Both Alkenyl and Indolyl
Glucosinolates," Canola Research Summary 1985-1989, Ca-
technology should also result in new lines with cold tem-
nola Council of Canada, Winnipeg, Manitoba, 1989, p. 54.
perature hardiness and frost resistance that can
germinate at much lower soil temperatures and permit 17. L. L. Diosady, L. J. Rubin, C. R., Phillips, and M. Naczk, "Ef-
fect of Alkanol-Ammonia-Water Treatment on the Glucosi-
early seeding. As breeders and genetic engineers manage nolate Content of Rapeseed Meal," CaTi. Inst. Food ScL Tech-
to tailor rapeseed/canola, segregating the crop on the basis nol. J. 18, 311-315 (1985).
of specific characteristics will evolve. Processors may de- 18. B. Loof, "Cultivation of Rapeseed," L. A. Appelqvist and R.
velop contracts with farmers to plant varieties that provide Ohlson, eds., Rapeseed: Cultivation, Composition, Processing
products with the desired end-use properties. In addition and Utilization, Elsevier, Amsterdam, 1972, pp. 49-59.
to the breeding programs, modifications in canola process- 19. S. R. Rimmer and L. Buchwaldt, "Diseases," in D. S. Kimber
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products while being environmentally safe. Utilization, CAB International, Wallingford, UK, 1995, pp.
111-140.
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74. J. M. Snyder, E. N. Frankel, and E. Selke, "Capillary Gas
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to accelerated storage at 6O0C, Lebensm.-Wiss. TechnoL 26, GENERAL REFERENCES
205-209 (1993).
76. Federal Register, 42, 44335-48336 (1977). References 9, 25, 78, and 89 are also good general references.
77. M. D. Pickard et al., "Processing of Canola Seed for Quality L. A. Appelqvist and R. Ohlson, Rapeseed Cultivation, Composi-
Meal," in R. Salman and D. R. Clandinin, eds., Canola Meal tion, Processing and Utilization, Elsevier, Amsterdam, 1972.
for Livestock and Poultry, Canola Council of Canada, Winni- D. S. Kimber and D. I. McGregor, Brassica Oilseeds: Production
peg, Canada, 1989, pp. 3-4. and Utilization, CAB, International, Wellingford, UK, 1995.
78. Anonymous, "What's Black and White and Read All Over?" J. K. G. Kramer, F. D. Sauer, and W. J. Pigden, eds., High and
Canola Digest 22, 1 (1988). Low Erucic Rapeseed OilsProduction, Usage, Chemistry and
79. H. J. Nieschlag et al., "Synthetic Wax Esters and Diesters Toxicological Evaluation, Academic Press, New York, 1983.
from Crambe and Limnanthes Seed Oils," Ind. Eng. Chem. G. Robbelen, R. K. Downey, and A. Ashri, Oil Crops of the World,
Prod. Res. Dev. 16, 202-207 (1977). McGraw-Hill, New York, 1989.
R. E. Salmon and D. R. Clandinin, Canola Meal for Livestock and
80. D. L. van Dyne, M. G. Blase, and K. D. Carlson, Industrial
Poultry, Canola Council of Canada, Winnipeg, Manitoba.
Feedstocks and Products from High Erucic Acid Oil: Crambe
D. H. Scarisbrick and R. W. Daniels, Oilseed Rape, Collins, Lon-
and Industrial Rapeseed, University of Missouri, Columbia,
don, 1986.
1990.
D. Swern, Bailey's Industrial Oil and Fat Products, 4th ed., John
81. H. J. Nieschlag and I. A. Wolff, "Industrial Uses of High Er- Wiley & Sons, New York, 1985.
ucic Oils," J. Am. Oil Chem. Soc. 41, 1-5 (1971). M. Vaisey-Genser and N. A. M. Eskin, Canola Oil: Properties and
82. T. K. Miwa and I. A. Wolff, "Fatty Acids, Fatty Alcohols, Wax Performance, Canola Council of Canada, Winnipeg, Manitoba
Esters and Methyl Esters from Crambe abyssinica and Lu- 1987.
naria annua Seed Oils," J. Am. Oil Chem. Soc. 40, 742-744
(1963).
83. J. L. Greene, Jr. R. Perkins, Jr., and I. A. Wolff, "Aminotri- N. A. M. ESKIN
decanoic Acid from Erucic Acid," Ind. Eng. Chem. Prod. Res. B. E. MCDONALD
Dev. 8, 171-176 (1969). University of Manitoba
84. R. B. Perkins, Jr. et al., "Nylons from Vegetable Oils: -13, Winnipeg, Manitoba, Canada
-13/13 and - 6/13," Mod. Plastics 46, 136-139 (1969).
85. S. P. Chang, T. K. Miwa, and I. A. Wolff, "Alkyl Vinyl Esters
of Brassylic Acid," J. Polym. Sd., Part A-I, 5, 2457-2556 CARAMEL. See COLORANTS: CARAMEL.
(1967).
86. S. P. Chang, T. K Miwa, and W. H. Tallent, "AUyHc Prepoly-
mers from Bassylic and Azelaic Acids," J. Appl. Polym. Sd. CARBOHYDRATES: CLASSIFICATION,
18, 319-334 (1974). CHEMISTRY, AND LABELING
87. H. J. Nieschlag et al., "Brassylic Acid Esters as Plasticizers
for Polyviny!chloride," Ind. Eng. Chem. Prod. Res. Dev. 3, Carbohydrates can be, and are, classified in several differ-
146-149 (1964). ent ways. They are often classified according to function-
88. H. J. Nieschlag et al., "Diester Plasticizers from Mixed ality in the minds of food scientists, for example, as sweet-
Crambe Dibasic Acids," Ind. Eng. Chem. Prod. Res. Dev. 6, eners, nonsweet (or only slightly sweet) bulking agents,
201-204 (1967). texturizing materials, suspending agents, and so on. While
89. FAO/WHO, Codex Standards for Edible Low Erucic Acid tables generally have not been constructed in this way,
Rapeseed Oil. Codex Standard 123-1981. Codex Alimentar-
ious Commission, Joint Food and Agriculture Organization/
that is the approach taken later in this article. First the
World Health Organization Food Standards Programme, more traditional method will be presented. Both types of
April 1982. classification are included in Table 1.
90. M. Vaisey-Genser, "Regulations Related to Canola Oil," in M.
Vaisey-Genser and N. A. M. Eskin, eds., Canola Oil: Proper- MONOSACCHARIDES
ties and Performance, Canola Council of Canada, Winnipeg,
Canada, 1987, pp. 10-15.
91. Health and Welfare Canada, The Food and Drugs Act and Monosaccharides, often called simple sugars, are individ-
Regulations, Supply and Services Canada, Ottawa, 1953, ual carbohydrate molecules that cannot be hydrolyzed to
amended to September 1986. smaller, simpler carbohydrate units. The only ones found
92. Food and Drug Administration, Direct Food Substances Af- in food, beverage, and confectionery products to any ap-
firmed as Generally Regarded as Safe; Low Erucic Add Rape- preciable extent are D-glucose and D-fructose. Most mono-
seed Oil. Federal Food, Drug and Cosmetic Acit 21 CRF Part saccharides present in prepared food, beverage, and con-
Table 1. Major Carbohydrate Ingredients Table 1. Major Carbohydrate Ingredients (continued}
Natural Derived Natural Derived
Monosaccharides
Sources of fiber
Glucose/dextrose0 SorbitoP
Fructose" XylitoF Cellulose (powdered, microcrystalline, microfibrillated,
Mannitol microreticulated)
Glucono-($-lactone (glucono-delta-lactone) Brans (wheat, rice, barley, corn, oat)
/?-glucan preparations
Oligosaccharides Ordinary food gums6
6 Psyllium gum
Sucrose Hydrogenated glucose syrup
Resistant starch
Lactosec (maltitol syrup)
Polydextrose
Maltodextrinsa
Sugar beet fiber
Fruit fiber preparations
Carbohydrate sweeteners
a
See SWEETENERS: NUTRITIVE.
Sugar6 6
See SUGAR: SUCROSE.
Glucose (corn) syrups" c
See LACTOSE.
High-fructose (corn) syrups" d
See STARCH.
Honey" e
See GUMS.
Molasses" '"See FIBER, DIETARY.
Sorbitol"
D-Glucose
glucose oxidase
Reduction
D-Glucose D-Glucitol
(sorbitol)
D-Fructose
Figure 2. Reduction of D-glucose to sorbitol.
Glucose is isomerized to fructose by the enzyme glucose The upper limit to the number of saccharide (glycosyl)
oxidase, which is the basis for the production of high- units in an oligosaccharide is undefined. It is often stated
fructose syrups (high-fructose corn syrups, HFCS). First to be 10, sometimes 20. There are 2 monosaccharide units
starch is completely enzyme-converted to D-glucose, which in a disaccharide, 3 in a trisaccharide, 4 in a tetrasacchar-
is then isomerized to D-fructose. Generally, two fructose ide, 10 in a decasaccharide, and so on. Chains containing
syrups are made, a 42% fructose and a 55% fructose syrup. more than 20 units are generally considered to be polymer
Crystalline fructose is also available from this process. molecules, that is, polysaccharides. With the exception of
In addition to starch being completely converted to glu- only a few naturally occurring oligosaccharides, the gly-
cose (crystalline and solution/syrup form), various glucose cosyl (generally pyranosyl, occasionally furanosyl) units in
syrups (corn syrups) are also produced from it. Such syrups oligo- and polysaccharides are joined together by glycosidic
are described by their dextrose (glucose) equivalence (DE), linkages in a head-to-tail fashion. As a result, each oligo-
which is defined as the percent reducing sugar calculated saccharide has one, and only one, reducing end, that is, an
as D-glucose on a dry-weight basis. Thus, the DE is a mea- end with a carbonyl or hemiacetal group (Fig. 5), but be-
sure of the degree of hydrolysis. D-Glucose has a DE value cause most oligosaccharides are produced by depolymeri-
of 100 and starch a DE value of O. Glucose syrups normally zation of polysaccharides, and because polysaccharides are
have DE values ranging from -25% to >95%. A DE 25 often branched and may have many nonreducing ends,
syrup contains 5% glucose, 6% maltose, 11% malto- oligosaccharides may have more than one nonreducing
triose, and 78% higher oligosaccharides. A DE 80 syrup end.
contains about 80% glucose. Depolymerization of starch molecules produces a series
Reactions of hydroxyl groups are of little significance in of branched (see "Polysaccharides") and unbranched oli-
monosaccharides of foods, except as they are involved in gosaccharides known chemically as maltooligosaccharides
hemiacetal and lactone ring formation. However, an im- (Fig. 5) and, perhaps, larger fragments, depending on the
portant process that can occur with any carbohydrate con- extent of depolymerization. Commercially, these mixtures
taining a free, or potentially free, aldehydo or keto group are known as, and labeled, maltodextrins. A range of mal-
also involves the remainder of molecule. Nonenzymic todextrin products with different properties are produced.
browning begins with a reaction known as the Maillard Mixtures of starch depolymerization products with smaller
reaction, which is a chemical reaction between an amino average degrees of polymerization, but large enough to al-
group of an amino acid or protein molecule and reducing low conversion to a dry powder form (rather than a syrup)
sugars, which are any carbohydrate molecules with a car- are known as, and labeled, corn syrup solids, glucose syrup
bonyl group (free or in the form of a hemiacetal). The end solids, dried glucose syrup, or glucose syrup, dried.
products of a series of steps in several related pathways The primary exception to the head-to-tail linkage ar-
are flavors, aromas, and dark-colored soluble and insoluble rangement is found in the structure of the disaccharide
polymers. sucrose (1,2) (see the article SUGAR: SUCROSE), in which the
Heating sugars in the absence of compounds containing linkage is from hemiacetal group to hemiacetal (hemi-
amino groups to a sufficient temperature effects a complex ketal) group (Fig. 6), leaving the molecule with no free or
series of pyrolytic reactions resulting in the production of potentially free carbonyl group. Therefore, sucrose is clas-
caramel colors and flavors. sified as a nonreducing sugar. Tri- and tetrasaccharides
related to sucrose (raffinose, and stachyose, respectively)
OLIGOSACCHARIDES
Derived
From cellulose Carboxymethylcelluloses (CMC),
hydroxypropylcelluloses (HPC),
hydroxypropylmethylcelluloses (HPMC),
methy!celluloses (MC)
From starch Starch acetates, starch 1-
octenylsuccinates, starch phosphates,
starch adipates, starch succinates,
hydroxypropylstarches, dextrins
Synthetic
Polydextrose
Xanthophylls are pigments that contain hydroxyl, car- whereas the trivial name is a single work (eg, fucoxanthin).
bonyl, epoxide, ester, and carboxylic acid groups. The con- In the IUPAC system the central chain is assumed to be
vention today is to indicate the source and add the suffix unsaturated and all-trans. Any departure from this struc-
xanthin (eg, tunaxanthin). Some of the older trivial names ture is specified. Thus ^-carotene is /?, ^-carotene. The term
such as lutein denoted their yellow color. Structural fea- nor indicates that a methyl is missing, and seco indicates
tures are indicated by the prefix iso, as in isozeaxanthin; a break in the ring structure such as 5,6, SECO, /?, /?-
the hydroxyl group in zeaxanthin is in the three position, carotene-5,6-dione (semi-/?-carotenone). The change in the
and it is in the four position in isozeaxanthin c/s-Lycopene hydrogenation level to form saturated positions as well as
would indicate a departure from the expected all-trans acetylenes and allenes can be designated by hydro and de-
structure. hydro.
In recent years an attempt has been made to limit the Oxygenated derivatives of carotenoid hydrocarbons are
number of trivial names by building on a known name such named by use of suffixes and prefixes according to the rules
as ^-carotene. Thus astaxanthin might be 3,3'dihydroxy- of general chemical nomenclature. The principal group is
4,4' -diketo-/?-carotene. chosen and is cited by use of a suffix, and the other groups
The systematic method of carotenoid nomenclature are cited as prefixes. The sequence is as follows: carboxylic
uses the IUPAC convention (14-15) (Fig. 1). The advantage acid, ester of carotenoid acid, aldehyde, ketone, alcohol,
is that any carotenoid can be exactly named, including ester of carotenoid alcohol, and epoxide. Apo-carotenoids
chiral centers. The disadvantage is that the name for a are found naturally as well as occurring synthetically. The
complicated compound can take two or three lines, apo designates where the parent compound has been
(3-Carotene
O H CH3 I
HO-C-C-C-CH2-CH2OH NADPH
H OH
Mevalonic acid
atp (3)
CH3 CH3
CH 2 =CCH 2 CH 2 -OPP CH3-C=CHCH2OPP
Isopentenyl pyrophosphate Dimethylallyl
I pyrophosphate
H
Sterols * Squalene-\_ Farnesyl pyrophosphate C _ 15
Geranylgeranyl pyrophosphate C_ 2 o
v
Phytoene C-40
4(-2H)
were fed to rats, and it was found that the conversion of /?- Generally the concentration of the carotenoids in vari-
carotene to vitamin A was inhibited (25). ous tissues is low but can vary widely. The cornea of the
eye narcissus contains 18% ^-carotene (dry), whereas the
concentration in foods is much lower. It has been estimated
OCCURRENCE IN NATURE
that the annual production of carotenoids is in on the order
of 108 tons. The major pigment is fucoxanthin, the pigment
As indicated in Table 1 the carotenoids are widely distrib- in marine brown algae. Other major pigments include
uted in foods and are the most widespread group of pig- those found in green leaves, mainly lutein, violaxanthin,
ments in nature. They are present without exception in and neoxanthin. By contrast, ^-carotene occurs widely but
photosynthetic tissue; occur with no definite pattern in in smaller amounts. It is of interest that (note: zea is major
nonphotosynthetic tissues such as roots, flower petals, pigment in some algae) 3,3'-dihydroxy-a-carotene (lutein)
seeds, fruits, vegetables; and are found sporadically in the is a major pigment, whereas 3,3'-dihydroxy-/?-carotene
Kingdom Protista, including the (fungi-yeast mushrooms (zeaxanthin) is a minor pigment in nature. In contrast, the
and bacteria). The red, yellow, and orange pigments in the major hydroxarbon carotenoid found in nature is /?-
skin, flesh, shell, or exoskeleton of some animal species are carotene, whereas a-carotene is a minor pigment. A typical
due to these pigments. These would include the lobster, percentage profile of the xanthophylls of a green plant
shrimp, salmon, goldfish, and flamingo. People who con- could be lutein, 40%; violaxanthin, 34%; neoxanthin, 19%;
sume large amounts of tomato juice may turn orange or cryptoxanthin, 4%; and zeaxanthin, 2%. /?-carotene, lyco-
red because of an intake of the pigments. The carotenoids, pene, and capsanthin can be high in some tissues such as
which cannot be made by animals, are the precursors to the sweet potato, tomato, and red pepper. By contrast, the
vitamin A, but unlike vitamin A, are not toxic in large carrot is a major course of a-carotene where the concentra-
doses (26). tion can be 30 to 40%.
Phytoene (C40)
Phytofluene
- Carotene
Neurosporene
a - Zeacarotene 13 - Zeacarotene
Lycopene
8 - Carotene y - Carotene
Rhodopin
a - Carotene ft - Carotene
Rhodovibrin
a - Cryptoxanthin Cryptoxanthin
Spirilloxanthin
Lutein Zeoxanthin
The level of carotenoids is often directly related to the epoxide has been isolated from tomatoes as a minor pig-
quality of food. The lack of pigments as in white butter or ment. Because phytofluene is fluorescent, it must be ac-
salmon, for example, is a quality defect (27). However, flour counted for in the fluorometric analysis of vitamin A (25).
is bleached to destroy the carotenoids, and /7-carotene is The alicyclic carotenoids (eg, /?-carotene) are very
often removed from red palm oil to make it colorless. common in higher plants, bacteria, fungi, algae, and
The acyclic pigments phytoene, phytofluene, zeta- animals. It has been estimated, on the basis of structure,
carotene, neurosporene, and lycopene are often found in that some 50 to 60 alicyclic compounds have potential vi-
carotenoid-producing systems such as higher and lower tamin A activity. Apricots are an excellent source of (1-
plants. They are not often found in animal tissue. Of these, carotene (60%), whereas the level in tomatoes (10%) and
lycopene is the most common and may occur in large peaches (10%) is much lower. Papaya, if it is yellow/orange,
amounts in the tomato, watermelon, orange, pink grape- is a good source, whereas the red flesh papaya contains
fruit, and some apricots. Further reactions in products of mainly lycopene. Where the flesh is green, some plastid
lycopene lead to the closing of one or both rings. However pigments would be present and thus some ^-carotene
in some oranges (Valencia) 3,4-didehydrolycopene is found. would be present. Red grapes, pears, figs, red apples, and
There have been a number of acyclic xanthophylls isolated beet root, although brightly colored, are not good sources
mainly from the purple photosynthetic bacteria. The 1,2- of /7-carotene.
^-Carotene has been isolated from certain tomato vari- sults in a lower price for the shrimp, particularly on the
eties where apo-polycis-isomers of /?, a, and e-carotene, and Japanese market. When cooked, the complex is broken and
lycopene have been found. the red color is seen. The lobster can be green, black, red,
Vegetables may be excellent sources of the provitamin or blue because of various protein-astaxanthin complexes
A carotenoids. Spinach may have up to 4.0 mg/100 g /?- all of which are broken with heat, yielding a red pigment.
carotene and carrots may have as high as 6.0 mg/100 g of When treated with alkali, astaxanthin is converted to as-
^-carotene. Yellow corn (maize) contains small amounts of tacene.
/^-carotene and /?-zeacarotene. Sweet potatoes may be pur- Aromatic carotenoids have recently been isolated from
ple, white, or bright orange. The two former potatoes are photosynthetic bacteria and some sea sponges. Carotenoid
low in carotenoids and the latter may be greater than 9 epoxides are fairly common in nature. The so-called vio-
mg/100 g. Squash, broccoli, peas, and pumpkin contain laxanthin cycle is an example of the natural occurrence of
relatively large amounts of carotenes. Most vegetable oils epoxidation.
are slightly yellow indicating a small amount of carote-
noids. The red palm oil produced in Brazil, Southeast Asia, zeaxanthin ^ antheraxanthin ^ violaxanthin
and parts of Africa may contain large amounts of /?- and OL-
carotene (50 mg/100 g total carotenoids). Egg yolks are a
EFFECT OF AGRICULTURAL PRACTICES
rich source of carotenoids (lutein and zeaxanthin) but rela-
tively poor sources of ^-carotene. Green peppers are a bet-
A number of agricultural practices, particularly those with
ter source of carotene than are the red peppers. Wheat
plants, directly affect the carotenoid content. Thus the nu-
flour is low in carotene and this amount is further lowered
trient content of edible plants can vary severalfold to as
in the bleaching process.
much as 20 times (29). The major changes are caused by
Hydroxylated carotenoids are very common in plants,
genetic manipulation. However, a number of factors such
where lutein and zeaxanthin are to a lesser extent, /?-
as sunlight, rainfall, topography, soils, location, season,
cryptoxanthin are major pigments. Lutein is a common
fertilization of soils, and maturity may affect carotene con-
pigment in freshwater fish, whereas tunaxanthin (3,3'-
tent. Thus the nutritional tables give an average value
dihydroxy e-carotene) is common in marine fish. Peaches
with an understood large variation. A number of countries
are a good source of ^-cryptoxanthin. Many fruits contain
have developed nutritional tables that, when compared,
xanthophyll esters. In the persimmon the carotenoid al-
show a great variation for the same fruit or vegetable. In
cohol is ^-cryptoxanthin. Corn varieties are selected for
the past, genetic manipulation has been concerned with
their high content of zeaxanthin and lutein. These pig-
the color, flavor, texture, and yield. Today there is more of
ments are fed in order to pigment the skin and egg yolks.
an effort being made to produce foods that are nutritionally
The xanthophylls with hydroxyl or keto substitution in
superior. Thus, interest is being shown in developing not
the four position are common in various animal tissues.
only the color but also the quality of the color (eg, more /?-
Echinenone (4-keto-/?-carotene) is widely found in marine
carotene). No agricultural practice has been as effective as
invertebrates and algae and canthaxanthin (4,4'-keto-/?-
genetic manipulation. High ^-carotene tomatoes have been
carotene). The usual epoxides are in the five, six position
developed but because of the yellow color were not popular.
and these are easily converted to the 5,8-epoxide with acid.
Sweet potatoes can vary from O to 7 mg/100 g of carotene
Where a keto group is in the four position, in-chain epox-
and the carotene from carrots can be increased five times.
ides are formed (eg, 9,10-epoxides of canthaxanthin). The
Generally light has a positive effect on carotene synthesis.
1,2-epoxides of acylic pigments have been reported in to-
Fruit grown in the dark, however, will develop some color
mato leaves. The allenic seaweed pigment fucoxanthin is
(30). Temperature has an effect, but this depends on the
thin. The cyclopentyl ketones are found in red peppers and
product. The most pronounced effect is on the ripening of
are probably formed by a pinacolic rearrangement of the
the tomato. In temperatures below 270C the synthesis of
epoxides of zeaxanthin.
lycopene is favored, whereas a yellow tomato results at a
The acetylenic carotenoids are found in diatoms, Eu-
higher temperature. Gamma irradiation also affects the
glena, giant scallops, mussels, and starfish. A number of
formation of carotene (31).
apo-carotenoids are formed in some fruit, bacteria, orange
Most vegetables and fruits increase in carotene during
peel, and fungi. The most well known apo-compound is
the ripening stage. The carotene content of the carrot in-
bixin, the pigment in annatto seeds. Crocin is an apo-
creases until a level in maturity is reached. The /?-carotene
compound occurring in saffron. In a sense, retinol can be
level falls off upon further growth. In the case of the red
considered a degraded /?-carotene. The carotenoid acid, to-
pepper, the conversion from green to red lowers the caro-
rularhodin, is a common pigment in Rhodotorula yeast.
tene content. Because of cultural practices and shipping
Canthaxanthin is found in edible mushrooms, blue-green
constraints, fruits may be picked green and thus the full
algae, trout, brine shrimp, and flamingos.
color may not develop.
Astaxanthin is the pigment of the salmon and the in-
vertebrates, annelida and Crustacea. Recently it has been
isolated from red yeast and Adonis flowers (28). Shrimp ANALYSIS
raised in intensive culture are often blue because of a pro-
tein complex with astaxanthin. This complex extends the A universal extraction and analysis scheme for the carot-
chromophore resulting in a blue color. This has been mis- enoids is not possible due to the wide variation in carote-
takenly described as a disease, the condition, however, re- noid structure. Thus, numerous methods are suggested for
the separation of carotenoids from such things as food- destroyed by some enzymes (eg, lipoxygenase), and are
stuffs and blood plasma. The classic methods used by most usually bleached by light. Most carotenoids are fat soluble
investigators rely on some method of extraction and a chro- and thus are not subject to leaching losses. Generally they
matographic separation of the carotenoids (32,33). The are fairly stable to the heat involved in canning but are
methods require some sort of size reduction to increase rapidly lost on dehydration because of oxidation.
surface area followed by extraction with a suitable solvent Although the most stable form of the carotenoids is the
or solvent mixture. Often a bipolar solvent is used to ex- all-trans form, the cis-geometrical isomer can form upon
tract nonpolar carotenoids from polar tissue. Ethyl alcohol heating, especially in the presence of H+ . The cis-isomer
and acetone are examples of bipolar solvents, and CHCl3/ carotenoids are naturally present in the tangerine tomato.
MeoH is an example of a bipolar solvent mixture. The ex- It has been shown that if ^-carotene activity was set at
traction may be followed by saponification, removal of al- 100%, the neo-/?-carotene vitamin A activity was 38%, and
kali, transfer to a developing solvent, and chromatography the neo-a-carotene activity was 13%. The transformation
under vacuum or pressure. The column may be developed from trans to cis results in a loss of extinction and a shift in
with a gradient of solvents, and the pigments are sepa- absorption maxima to shorter (2-5 mm). Cooking causes
rated by elution or are cut from the column and extracted. the formation of cis isomers from all-trans /^-carotene (38).
Often rechromatography is required of some bands, fol- Broccoli lost 13%, spinach lost 7%, and the sweet potato lost
lowed by verifying chemical reactions. The quantity of each 32% of the all-trans isomer. A 15% loss of vitamin A was
purified fraction is determined by spectroscopy. The reported, mainly due to a cis-trans isomerization of a- and
method requires several hours, and in some cases artifacts /?-carotene during canning. High-temperature short-time
(cis-trans isomers, epoxides) are formed due to the long (HTST) processing was shown to have less effect on the car-
exposure to solvents, absorbents, light, and oxygen. Al- otene in the sweet potato than conventional cooking (35).
though the method does give a separation of provitamin A Heat processing produced enough acid in pineapple to
precursors from inactive carotenoids, it is time-consuming
cause the formation of cis isomers. This could result in a
and requires skilled technical operators. Thus, the method
lighter yellow color.
may not be suitable for analysis of the large number of food
items for a table of food compositions. A much simpler The formation of 5,6-and 5,8-epoxides of ^-carotene in
method has been developed that chromatographically model systems has been studied. Diphenylamine, a free-
separates the carotenes from the oxygenated compounds, radical inhibitor stopped the loss of ^-carotene. It is gen-
but it may not separate individual carotenes, their cis iso- erally thought that epoxide formation is the initial step in
mers or carotenoid esters (34). Therefore, this method the degradation of the carotenoid. Several reports have
tends to overestimate provitamin A activity, especially if been published that show the complexity of the reactions.
/^-carotene represents only a small part of the total. High- Stored hydrogenated oils and enzymatic-coupled oxidation
performance liquid chromatography (HPLC) is clearly the of carotenoids result in the formation of epoxides and other
method of choice, and the more recent values in the nutri- products.
tional tables are generally determined by this method. A A number of studies have reported an apparent in-
number of reports have appeared that show the general crease in the level of carotenes in various canned products
over estimation of the Association of Official Analytical over the fresh product. There are two reasons for this sur-
Chemists (AOAC) method. A modified AOAC method and prising result. Where soluble solids are leached out of the
chromatographic procedures that separated the individual products during cooking and storage, the fat-soluble car-
components were used to estimate the provitamin A con- otenes appear to increase in amount. It has also been ob-
tent of Clingstone peaches (35). served that the fresh control may have an active lipoxy-
The U.S. RDA for 100 g was much higher by the AOAC genase-like enzyme that bleaches the carotenoids. When
method than by the complete separation (60% vs 11% of antioxidants were added to the fresh sample before ex-
the RDA for raw, 12% vs 6% for canned). traction, the vitamin A value in the fresh product in-
The comparison of the AOAC method with a stepwise creased.
gradient, a saponification step, and HPLC has been pub- Dehydration and size reduction of fruits and vegetables
lished. The AOAC method and HPLC were comparable for increase surface area and, if products are not protected
green vegetables. For the carrot and pumpkin, the AOAC from light and oxygen, result in poor stability of the carot-
method was higher for both vegetables than the gradient enoid pigments. The shelf life of the carotenoids in the
elution and HPLC method. Where fruit xanthophylls were dry state is shorter than in the wet state. Different dehy-
esterified, these compounds were chromatographed with/?- dration methods result in varying losses of carotenes.
carotene, and thus the estimation was higher in the AOAC Retention of carotene in fresh carrots varies; fresh carrots
method when the fruit extract was not saponified (36). retain more than (100%), blanched (95%), freeze-dried
A number of papers (37) have shown that the open col- (89%), air-dried (80%), and puff-dried (12%). Carotenoid
umn packet with 40 to 50 jum gives good separation of vi- oxidation in foods is generally associated with unsaturated
tamin A compounds as well as carotenoid compounds. The fatty acids and is usually autocatalytic. The oxidation may
procedure used a pipette for the injector. Nitrogen gas or or may not be enzymatic in nature and is directly related
vacuum is used in place of a pump. to the available water (A117), oxygen, heat, and certain met-
EFFECT OF FOOD PROCESSING als. Generally antioxidents are effective in slowing the re-
action. The decomposition products from a simulated de-
The carotenoids are altered or partly destroyed by acids, oderization of red palm oil were isolated. Beta 151- and
usually but not always stable in inorganic bases, can be /?14'-apo-carotenals and 13 apo-carotenone were isolated
from the reaction mixture and a pathway for the reaction 1 IU = 0.3 jug retinol
was suggested. 0.6 jug ^-carotene
1.2 jug other provitamin A carotenoids.
CAROTENOIDS AS FOOD COLORS
It was the color of the carrot that first interested research- a-Carotene on the preceding basis would be half as
ers 160 years ago to start work on carotenoids. Many years active as ^-carotene. The metabolism of a-carotene has
later it was again the color that was the means of identi- been shown to result in the liver storage of retinol and a-
fying compounds separated by chromatography. It is the vitamin A. The latter compound does not combine with
same today as it has always been; color is one of the means retinol binding protein (RBP). It can induce hypervita-
by which we identify the quality of food. People often reject minosis A because it is not delivered to the tissues. There
the unfamiliar. Most pigment changes such as the changes is some confusion in regard to the capacity of the diepox-
in chlorophyll on thermal processing, the bleaching of an- ide to serve as a vitamin A source. The compound is listed
thocyanins, the browning of fresh meat, or the off-coloring as active in vivo but not active in vitro. Recently, radio-
of flavonoids do not in themselves affect the product. In active /?-carotene-5,6,5',6'-diepoxide and luteochrome
case of the destruction of carotene, loss or change in color (5,6,5',8'-/?-carotene-diepoxide) were fed to rats and C14
would result in poorer quality, but also may result in loss retinol was not detected in the liver. The absorption or
of vitamin A activity. ^-Carotene has 11 double bonds in conversion to retinal is enhanced by bile salts, proteins,
conjugation, which is the reason for its yellow-orange color. lipids, and zinc. It is not clear what the effect of various
Any disruption in the chromophore, such as that which is nonprovitamin A compounds have on the bioavailability
depicted in Figure 2 would result in bleaching. of the provitamin A compounds. Lycopene is reported to
enhance carotene uptake. It was found that nonprovi-
tamin A compounds may decrease the utilization of pro-
CONVERSION OF CAROTENOIDS TO VITAMIN A vitamin A pigments, whereas /?-cryptoxanthin and a-
carotene promote utilization.
The carotenoids of fruits, vegetables, and animal products Because of the uncertainty of some of the artificial pig-
are generally fat soluble and are associated with the lipid ments and because of the delisting of several (eg, Red No.
fractions. In some cases they may be in the crystalline 2 in the United States, Red No. 40 in the United Kingdom),
state, as lycopene is in the tomato. During the digestion interest has increased for using carotenoids as food color-
process, esterases, lipases, and proteases act on the carot- ants.
enoids, which are solubilized by the bile salts. Within the We can consider the use of carotenoids as following a
mucosal cell ^-carotene and the other provitamin A, carot- direct or an indirect route. As a case of the former, mar-
enoids are split by carotenoid dioxygenase(s) resulting in garine might be colored with ^-carotene. Examples of the
an oxidative cleavage. In theory a molecule of ^-carotene latter might be the coloring of poultry skin, or eggs, or
should yield two molecules of retinal. Retinol is formed by salmon flesh with the appropriate pigment. Some confu-
reduction of retinal. It is esterified and transported to the sion exists regarding natural and artificial pigments. The
liver for storage. There is some difference of opinion as to infrared fingerprints for synthetic and natural ^-carotene
whether there is a central cleavage enzyme or whether are identical. Many people prefer the term nature-identical
there is also a random-splitting enzyme that acts on vari- to describe the synthetic carotenes.
ous places on the chain. The carotenes may also be ab- One of the most common natural coloring preparations
sorbed, carried by low-density lipoproteins and deposited is obtained by extracting the seeds of the Bixa orellana
in the skin, fat, and various organs. The extent of accu- tree, which grows in the tropics. The apo-compound bixin
mulation, rate of accumulation, time to reach saturation, is the main component of the oil-soluble annatto prepara-
and turnover time were different for each tissue. Liver ad- tions, and nor-bixin is the 6,6'-diapo-dicarboxylic acid
renal and ovary have high concentrations of /^-carotene. (bixin has one methyl ester). Bixin is most stable at pH 8
Animals differ in the efficiency of the splitting reaction. and shows a diminished stability in the 4 to 8 pH range.
The rat is generally regarded as very efficient. The mink In general, annatto extracts have a good shelf life. Annatto
and the fox are relatively inefficient in this reaction. Man oil applications include the coloring of butter, bakery prod-
is average with a ratio of about 6:1. The cat does not con- ucts, and salad oil. Combined with paprika, annatto oils
tain the enzymes necessary to utilize provitamin A caro- are used to color cheese. Water-soluble preparations may
tenes. be used in ice cream.
Generally, for a compound to be active it must have an Saffron consists of the dried stigmas of Crocus sativus.
unsaturated central chain and an unsubstituted/?-ring. On It contains crocin, the digentiobioside of crocetin. The prep-
the basis of structure out of the greater than 600 carote- aration is yellow in color. Saffron is also used as a spice
noids listed, the provitamin A compounds would be be- and is widely accepted in such foods as soups, meat prod-
tween 50 and 60. Vitamin A conversion factors include: ucts, and cheese. Formerly, it was used in cakes and other
bakery products.
^- . , //g/?-carotene Tomato extracts are red because of the pigment lyco-
RE = jug retinol +
6 pene. The color of the product would be red to orange de-
jug other provitamin A compounds pending on the medium. Lycopene is not stable, and its use
+
12 is limited.
Carrot extracts, carrot oil, and red palm oil contain thaxanthin, /?-apo-8'-carotenal, and more recently astax-
large amounts of a- and ^-carotene. These were used in fat- anthin are produced by commercial chemical synthesis. A
based products. They have the advantage of being natural great many other carotenoids have been synthesized that
but have limited use because of the lower price of synthetic at the moment have no commercial significance.
^-carotene. Recently, hypersaline algae have been cultured The Roche synthesis of ^-carotene starts from/Monone
for their ^-carotene content. and is related to the vitamin A synthesis. The /?-ionone
Oleoresin paprika is an oil extract of paprika. The main may be prepared from citral, a constituent of lemongrass
carotenoids are capsanthin and capsorubin. The color of oil, or prepared synthetically from acetylene as a starting
products colored by paprika vary from red to pinkish yel- material. In the ^-carotene procedure, /?-ionone is con-
low. Oleoresin paprika can be used in salad dressings, verted to C-14 aldehyde, which, through further chain-
sauces, meat products, and processed cheeses. The indirect lengthening steps, is converted to C-19 aldehydes. These
coloring of trout with oleoresin paprika resulted in a yellow are joined through a Grignard reaction to form the C-40
rather than a red hue of the flesh. diol, which, through allylic rearrangement and dehydra-
The synthetic pigments have a number of advantages tion, is converted to 15,15-dehydro-/?-carotene. A partial
over the natural product extracts. Although the principal hydrogenation and rearrangement yields trans-ft-carotene.
advantage is price, it should not be overlooked that the Crystalline carotenoids produced by chemical synthesis
large variation in quality is not a problem with the syn- are of high purity and uniform color. The vast majority of
thetic FDC dyes. The major synthetic carotenoids that are carotenoids, when pure, can be obtained in crystalline
marketed include ^-carotene, /?-apo-8'-carotenal, and can- form. In general, the melting points of crystalline carote-
thaxanthin. All occur naturally, and only canthaxanthin noids are fairly high and quite sharp for the pure com-
does not have vitamin A activity. pounds. The synthesis of the carotenoid series of com-
^-Carotene is widely encountered in nature. In foods it pounds employs a variety of organic synthetic techniques.
has been used in butter, margarine, salad oil, popcorn, The literature on the synthesis of the various carote-
baked goods, confections and candy, eggnog, coffee whit- noids is extensive, and the details are certainly beyond this
eners, juices, and soups to name a few. /?-apo-8'-carotenal chapter.
has been isolated from oranges and several natural
sources. However the main source is the chemical synthe-
sis. It is also yellow, and its uses are similar to those for /?- FUNCTION OF CAROTENOIDS
carotene.
Canthaxanin (rosanthin) (4,4'-diketo-/?-carotene) is It is tempting to propose a single universal function for the
used where a red color is desired. It was first isolated from carotenoids since they are found in such diverse tissues.
the mushroom, but it is also a widely distributed animal Failing this, it is tempting to ascribe some function, wher-
pigment. Many crustaceans, especially brine shrimp, and ever a carotenoid is found. Although the function of the
birds, notably the flamingo, contain canthaxanthin. One of carotenoids has been proven in some cases, their universal
its main uses is as a pigmenting agent for salmon. Al- function, if any, remains to be determined. Where the func-
though a red color is obtained, it has been observed that tion has been proven, it generally is with some aspect of
the pigment tends to cook out. Recently canthaxanthin has the light-absorbing property of the carotenoid pigment.
been used in simulated meats, shrimp, crab, and lobster The critical role of these pigments in photosynthesis has
products. been the best documented. Phototropism and phototaxis
Synthetic astaxanthin is now available and is approved responses of plants seem to be related to the light absorp-
for use in Europe and the United States. This is the major tion spectra of the carotenoids. Functions in animals are
pigment in a number offish and shellfish species. The color related to the antioxidant and to the light-absorbing prop-
tends to be more stable than canthaxanthin. When shrimp erty of these pigments. The function in vitamin A forma-
are raised in intensive culture, often the blue carotenopro- tion has been discussed. Because these pigments are found
tein is found. This can be corrected by feeding more green in many reproductive tissues, it has been suggested that
algae or astaxanthin. Marigold flowers contain mainly Iu- they have a role in reproduction. The results in this area
tein and are fed to chickens to supply yellow-orange pig- are less convincing than those in other areas.
ments for the skin and egg yolks. In the photosynthetic process the carotenoids have been
The crystalline carotenoids are not absorbed or metab- shown to be active in the light-gathering process (eg, they
olized by animals. This problem has been solved by the absorb light at wavelengths not absorbed by chlorophyll).
development of special water-soluble forms marketed to In Chlorella, other green algae, and higher plants, the light
satisfy various product needs. Two approaches have been
absorbed by the carotenoids was used at low efficiency. In
primarily employed: the production of oil suspensions of
the diatom and brown algae the energy transfer is com-
micropulverized crystals and the development of emul-
sions or beadlet forms containing the carotenoid in super- parable to chlorophyll where the main pigment in fucoxan-
saturated solution or finely colloidal forms in liquid or dry thin. In the photosynthetic process two photo systems are
products. involved. In general, more carotenes are found in photo-
system I and xanthophylls in photosystem II.
CAROTENOIDS BY CHEMICAL SYNTHESIS The role of the carotenoids in photoprotection of pho-
tosynthetic bacteria has been well documented. A mutant,
The total synthesis of /?-carotene was reported in 1950. which only produced the colorless polyenes phytoene and
Since that date /?-carotene, retinol, cis-retinoic acid, can- phytofloene, was compared with the wild type Rhodopseu-
dowonas sphaeroides. The wild type showed good growth In animals the major function of carotenoids is as a pre-
under all conditions of light and oxygen. However, the mu- cursor to the formation of vitamin A. It is assumed that in
tant could only grow under anaerobic-light or aerobic-dark order to have vitamin A activity a molecule must have one-
conditions. half of the structure similar to that of ^-carotene. Recently
Under light with O2, massive killing resulted at room it has been shown that astaxanthin can be converted to
temperature and bacterial chlorophyll was destroyed. If zeaxanthin in trout where the fish is sufficient in vitamin
the mutant was grown in the dark with air, chlorophyll A. !Vitiated astaxanthin was converted to retinol in strips
disappeared. Where chlorophyll was missing, light and O2 of duodenum or inverted sacks of trout intestines. Astax-
have no effect. anthin, canthaxanthin, and zeaxanthin can be converted
Diphenylamine (DPA) inhibits the formation of colored to vitamin A and A2 in guppies.
carotenoids. When the wild type blue-green bacteria is We have become increasingly aware of a mounting body
treated with DPA, it is destroyed like the mutant. At low of evidence that suggests that the carotenoids can function
temperatures, killing proceeds in the mutant but bacterial in medical applications apart from their role as vitamin A
chlorophyll is not destroyed. precursors. The symptoms of erythropoietic Protoporphy-
Corynebacterium poinsettiae is not photosynthetic, and ria can be relieved by large doses of ^-carotene (38). This
both the wild type and the carotenoid-less mutant can tol- pigment was deposited in the skin of patients who lacked
erate high intensities of light in the presence of air. When skin pigmentation.
the exogenous dye, toluidine blue, is added as a photosen- As of late some carotenoids have been claimed to be ef-
sitizing pigment, the carotenoid-less mutant is killed. The fective in the treatment of cancer, particularly cancer of
mechanism involves the simultaneous interaction of visi- epithelial origin. Other carotenoids such as canthaxanthin
ble light, a photosensitizing dye, and O2. Generally, the and phytoene with no vitamin A activity were, in cases,
carotenoids are effective for visible light but have no effect found to be as effective as ^-carotene.
in ultraviolet, gamma, or X radiation. Some of the first studies were based on epidemiological
The reactions are listed as follows: studies. In one such study it was shown that the partici-
pants who consumed diets rich in carotenoids developed
CHL + hv - *CHL excited state fewer lung cancers whether or not they smoked. This study
assumed that the active ingredients are the carotenoids
*CHL + -> photosynthesis or 3CHL triplet-excited
contained in fruits and vegetables.
state intersystem crossing
More recently a number of animal studies have shown
3
CHL + 3O2 - 1CHL + 1O2 that ^-carotene or other carotenoids can prevent or slow
or 3CHL + 1CAR -> 1CHL + 3CAR down the growth of skin cancer and other cancerous tu-
3 mors. Review have been published on the role of the ca-
CAR 1CAR - harmless decay
rotenoids in relation to cancer. Human studies are pres-
1
O2 + CAR CAR O2 CAR can be regenerated ently being conducted (39,40).
or 1O2 + A A O2 photodynamic action
1
O2 + 1CAR 3O2 + 3CAR BIBLIOGRAPHY
3 1
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20. L. C. Raymundo, A. E. Griffiths, and K. L. Simpson, "Effect of
Dimethyl Sulfoxide (DMSO) on the Biosynthesis of Carote-
noids in Detached Tomatoes," Phytochemistry 6, 1527-1532 KENNETH L. SIMPSON
(1967). University of Rhode Island
21. L. C. Raymundo, A. E. Griffiths, and K. L. Simpson, "Biosyn- Kingston, Rhode Island
thesis of Carotenoids in the Tomato Fruit," Phytochemistry 9,
1239-1245 (1970).
22. M. Elahi et al., "Effect of CPTA Analogs and Other Nitroge- See also COLORANTS: CAROTENOIDS.
nous Compounds on the Biosynthesis of the Carotenoids in
Phycomyces blakesleeanus Mutants," Phytochemistry 14,133-
381 (1975). CENTRIFUGES: PRINCIPLES
23. R. J. H. Williams, G. Britton, and T. W. Goodwin, "Biosynthe- AND APPLICATIONS
sis of Cyclic Carotenes," Biochem. J. 105, 99-105 (1967).
24. R. E. Tefft, T. W. Goodwin, and K. L. Simpson, "Aspects of the Centrifuges are used widely in food processing to separate
Stereospecificity of Torularhodin Biosynthesis," Biochem. J. liquids from solids, liquids from liquids, and even to sepa-
Ill, 921-927 (1970). rate two immiscible liquids from the accompanying solids.
25. S.-I. Huang, Ph.D. Thesis, "Inhibitory Effects of Cellulose and Centrifuges can be blanketed with inert gas and operate
Nonprovitamin A Carotenoids on Beta-Carotene Utilization under high temperatures and pressures, as well as dis-
in Rats," University of Rhode Island, 1995.
charge centrate under pressure to retard foam and oxida-
26. T. W. Goodwin, The Biochemistry of the Carotenoids, Vol. 1,
2nd. ed., Academic Press, Orlando, FIa., 1980, p. 377. tion. They rinse the mother liquor from solids. They can
27. J. Ostrander et al., "Sensory Testing of Pen Reared Salmon be cleaned in place, and some can be steam sterilized. Cen-
and Trout," J. Food ScL 41, 386-390 (1975). trifuges may also be used to separate large particles from
28. T. Kamata and K. L. Simpson, "Study of Astaxanthin Diester similar small particles when they are operated as classi-
Extracted from Adonis aestivalis,n Comp. Biochem. Physiol. B fiers.
86, 587-596 (1987). Centrifuges were first used in the 188Os to separate
29. R. S. Harris, "Effects of Agricultural Practices on the Com- milk from cream. They use rotational acceleration to sepa-
position of Foods," in R. S. Harris and E. Karmas, eds., Nu- rate heavier phases from lighter phases, similar to a
tritional Evaluation of Food Processing, 2nd ed., AVI Publish- gravity-settling basin. The separating force is measured in
ing, Westport, Conn., 1957, pp. 33-57. units called g's, which are units of acceleration; Ig = 980
30. L. C. Raymundo, C. O. Chichester, and K. L. Simpson, "Light cm/s.2
Dependent Carotenoid Synthesis in the Tomato Fruit," J. Centrifuges usually generate at least 1,200 g for low-
Agric. Food Chem. 24, 59-64 (1976).
speed machines and up to 63,000 g for small tubular cen-
31. C. N. Villegas et al., "The Effect of Gamma Irradiation on the
Biosynthesis of Carotenoids in the Tomato Fruit," Plant Phys- trifuges. From a process standpoint, a higher g force re-
iol. 50, 694-697 (1972). sults in a higher capacity for a given centrifuge; capacity
32. B. H. Davies, "Analytical MethodsCarotenoids," in T. W. is measured by volume throughput, degree of solids con-
Goodwin, ed., Chemistry and Biochemistry of Plant Pigments, centration, clarity of the liquid, and entrainment of one
Vol. 2, 2nd ed., Academic Press, Orlando, FIa., 1976, pp. 38- phase in another. Also, because the length of time the fluid
165. is held under high g affects the separation, the volume of
Best
Not recommended
Not applicable
G Force
High flow rate
Solids dryness
High solids rate
Low solids rate
Liquid capacity
Thickening
Abrasion resistance
Rinse efficiency
Antifoam
Pressure/sealing
Continuous
Operator attention
Figure 1. Properties of different centrifuge types.
Figure 2. Basket centrifuge: imperforate bowl. Low g force (500- Figure 3. Basket centrifuge: perforate bowl. Same as Figure 2
1,000 g) and intermittent feed limit these to applications where except that the liquid filters through the solids. Excellent rinsing
moderate solids dryness is needed. Capacity: 100-200 L/min. capability. Very dry cakes if the particle size is large enough to
filter well.
Figure 4. Disc stack centrifuge. The solid bowl disc centrifuge is
a solid bowl version liquid-liquid separator operating at 5,000- Figure 5. Disc stack centrifuge: nozzle version. Same as Figure
10,000 g with some models as high as 15,000 g. They can handle 4 except that the solids are continuously discharged as a pumpable
a wide range of rates up to 2,400 L/min. slurry. Rates as high as 5,000 L/min are possible.
Figure 7. Decanter centrifuges. Solid bowl decanter centrifuges develop 1,000-3,000 #. They are
used where large volumes of solids are present and the solid phase must be as dry as possible.
Rates vary from 8 to 4,000 L/min. Very high speed decanters from 5-10,000 g are available but
rates are lower, 10-200 L/min.
Light phase
Heavy phase
Feed
Table 1. Production of Cereal Grains, in 103 Metric Tons, During 1996-1997 in Various Production Areas
Production area Wheat Rye Rice Corn Oats Barley
North America 95,367 538 6930 266,214 6714 24,578
South America 22,276 50 11,337 56,550 865 1,285
W.Europe 99,970 5,765 1,600 34,969 7,313 52,937
E.Europe 26,300 6,151 42 25,315 2,526 9,708
R Soviet Union 64,309 9,456 839 4,824 10,322 29,765
Africa 21,881 9,704 40,513 164 8,101
Asia 229,106 250 347,667 161,190 902 20,350
Oceania 23,786 20 1,006 516 1,747 7,017
Total World 583,007 22,233 379,125 590,091 30,553 153,743
Source: USDA-NASS Agricultural Statistics 1998. Data for sorghum were not available.
are called soft, and the term hard is reserved for the Rice varieties vary in their kernel shape and properties.
very hard durum wheats. In the United States the They are classified as long, medium, and short grain. Long-
term hard is used for bread wheats; soft is reserved grain rice accounts for about 50%, medium-grain rice for
for wheats used to produce cookies, cakes, and so on; 40%, and short-grain rice for about 10% of the U.S. rice
and durum for those tetraploid wheats used to pro- production. California is practically the exclusive producer
duce alimentary pastes. of short-grain rice. California and Louisiana lead in
4. Geographic region of growth. medium-grain rice production. Growers in Arkansas,
Texas, and Mississippi produce mostly long-grain rice.
5. End use properties: protein content, physical dough
properties, bread-making quality. Barley
6. Variety.
Barley is a winter-hardy and drought-resistant grain. It
7. Composite designations (14-17). matures more rapidly than do wheat, oats, or rye and is
used mainly as feed for livestock and in malting and dis-
Corn tilling industries. The two main types of barley, two-row
and six-row, differ in the arrangement of grains in the ear.
Corn (called maize in much of the world) is now the most The former predominates in Europe and parts of Australia;
popular grain for use as animal feed in temperate regions. the latter is more resistant to extreme temperatures and
In many tropical areas, it is a basic human food. There are is grown in North America, India, and the Middle East
five major types of corn: flint, dent, floury, pop, and sweet. (24,25).
Dent varieties, grown most widely in the United States, Although barley is grown throughout the world, pro-
provide high yields and are used to a large extent as feed duction is concentrated in the northern latitudes. Since
grain. Flint corn, with a somewhat higher food value, is 1950 the world production of barley tripled with most of
common in Europe and South America. It is valued for its its increase in Europe. The former USSR is the largest bar-
physical properties and as a raw material in the production ley producer. Barley is adaptable to a variety of conditions
of certain Central American foods (tortilla and arepa). Pop, and is produced commercially in 36 states in the United
sweet, and floury corn are relatively minor food crops States. In the United States, the use of barley as a live-
(18-21). stock feed is declining, while the use for processing into
In corn, the starch contains about 25% amylose and 75% malt is increasing.
amylopectin. Mutants of corn are grown in which the
starch is almost entirely amylopectin (called waxy) or 70 Oats
to 80% amylose (amylomaize types). These starches vary
widely in their physical properties (gelatinization charac- Oats are grown most successfully in cool, humid climates
teristics, water-binding capacity, gel properties, etc) and and on neutral to slightly acidic soil. The bulk of the crop
usefulness in various foods and industrial applications. is consumed as animal feed (primarily for horses). A cov-
Maize is generally deficient in the basic amino acids. ered cereal, the oat hull must first be removed before fur-
However, high-lysine and high-lysine-tryptophan genetic ther processing. The resulting product is called a groat.
mutants have improved the nutritional properties of corn Heavy oats (with high groat to hull ratios) are processed
and are now available as dent or flint corn. In the future into rolled oats, breakfast foods, and oatmeal (26).
those mutants are likely to be acceptable for the production The world production of oats is about one-tenth of the
of maize-based foods. world production of wheat and slightly over one-fourth of
The United States accounts for more than half of the the world production of barley. The chief oat-producing
total world corn production and about 80% of the annual states in the United States are in the north-central Corn
world corn exports. In the United States, most corn is used Belt and farther northward. About 90% of the oat is left on
as feed or seed or in the production of alcoholic beverages. the farm as a feed, and only a small proportion is processed
Only about 10% is used as food. This includes the produc- as food or used for industrial products. The use of oats
tion of starch, corn syrups, breakfast cereals, and various in food processing is increasing, especially in breakfast
foods. Livestock feed accounts for almost 85% of the total cereals.
U.S. domestic use. The main importers of U.S. corn are
Western Europe and Japan, primarily for livestock feed. Sorghum
Sorghum is the fifth most widely grown grain in the world.
Rice However, sorghum production is less than 5% of the total
grain production. There has been a small increase in the
Rice is the staple food of about half of the human race, area planted and harvested with sorghum, but the in-
providing more than one-fifth of the total food calories con- crease in production has been substantial because of in-
sumed by the people of the world. Most rice is produced in creases in yield. This has resulted from the development
the Far East and is primarily consumed within the borders of high-yielding hybrids. The primary sorghum-producing
of the country of origin. Asia, which has nearly 60% of the regions are Asia, Africa, and North America. The primary
world population, produces and consumes about 90% of the sorghum-producing countries are the United States,
world rice production. The United States produces less China, India, Argentina, Nigeria, and Mexico. These coun-
than 2% of the world crop, but accounts for about 30% of tries produce more than 75% of the world total, with the
the world rice trade (22,23). United States producing about 30%.
More than 50% of the worldwide production of sorghum Kernel Structure
is destined for human consumption. However, in the
United States, sorghum is grown almost entirely as a feed The cereal grain is a one-seeded fruit (called a caryopsis),
grain for local use or for export. Sorghum is produced un- in which the fruit coat adheres to the seed at maturity. As
der a wide range of climatic conditions. It tolerates limited the fruit ripens, the pericarp (fruit wall) becomes firmly
attached to the wall of the seed proper. The pericarp, seed
moisture conditions and adapts to high temperature con-
ditions (27,28). coats, nucellus, and aleurone cells form the bran. The em-
bryo comprises only a small part of the seed. The bulk of
The nucellar tissue of some varieties of sorghum con-
the seed is taken up by the endosperm, which is a food
tains pigments that complicate production of acceptable
reservoir for the germinating plant.
and white sorghum starch. Varieties with no nucellar tis-
The floral envelopes (modified leaves known as lemma
sue persisting to maturity could be used for starch produc-
and palea), or chaffy parts, within which the caryopsis de-
tion, but the ready availability of corn and other problems
velops, persist to maturity in the grass family. If the chaffy
with the wet-milling of sorghum has discouraged such at-
structures envelop the caryopsis so closely that they re-
tempts. Waxy (starch) sorghums are potentially promising
main attached to it when the grain is threshed (as with
for special food uses. Some sorghums are rich in condensed rice and most varieties of oats and barley), the grain is
tannins. This reduces both their palatability and feed considered to be covered. However, if the caryopsis readily
value. separates from the floral envelopes when the grain is
threshed, as with common wheats, rye, hull-less barleys,
Rye and the common varieties of corn, these grains are consid-
ered to be naked.
Rye is characterized by its good resistance to cold, pests,
and diseases, but it cannot compete with wheat or barley Wheat. The structure of the wheat kernel is shown in
on good soils and under improved cultivation practices. Ap- Figure 1 (35). The dorsal or back side of the wheat grain
proximately 90% of the world's rye production is in Europe is rounded, while the ventral side has a deep groove or
(mainly in Poland and Germany) and in the former USSR. crease along the entire longitudinal axis. At the apex or
Rye is considered a grain for use in bread in Europe, but small end (stigniatic end) of the grain is a cluster of short,
its proportion in mixed wheat-rye bread is decreasing. fine hairs known as brush hairs. The pericarp, or dry fruit
Much of the rye is used as a feed grain and a small pro- coat, consists of four layers: the epidermis, hypodermis,
portion in the distilling industry (29). cross cells, and tube cells. The remaining tissues of the
grain are the inner bran (seed coat and nucellar tissue),
endosperm, and embryo (germ). The aleurone layer con-
PHYSICAL PROPERTIES AND STRUCTURE sists of large rectangular, thick-walled, starch-free cells.
Botanically, the aleurone is the outer layer of the endo-
sperm, but as it tends to remain attached to the outer lay-
Optimal utilization of cereal grains requires knowledge of ers during wheat milling. It is shown in the diagram as the
their structure and composition. The practical implications innermost bran layer.
of kernel structure and composition are numerous (30-32). The embryo (germ) consists of the plumule and radical,
They relate to the various stages of grain production, har- which are connected by the mesocotyl. The outer layer of
vest, storage, marketing, and use. the scutellum, the epithelium, may function as both a se-
Some physical properties of cereal grains are listed in cretory or an absorptive organ. In a well-filled wheat ker-
Table 2 (33). Table 3 summarizes approximate grain size nel, the germ comprises about 2 to 3% of the kernel, the
and the proportions of the principal parts comprising the bran 13 to 17%, and the endosperm the remainder. The
mature kernels of different cereals (34). inner bran layers (aleurone) are high in protein, whereas
the outer bran (pericarp, seed coats, and nucellus) is high Barley. The husks of barley are cemented to the kernel
in cellulose, hemicelluloses, and minerals. The germ is and remain attached after threshing. The husks protect
high in proteins, lipids, sugars, and minerals; the endo- the kernel from mechanical injury during commercial
sperm consists largely of starch granules embedded in a malting, strengthen the texture of steeped barley, and con-
protein matrix. The structure of rice, barley, oats, rye, and tribute to more uniform germination of the kernels. The
triticale are similar in structure to wheat, except that rice husks are also important as a filtration bed in the sepa-
has no crease. ration of extract components during mashing and contrib-
ute to the flavor and astringency of beer. The main types
Rice. Rice is a covered cereal. In the threshed grain of cultivated covered barley, differ in the arrangement of
(termed rough or paddy rice), the kernel is enclosed in a grains in the ear, two-rowed and six-rowed ear. The axis of
tough siliceous hull that renders it unsuitable for human the barley ear has nodes throughout its length. The nodes
consumption. Once this hull is removed during processing, alternate from side to side. In the six-rowed types of barley,
the kernel (or caryopsis), comprised of the pericarp (outer three kernels develop on each node, one central kernel and
bran) and the seed proper (inner bran, endosperm, and two lateral kernels. In the two-rowed barley, the lateral
germ), is known as brown rice or sometimes as unpolished kernels are sterile and only the central kernels develop.
rice. Brown rice is in little demand as a food. Unless stored The kernel of covered barley consists of the caryopsis
under favorable conditions, it tends to become rancid and and the flowering glumes (or husks). The husks consist of
is more subject to insect infestation than are the various two membranous sheaths that completely enclose the car-
forms of milled rice. When brown rice is milled further, the yopsis. During development of the growing barley, a ce-
bran and germ are removed to produce the purified endo- menting substance causing adherence is secreted by the
sperm marketed as white rice or polished rice. Milled rice caryopsis within the first two weeks after pollination. The
is classified according to size as head rice (whole endo- husk in cultivated malting barley amounts to about 8 to
sperm) and various classes of broken rice, known as second 15% of the grain. The proportion varies according to type,
head, screenings, and brewer's rice, in order of decreasing variety, grain size, and climatic conditions. Large kernels
size. have less husk than small kernels. The husk in two-rowed
barley is generally lower than that in six-rowed barley. As
Corn. The corn grain is the largest of all cereals (Fig. in wheat, the caryopsis of barley is a one-seeded fruit in
2) (35). The kernel is flattened, wedge shaped, and broader which the outer pericarp layers enclose the aleurone, the
at the apex than at its attachment to the cob. The aleurone starchy endosperm, and the germ. The aleurone layer in
cells contains relatively high levels of protein and oil. They barley is at least two cell layers thick; in other cereal grains
also contain the pigments that make certain varieties ap- (rice excepted), it is one cell layer thick.
pear blue, black, or purple. Each corn kernel contains two
types of starchy endosperms, horny (vitreous) and floury Oats. The common varieties of oats have the fruit (car-
(opaque). The horny endosperm is tightly packed. The yopsis) enveloped by a hull composed of the floral enve-
starch granules in this region are polyhedral in shape, In lopes. Naked or hull-less oat varieties are known but not
dent corn varieties, horny endosperm is located on the grown extensively. In light thin oats, hulls may comprise
sides and back of the kernel and bulges toward the center as much as 45% of the grain. In very heavy or plump oats,
at the sides. The floury endosperm fills the crown (upper the hull may represent only 20%. The hull normally makes
part) of the kernel and extends downward to surround the up about 30% of the grain. Oat kernels, obtained by re-
germ. The starch granules in the floury endosperm are el- moving hulls, are called groats.
lipsoidal in shape. As dent corn matures, the endoperm
shrinks causing an indentation at the top of the kernel. In Sorghum. Sorghum kernels are generally spherical to
a typical dent corn, the pericarp comprises about 6%, the flattened spheres, have a kernel mass of 20 to 30 mg, and
germ, 11%, and the endosperm, 83% of the kernel by may be white, yellow, brown, or red. Sorghum has both
weight. Flint corn varieties contain a higher ratio of horny vitreous and opaque regions within the kernel similar to
to floury endosperm than do dent corn. that of corn. Sorghum grains contain polyphenolic corn-
Figure 1. A wheat kernel. Longitudinal section (enlarged ca 12 X). Source: Ref. 35.
Figure 2. A corn kernel. Longitudinal section (enlarged ca 8 X). Source: Ref. 35.
pounds, primarily in the outer kernel layers and to some is sprouted) and vitamin D. Yellow corn differs from white
degree in the endosperm. These compounds are colored corn and the other cereal grains in containing carotenoid
and impart various colors to certain foods from sorghums. pigments (principally cryptoxanthin, with smaller quan-
Condensed tannins, present only in some sorghum lines, tities of carotenes). These are convertible by the body to
are polyphenolic compounds that interact with and precip- vitamin A. Wheat also contains yellow pigments, but they
itate protein. Those tannins impart a bird resistance to the are almost entirely xanthophylls, which are not precursors
sorghum. This may be important if the sorghum is grown of vitamin A. The oils of the embryos of cereal grains are
in small plots in a forest (such as parts of Africa). However, rich sources of vitamin E. The relative distribution of vi-
the tannins also reduce nutritional value and germin- tamins in the kernel is not uniform, although the endo-
ability. sperm invariably contains the lowest concentration.
The protein contents of wheat and barley are important
Composition quality indices for the manufacture of various foods. For
example, the quantity and quality of wheat protein is criti-
The chemical composition of the dry matter of different cal in bread making. Cereal grains contain water-soluble
cereal grains, as with other foods of plant origin, varies proteins (albumins), salt-soluble proteins (globulins),
widely (36). A proximate analysis of the principal cereal aqueous alcohol-soluble proteins (prolamins), and acid-
grains is summarized in Table 4. Variations are encoun- and alkali-soluble proteins (glutelins). The prolamins are
tered in the relative amounts of proteins, lipids, carbohy- characteristic of the grass family, and together with the
drates, pigments, vitamins, and ash. Mineral elements glutelins, comprise the bulk of the proteins of cereal grains.
that are present and the quantities of them also vary The following are names given to prolamins in proteins of
widely. As a food group, cereals are characterized by rela- the cereal grains: gliadins in wheat, hordeins in barley,
tively low protein and high carbohydrate contents. The car- zeins in maize, avenins in oats, kaffirins in grain sorghum,
bohydrates consist of starch (90% or more of the total), pen- and secalins in rye.
tosans, and simple sugars (monosaccharides). The various proteins are not distributed uniformly in
The various components are not distributed uniformly the kernel. Thus, the proteins isolated from the inner en-
through the different kernel structures. The hulls and per- dosperm of wheat consist chiefly of prolamins (gliadin) and
icarp are high in cellulose, pentosans, and ash; the germ glutelins (glutenin). The embryo proteins consist of nucleo-
is high in lipid and rich in proteins, sugars, and ash com- protein, an albumin (leucosin), and globulins, whereas in
ponents. The endosperm contains the starch and is lower wheat bran a prolamin predominates with smaller quan-
in protein content than the germ and, in some cereals, than tities of albumins and globulins. In the presence of water,
bran. It is also low in crude fat and ash. As a group, cereals the wheat endosperm proteins, gliadin, and glutenin form
are low in nutritionally important calcium. Its concentra- a tenacious colloidal complex known as gluten. Gluten is
tion and that of other ash components is greatly reduced mostly responsible for the superiority of wheat over the
by the milling processes used to prepare refined flours and other cereals in the manufacture of leavened products be-
grits. In these processes, hulls, germ, and bran, which are cause it makes possible the formation of a dough that re-
the structures rich in minerals and vitamins, are in large tains the carbon dioxide produced by yeast or chemical
part removed. leavening agents. The gluten proteins collectively contain
All cereal grains contain vitamins of the B group, but 17.55% nitrogen. Consequently in estimating the crude
all are completely lacking in vitamin C (unless the grain protein content of wheat and wheat products from the de-
termination of total nitrogen, the factor 5.7 is normally
employed rather than the customary value of 6.25. The
latter value is based on the assumption that proteins con-
Table 4. Approximate Analysis of Important Cereal
Grains, Percentage of Dry Mass
tain an average of 16% nitrogen.
In general, cereal proteins are not as high in biological
Cereal Nitrogen Protein Fat Fiber Ash NFE value as are those of certain legumes, nuts, or animal prod-
Barley (grain) 1.2-2.2 11 2.1 6.0 3.1 ucts. Most cereals are low in Iysine and tryptophan. Oats
(kernel) 1.2-2.5 9 2.1 2.1 2.3 78.8 are a notable exception to this generalization. The biologi-
Maize 1.4-1.9 10 4.7 2.4 1.5 72.2 cal value of whole cereal grains is greater than that of re-
Millet 1.7-2.0 11 3.3 8.1 3.4 72.9 fined milled products, which consist chiefly of the endo-
Oats (grain) 1.5-2.5 14 5.5 11.8 3.7 sperm. Studies have shown that adults, if satisfying their
(kernel) 1.7-3.9 16 7.7 1.6 2.0 68.2 calorie needs, will not be protein deficient on nearly 100%
Rice (brown) 1.4-1.7 8 2.4 1.8 1.5 77.4 cereal diets. This may not be true for young children or
(milled) 0.8 0.4 0.8
Rye 1.2-2.4 10 1.8 2.6 2.1 73.4
pregnant women. In general, American and Western Eu-
Sorghum 1.5-2.3 10 3.6 2.2 1.6 73.0 ropean diets normally include animal products as well as
Triticale 2.0-2.8 14 1.5 3.1 2.0 71.0 cereals and, thus, satisfy protein requirements many times
Wheat (bread) 1.4-2.6 12 1.9 2.5 1.4 71.7 over. Under these conditions, the different proteins tend to
(durum) 2.1-2.4 13 1.5 70.0 supplement each other.
Wild rice 2.3-2.5 14 0.7 1.5 1.2 74.4 The predominant form of carbohydrate in cereals is
Note: Typical or average figure. NFE = nitrogen free extract (an approxi-
starch, which is the primary source of calories provided by
mate measure of the starch content). the grains. Most of the carbohydrates are in the starchy
Source: Ref. 32. endosperm.
Table 5. FDA Cereal Enrichment Standards
Product Thiamine (mg/lb) Riboflavin (mg/lb) Niacin (mg/lb) Iron (mg/lb) Calcium (mg/lb) Vitamin D (lU/lb)
Flour" 2.9 1.8 24 20 (960)
Self-rising flour 2.9 1.8 24 20 960
Corn grits 2.0-3.0 1.2-1.8 16-24 13-26 (500-750) (250-1000)
Corn meal 2.0-3.0 1.2-1.8 16-24 13-26 (500-750) (250-1000)
Rice 2.0-4.0 1.2-2.4 16-32 13-26 (500-1000) (250-1000)
Macaroni products 4.0-5.0 1.7-2.2 27-34 13-16.5 (500-625) (250-1000)
Noodle products 4.0-5.0 1.7-2.2 27-34 13-16.5 (500-625) (250-1000)
Bread" 1.8 1.1 15 12.5 (600)
U.S. RDA (mg or lU/day) 1.5 1.7 20 18 1000 400
0
In addition, flour is to contain 0.7 mg/lb and bread 0.43 mg/lb of folic acid. The figures in this table are the nutrient levels to be present in the final products
as set forth by the Food and Drug Administration (21 CFR 101.9, 137 and 139). Figures in parentheses are optional. When figures are shown as a range,
these indicate minimum/maximum values. When one figure is shown, it is the minimum required. Calicum is added by the milling company. It cannot be
included in the enrichment product. Enriched pasta products are normally made from flours enriched to these levels. Macaroni products with fortified protein
must have the maximum figures but no Vitamin D. If enriched bread is manufactured using at least 62.5% of enriched flour, the bread will meet standards
for enriched bread.
U.S. RDA (recommended daily allowances) as published in the 1986 21 CFR 104.20.
The lipids in cereals are relatively rich in the essential in making yeast-leavened breads. Soft red winter, soft
fatty acid linoleic acid. Saturated fatty acids (mainly pal- white, and white club wheats are especially suited for mak-
mitic) represent less than 25% of the total fatty acids of ing chemically leavened baked goods (cookies, cakes). Am-
most grains. ber durum wheat is prized for the manufacture of semolina
In summary, cereal grains are a diverse yet primary used to produce alimentary pastes (macaroni, vermicelli,
source of nutrients. Their high starch contents make etc). Red durum is used primarily as a poultry and live-
them major sources of calories. They also contribute to stock feed.
human needs for proteins, lipids, vitamins, and minerals. The wheat in each subclass is sorted into a number of
Vitamins and minerals lost during milling to produce re- grades on the basis of quality and condition. The tests gen-
fined food products can be, and in many countries are, re- erally used to determine the grade of grain and its con-
placed by nutrient fortification (Table 5). The composition formity to the official U.S. grain standards include plump-
of cereal grains and their milled products makes them ness, soundness, cleanliness, dryness, purity of type, and
uniquely suited for producing wholesome, nutritional, and the general condition of the grain (37,38).
consumer-acceptable foods. Other cereals are graded in a similar manner. Corn is
divided into three classes: yellow, white, and mixed. These
class designations apply to dent-type corn only. If the corn
STANDARDS AND CLASSIFICATION consists of at least 95% flint varieties, the word flint is
used. If the corn contains more than 5% but less than 95%
At the turn of the century, many organizations in the flint varieties, the corn is designated as flint and dent.
United States and in several other grain-producing coun- Waxy corn is corn of any class consisting of at least 95%
tries tried to develop uniform grain standards. The de- waxy corn. For many years moisture content was a grading
mand for uniform grades and application of the standards factor for corn and sorghum. Especially at the beginning
resulted in the introduction during 1903 to 1916 of 26 bills of the harvest, moisture content is the single most impor-
calling for the same in the U.S. Congress. tant quality factor of corn (high being problematic). Broken
Those bills and the extensive hearings that accompa- corn and foreign material (BCFM) is determined by sieving
nied them culminated in the U.S. Grain Standard Act, through a 12/64 in. (4.76 mm) sieve.
which was passed August 11, 1916, and amended in 1940 Rough rice is divided into three classes: long, medium,
to include soybeans. This act provides in part for the es- and short. There are separate standards for rough, brown,
tablishment of official grain standards, the federal licens- and milled rice. All rough rice is graded on the basis of
ing and supervision of the work of grain inspectors, and milled rice yields.
the mechanisms for filing appeals concerning grades as- Barley is divided into three classes (with several
signed by licensed inspectors. The official U.S. standards subclasses): six-rowed (malting, blue malting, and
for grain cover wheat, corn, barley, oats, rye, sorghum, flax- barley), two-rowed (two-rowed malting and two-rowed),
seed, soybeans, mixed grain, and triticale. and barley. Plumpness is determined by sieving. The des-
According to U.S. grain standards, wheat is divided into ignation malting requires inclusion of only varieties
seven classes on the basis of type and color: hard red that have been approved as suitable for malting purposes.
spring, durum, red durum, hard red winter, soft red winter, Special grades and designations of oats are: heavy or extra
white, and mixed. The division of wheat into classes and heavy (test weights of 48.9-51.5 kg/hL and >51.5 kg/hL,
subclasses is according to suitability of different wheats for respectively), thin, bleached, bright, ergoty, garlicky,
specific uses. Hard red spring, hard red winter, and hard smutty, tough (moisture between 14 and 16%), and
white wheats are valued for the production of flours used weevily.
BIBLIOGRAPHY 26. F. H. Webster, ed., Oats, Chemistry and Technology, American
Association of Cereal Chemists, St. Paul, Minn., 1986.
1. Canadian International Grains Institute, Grain and Oilseeds, 27. H. Doggett, Sorghum, Longmans, Green, and Co., London,
Handling, Marketing, Processing, 2nd ed., Canadian Inter- United Kingdom, 1970.
national Grains Institute, Winnipeg, Canada, 1975. 28. L. W. Rooney, D. S. Murthy, and J. V. Mertui, eds., Interna-
2. R. C. Hoseney, Principles of Cereal Science and Technology, tional Symposium on Sorghum Grain Quality, Proceedings,
American Association of Cereal Chemists, St. Paul, Minn., INCRASAT Patancheru, A. P. India, 1982.
1986. 29. W. Bushuk, ed., Rye: Production, Chemistry, and Technology,
3. D. W. Kent-Jones and A. J. Amos, Modern Cereal Chemists, American Association of Cereal Chemists, St. Paul, Minn.,
6th ed., Food Trade Press, London, United Kingdom, 1967. 1987.
4. R. A. Olson and K. J. Frey, eds., Nutritional Quality of Cereal 30. Yearbook of Agriculture, U.S. Government Printing Office,
Grains, American Society of Agronomy, Madison, Wis., 1987. Washington, D.C., 1985.
5. Y. Pomeranz, Modern Cereal Science and Technology, VCH 31. Y. Pomeranz, Functional Properties of Food Components, Ac-
Publishers, New York, 1987. ademic Press, Orlando, FIa., 1985.
6. Y. Pomeranz, ed., Industrial Uses of Cereals, American Asso- 32. J. E. Kruger, D. R. Lineback, and C. E. Stauffer, eds.,Enzymes
ciation of Cereal Chemists, St. Paul, Minn., 1973. and Their Role in Cereal Technology, American Association of
7. Y. Pomeranz, ed., Advanced Cereal Science and Technology, Cereal Chemists, St. Paul, Minn., 1987.
VoIs. I-X, American Association of Cereal Chemists, St. Paul, 33. H. G. Muller, "Some Physical Properties of Cereals and Their
Minn., 1976-1990. Products as Related to Potential Industrial Utilization," in Y.
8. Y. Pomeranz, ed., Cereals '78: Better Nutrition for the World's Pomeranz, ed., Industrial Uses of Cereals, American Associ-
Millions, American Association of Cereal Chemists, St. Paul, ation of Cereal Chemists, St. Paul, Minn., 1973, pp. 20-50.
Minn., 1978. 34. D. H. Simmonds, "Structure, Composition, and Biochemistry
9. Y. Pomeranz and L. Munck, eds., Cereals: A Renewable Re- of Cereal Grains," in Y. Pomeranz, ed., Cereals '78: Better Nu-
source, Theory and Practice, American Association of Cereal trition for the World's Millions, American Association of Ce-
Chemists, St. Paul, Minn., 1981. real Chemists, St. Paul, Minn., 1978, pp. 105-137.
10. H. Hanson, N. E. Bourlaug, and R. G. Anderson, Wheat in the 35. From Wheat to Flour, Wheat Flour Institute, Chicago, 111.,
Third World, Westview Press, Boulder, Colo., 1982. 1965.
11. E. G. Heyne, ed., Wheat and Wheat Improvement, 2nd ed., 36. B. Holland, I. D. Unwin, and D. H. Buss, Cereals and Cereal
American Society of Agronomy, Madison, Wis., 1987. Products, Royal Society of Chemistry, Ministry of Agriculture,
12. Y. Pomeranz, ed., Wheat is Unique, American Association of Fisheries, and Food, London, United Kingdom, 1988.
Cereal Chemists, St. Paul, Minn., 1989. 37. C. M. Christensen, ed., Storage of Cereal Grains and Their
13. Y. Pomeranz, ed., Wheat Chemistry and Technology, 3rd ed., Products, 3rd ed., American Association of Cereal Chemists,
American Association of Cereal Chemists, St Paul, Minn., St. Paul, Minn., 1982.
1988. 38. J. L. Multon, ed., Preservation and Storage of Grains, Seeds,
14. N. L. Kent, Technology of Cereals With Special Reference to and Their By Products, Lavoisier Publishing, New York, 1988.
Wheat, Pergamon, Oxford, United Kingdom, 1960.
15. I. D. Morton, ed., Cereals in a European Context, VCH Pub- R. CARL HOSENEY
lishers, New York, 1987. R & R Research Services
16. W. R. Akroyd and J. Doughty, Wheat in Human Nutrition, Manhattan, Kansas
FAO Nutritional Studies No. 23, FAO, Rome, Italy, 1970.
17. J. Holas and J. Kratochvil, eds., Progress in Cereal Chemistry
and Technology, 2 Elsevier Science, New York, 1983.
See also WHEAT SCIENCE AND TECHNOLOGY.
18. R. W. Jugenheimer, Corn: Improvement, Seed Production and
Uses, John Wiley & Sons, New York, 1976.
19. P. J. Barnes, ed., Lipids in Cereal Technology, Academic Press,
Orlando, FIa., 1983. CHEESE
20. M. N. Leath, L. H. Meyer, and L. D. Hill, U.S. Corn Industry,
Report No. 479, U.S. Department of Agriculture, Economic
Research Service, Washington, D.C., 1982.
ORIGIN
21. S. A. Watson and P. E. Ramstad, eds., Corn: Chemistry and
Technology, American Association of Cereal Chemists, St. The first use of cheese as food is not known. References to
Paul, Minn., 1987. cheeses throughout history are widespread. "Cheese is an
22. B. O. Juliano, ed., Rice, Chemistry and Technology, 2nd ed., art that predates the biblical era" (1). The origin of cheese
American Association of Cereal Chemists, St. Paul, Minn., has been dated to 6000-7000 B.C. and the worldwide num-
1987. ber of varieties has been estimated at 500, with an annual
23. B. S. Luh, ed., Rice: Production and Utilization, AVI Publish- production of more than 12 million tons growing at a rate
ing, Westport, Conn., 1980. of about 4% (2). This food served as a source of vital nour-
24. W. G. Heid, U.S. Barley Industry, Agr. Econ. Report No. 395, ishment in huts and castles and on journeys; armies also
U.S. Department of Agricultural Economics, Statistics and used cheese. It also was a way of preserving food during
Cooperative Service, Washington, D.C., 1978. periods of shortages. A plausible tracing of the origin and
25. D. C. Rasmusson, ed., Barley, American Society of Agronomy development of cheese, as a food, around the world has
Madison, Wis., 1985. been published (1).
BIBLIOGRAPHY 26. F. H. Webster, ed., Oats, Chemistry and Technology, American
Association of Cereal Chemists, St. Paul, Minn., 1986.
1. Canadian International Grains Institute, Grain and Oilseeds, 27. H. Doggett, Sorghum, Longmans, Green, and Co., London,
Handling, Marketing, Processing, 2nd ed., Canadian Inter- United Kingdom, 1970.
national Grains Institute, Winnipeg, Canada, 1975. 28. L. W. Rooney, D. S. Murthy, and J. V. Mertui, eds., Interna-
2. R. C. Hoseney, Principles of Cereal Science and Technology, tional Symposium on Sorghum Grain Quality, Proceedings,
American Association of Cereal Chemists, St. Paul, Minn., INCRASAT Patancheru, A. P. India, 1982.
1986. 29. W. Bushuk, ed., Rye: Production, Chemistry, and Technology,
3. D. W. Kent-Jones and A. J. Amos, Modern Cereal Chemists, American Association of Cereal Chemists, St. Paul, Minn.,
6th ed., Food Trade Press, London, United Kingdom, 1967. 1987.
4. R. A. Olson and K. J. Frey, eds., Nutritional Quality of Cereal 30. Yearbook of Agriculture, U.S. Government Printing Office,
Grains, American Society of Agronomy, Madison, Wis., 1987. Washington, D.C., 1985.
5. Y. Pomeranz, Modern Cereal Science and Technology, VCH 31. Y. Pomeranz, Functional Properties of Food Components, Ac-
Publishers, New York, 1987. ademic Press, Orlando, FIa., 1985.
6. Y. Pomeranz, ed., Industrial Uses of Cereals, American Asso- 32. J. E. Kruger, D. R. Lineback, and C. E. Stauffer, eds.,Enzymes
ciation of Cereal Chemists, St. Paul, Minn., 1973. and Their Role in Cereal Technology, American Association of
7. Y. Pomeranz, ed., Advanced Cereal Science and Technology, Cereal Chemists, St. Paul, Minn., 1987.
VoIs. I-X, American Association of Cereal Chemists, St. Paul, 33. H. G. Muller, "Some Physical Properties of Cereals and Their
Minn., 1976-1990. Products as Related to Potential Industrial Utilization," in Y.
8. Y. Pomeranz, ed., Cereals '78: Better Nutrition for the World's Pomeranz, ed., Industrial Uses of Cereals, American Associ-
Millions, American Association of Cereal Chemists, St. Paul, ation of Cereal Chemists, St. Paul, Minn., 1973, pp. 20-50.
Minn., 1978. 34. D. H. Simmonds, "Structure, Composition, and Biochemistry
9. Y. Pomeranz and L. Munck, eds., Cereals: A Renewable Re- of Cereal Grains," in Y. Pomeranz, ed., Cereals '78: Better Nu-
source, Theory and Practice, American Association of Cereal trition for the World's Millions, American Association of Ce-
Chemists, St. Paul, Minn., 1981. real Chemists, St. Paul, Minn., 1978, pp. 105-137.
10. H. Hanson, N. E. Bourlaug, and R. G. Anderson, Wheat in the 35. From Wheat to Flour, Wheat Flour Institute, Chicago, 111.,
Third World, Westview Press, Boulder, Colo., 1982. 1965.
11. E. G. Heyne, ed., Wheat and Wheat Improvement, 2nd ed., 36. B. Holland, I. D. Unwin, and D. H. Buss, Cereals and Cereal
American Society of Agronomy, Madison, Wis., 1987. Products, Royal Society of Chemistry, Ministry of Agriculture,
12. Y. Pomeranz, ed., Wheat is Unique, American Association of Fisheries, and Food, London, United Kingdom, 1988.
Cereal Chemists, St. Paul, Minn., 1989. 37. C. M. Christensen, ed., Storage of Cereal Grains and Their
13. Y. Pomeranz, ed., Wheat Chemistry and Technology, 3rd ed., Products, 3rd ed., American Association of Cereal Chemists,
American Association of Cereal Chemists, St Paul, Minn., St. Paul, Minn., 1982.
1988. 38. J. L. Multon, ed., Preservation and Storage of Grains, Seeds,
14. N. L. Kent, Technology of Cereals With Special Reference to and Their By Products, Lavoisier Publishing, New York, 1988.
Wheat, Pergamon, Oxford, United Kingdom, 1960.
15. I. D. Morton, ed., Cereals in a European Context, VCH Pub- R. CARL HOSENEY
lishers, New York, 1987. R & R Research Services
16. W. R. Akroyd and J. Doughty, Wheat in Human Nutrition, Manhattan, Kansas
FAO Nutritional Studies No. 23, FAO, Rome, Italy, 1970.
17. J. Holas and J. Kratochvil, eds., Progress in Cereal Chemistry
and Technology, 2 Elsevier Science, New York, 1983.
See also WHEAT SCIENCE AND TECHNOLOGY.
18. R. W. Jugenheimer, Corn: Improvement, Seed Production and
Uses, John Wiley & Sons, New York, 1976.
19. P. J. Barnes, ed., Lipids in Cereal Technology, Academic Press,
Orlando, FIa., 1983. CHEESE
20. M. N. Leath, L. H. Meyer, and L. D. Hill, U.S. Corn Industry,
Report No. 479, U.S. Department of Agriculture, Economic
Research Service, Washington, D.C., 1982.
ORIGIN
21. S. A. Watson and P. E. Ramstad, eds., Corn: Chemistry and
Technology, American Association of Cereal Chemists, St. The first use of cheese as food is not known. References to
Paul, Minn., 1987. cheeses throughout history are widespread. "Cheese is an
22. B. O. Juliano, ed., Rice, Chemistry and Technology, 2nd ed., art that predates the biblical era" (1). The origin of cheese
American Association of Cereal Chemists, St. Paul, Minn., has been dated to 6000-7000 B.C. and the worldwide num-
1987. ber of varieties has been estimated at 500, with an annual
23. B. S. Luh, ed., Rice: Production and Utilization, AVI Publish- production of more than 12 million tons growing at a rate
ing, Westport, Conn., 1980. of about 4% (2). This food served as a source of vital nour-
24. W. G. Heid, U.S. Barley Industry, Agr. Econ. Report No. 395, ishment in huts and castles and on journeys; armies also
U.S. Department of Agricultural Economics, Statistics and used cheese. It also was a way of preserving food during
Cooperative Service, Washington, D.C., 1978. periods of shortages. A plausible tracing of the origin and
25. D. C. Rasmusson, ed., Barley, American Society of Agronomy development of cheese, as a food, around the world has
Madison, Wis., 1985. been published (1).
CLASSIFICATION 4. Before pumping the milk to the cheese vat, the milk
fat can be homogenized, if desired. The extent of this ho-
Cheeses have been classified in several ways. Several at- mogenization will depend on the cheese variety being
tempts to classify the varieties of cheese have been made. made (Fig. 1).
One suggestion consists of scheme that divides cheeses 5. A bacterial starter culture is added to the milk,
into the following superfamilies based on the coagulating which is at 30-360C, depending on the cheese being made.
agent. This inoculated milk is generally ripened (held at this tem-
perature) for 30-60 min to allow the lactic organisms to
1. Rennet Cheeses. Cheddar, brick, Muenster multiply sufficiently for their enzyme systems to convert
2. Acid Cheeses. Cottage, Quarg, cream some of the milk sugar (lactose) to lactic acid.
3. Heat-Acid. Ricotta, sapsago 6. After ripening, a milk-coagulating enzyme is added
4. ConcentrationCrystallization. Mysost with stirring. The milk in the vat is then allowed to set in
a quiescent state.
A more simple but incomplete scheme, would be to classify 7. The resulting coagulum is usually ready to be cut
cheeses as follows. 20-30 min after the enzyme addition. For most fresh
cheeses little or no coagulating enzyme is added. Coagu-
1. Very Hard. Parmesan, Romano lation is allowed to occur by the development of lactic acid
2. Hard. Cheddar, Swiss alone.
3. Semisoft. Brick, Muenster, blue, Havarti 8. When the coagulum is firm enough to be cut, a com-
4. Soft. Bel Paese, Brie, Camembert, feta bination of vertical and horizontal stainless steel knives
5. Acid. Cottage, baker's, cream, ricotta (wires) are pulled lengthwise and crosswise through the
coagulum in a rectangular vat. If an automatic enclosed
A broad look at cheeses might divide them into two large circular vat is used, the cutting is programmed to insure a
categories, ripened and fresh. curd-size range by the speed and timing of the automatic
knives.
Ripened 9. For most varieties a heal time is allowed where no
stirring is done for 5-15 min after cutting. This allows the
Cheeses can be ripened by adding selected enzymes or newly cut curd particles to firm up slightly and begin syn-
microorganisms (bacteria or molds) to the starting milk, to eresis (excluding whey from the particle during the shrink-
the newly made cheese curds, or to the surface of a finish ing process).
cheese. The cheese is then ripened (cured) under conditions
controlled by one or more of the following elements: tem- 10. Following the heal period, heat is applied to the
perature, humidity, salt, and time. jacket of the vat and gentle stirring begins. For most rip-
Depending on the style of cheese, the ripening can be ened cheeses the curds are cooked in the whey until the
principally carried out on the cheese surface or the interior. temperature of the mixture reaches 37-410C, depending on
The selection of organisms, the appropriate enzymes, and the variety. For some cheeses, for example, Swiss and Par-
ripening regime determine the texture and flavor of each mesan, this temperature can be as high as 530C. The
cheese type. cheese is generally cooked for 30 min. Fresh cheeses, such
as cottage, cream, and Neufchatel, are cooked at tempera-
Fresh tures as high as 51.5-6O0C to promote syneresis and pro-
vide product stability.
These cheeses do not undergo curing and are generally the 11. Generally, when the cook temperature is reached,
result of acid coagulation of the milk. The composition, as a 45-60 min period is allowed to promote curd firming and
well as processing steps, provides the specific product tex- the releasing of whey. During this stir-out time the con-
ture, while the bacteria used to provide the acid usually tents of the vat are agitated somewhat vigorously.
generate the characteristic flavor of the cheese.
12. From this point the whey is drained and the treat-
ment of the new curd depends on the nature of the final
CHEESEMAKINGGENERAL STEPS product.
1. Milk is clarified by filtration or centrifugation. For cheeses such as Cheddar, Monterey Jack, Colby,
2. Depending on the composition of the final cheese, the brick, and mozzarella the curd can be handled in a number
fat content is standardized in a special centrifuge (sepa- of ways. Cheddar can be made by allowing the curd to set-
rator). tle in a rectangular vat, then draining the whey from the
3. Depending on the variety, the milk is pasteurized curd. When the whey is removed, the curd is trenched
(generally at about 720C (1610F) for 16 s) or undergoes any down the middle of the vat, lengthwise. The curd is hand
equivalent heat treatment that renders the milk phospha- cut, turned over, and then piled, at intervals, one slab on
tase negative. Phosphatase is inactivated in the same another. During this time acid continues to develop and
range as the tuberculin bacilli. The phosphatase test in- whey continues to be exuded from the curd. When the
sures that the milk is free of tuberculin bacilli and other proper pH is reached (about 5.1-5.3) the curd is milled by
pathogens. machine into finger-size pieces and slowly dry-salted to
Figure 1. Natural cheese system flow
key. a, Receiving pump/air eliminator;
b, cyclone filter; c, balance tank; d, flow
direction control; e, cheese vat; f, CIP
system; g, CIP control panel. Source:
Courtesy of Sherping Systems,
Winsted, Minn.
provide about 1.6-1.8% salt in the final cheese. The salted times over a number of days and then punctured to create
curds are then packed into 40-lb stainless-steel hoops with air channels in which the mold grows; this develops the
porous netting lining the hoops or into 600-700-lb boxes. characteristic blue veining. This cheese may be salt brined
These containers are generally pressed at 15-20 psi to re- instead to obtain a 4% salt content in the final cheese. The
move more whey over several hours and then placed into cheese is cured for 60-120 days at 130C and 95% humidity
a vacuum chamber while under pressure to fuse the curd to achieve full veining and flavor.
particles into a solid mass. Swiss, Parmesan, and other varieties are handled some-
Several methods are used to arrive at a solid cheese what differently at the whey drainage step. For years these
block. One process provides for pumping the curds into a cheeses were manufactured in Europe in wheel-shaped
tower that allows whey drainage and compacting of the hoops; 20-lb wheels were used for Parmesan and 175-225-
curds by their own weight. At the bottom of the tower a Ib hoops, for Swiss. The principles are the same so the de-
portion of the curd is cut off to fit into a 40-lb hoop, which scription here will pertain to most U.S. products. For Swiss
travels to a press station and, finally, to a packaging sta- cheese the curds and whey are pumped to a large stainless-
tion. steel universal vat, which has been equipped with porous
In another method, curd and whey are pumped from the side plates, where the curd is allowed to settle evenly at
vat to a draining-and-matting conveyer (DMC) under con- the bottom. Large stainless-steel plates are used to press
trolled temperature and curd depth. When the curd has the curd at a precise depth of the curd mass. This pressing
reached the proper pH, the mat is cut and is automatically under whey results in a tightly fused cheese, required later
salted and transferred onto another conveyer where it is for eye development. The whey is drained and the huge
finally carried to a boxing operation (Fig. 2). curd block is kept under pressure for about 16 h while it
There is also a stirred-curd procedure used for mild- and continues to develop acidity. Then the 3,000-3,500-lb block
medium-flavored Cheddar as well as Colby, brick, mozza- is cut into sections of about 180 Ib and immersed into 20C
rella, etc. In this method the curd and whey are pumped saturated brine for 24 h. The surface of the blocks are then
to a drain table or automatic-finishing vat (AFV) where the dried. The blocks are packaged and boxed. These boxes are
whey is drained and the curds are continually stirred to stacked and banded to help keep the block shape as the
prevent matting. When the proper pH is achieved the cheese cures in a hot room at 20-250C. When the eyes have
cubes are salted and then boxed as previously described formed (about 18-28 days) the blocks are transferred to a
(Fig. 3). room at about 20C to prevent further eye development and
If stirred curd Cheddar is intended for use in process held for at least 60 days before cutting into retail sizes.
cheese it can be packed into 500-lb drums and used after The cheese can be held for longer periods if stronger Swiss
a short curing period. It should be noted that cheeses such flavor is desired.
as Monterey Jack and Colby, should not be placed under For Parmesan cheese, the curd is stirred while draining
vacuum to preserve a slight open texture. off the whey and then placed into round 20-lb hoops. After
Blue cheese is made in a similar manner up to this pressing, the round cheeses are allowed to surface dry be-
point, but the mold (Penicillium sp.) can be added to the fore brining. If salt has not been added during the stirring
starting milk or to the drained curds. This cheese is usually of the curds, additional brining time is required. The
formed in 5-lb hoops to promote an open texture. When the cheeses are held at 13-160C until the proper weight is
cheese is removed from the hoops it is dry-salted several reached (moisture reduced) and then vacuum packed in
Static plough blades
to turn curd and promote
free drainage of whey with
minimum curd damage
Draining belt
Guillotine
Conveyor to
next process
Discharge
conveyor
Curd Interchangeable
discharge curd mill
Figure 2. Cheese curd draining conveyor. Source: Courtesy of Sherping Systems, Winsted, Minn.
plastic bags with a tight seal. Some factories wax the smaller shapes to allow surface salting or brining and
cheese. This cheese requires a minimum of a 10-mo cure treatment of the cheese surface with selected bacteria or
time by federal regulation. Most of the U.S. Parmesan is molds to provide the characteristic flavors, and textures.
grated for use as a retail product. Fresh cheeses such as cottage, queso fresco, and cream
Mozzarella and provolone are among those cheeses re- are mostly acid in nature and, following cooking of the
ferred to as pasta filata varieties. Provolone has some Ii- curds, are treated differently. Cottage curds are washed
pase enzymes added to produce its characteristic flavor with filtered water and then combined with a cream dress-
and sometimes is sold naturally smoked or with smoke fla- ing. Queso fresco is pressed into loaves after salting and
vor added. These cheeses have traditionally been further eaten fresh after slicing. Cream cheese curd is separated
cooked, after whey drainage, in hot water and stretched by centrifugally and then standardized in regard to fat, salt,
hand with subsequent shaping into the familiar forms. To- and stabilizers. Stabilizers are added to prevent moisture
day, however, most mozzarella and provolone are mechan- release. It can then be packaged in small loaves, hot or
ically cooked under water and further stretched to provide chilled.
texture and then shaped in molding machines. The cheeses
RECENT DEVELOPMENTS
are then brined to the proper salt level.
Cheeses such as Camembert, Brie, Muenster, and Lim- A number of cheese varieties have been manufactured
burger are made in smaller equipment and formed into from milk concentrated by ultrafiltration (3,4). Patents
Salt dispenser
with oscillating Bulk salt receiver
boom spreader
Curd inlet
Heated salt hopper
Levelling screw
Curd discharge
trough with auger
Hot air blower
Peg stirrer with Salt metering unit
parking position clear
of curd on belt
Salting belt
Mellowing belt
Figure 3. Dual salt applicating and cheese curd mellowing system. Two stage continuous salting
and mellowing of milled or granular curd. Source: Courtesy of Sherping Systems, Winsted, Minn.
have been issued (5) and some procedures have been re- 1. Acid production and coagulation of milk.
duced to practice, but after more than 20 years of research 2. Acid gives firmness to the coagulum, which influ-
in this area only a minimal amount of the total world pro- ences cheese yield.
duction of cheese is made with ultrafiltered milk.
3. Developed acidity determines the residual amount of
Bactofugation used to remove microbes and spores from
animal rennet influencing cheese ripening; more
cheese milk has sparked some interest, especially in Eu-
acid curd binds more rennet.
rope (6). Microfiltration may find significant application in
special milk treatment prior to, or during, product manu- 4. The rate of acid development influences dissociation
facture. Significant developments in recombinant biotech- of colloidal calcium phosphate, which then influences
nology and fermentation technology may provide specific- proteolysis during manufacture and the rheological
ity previously not available for milk coagulation and properties of cheese.
cheese flavor development. New cultures, which are resis- 5. Acid development and production of other antimicro-
tant to phage, may be on the horizon. New cheese-making bials control the growth of certain nonstarter bacte-
technology may allow previously unattainable processes ria and pathogens in cheese.
and product control to become reality. 6. Acid development contributes to proteolysis and fla-
vor production in cheese.
Cheese Starter Cultures
Starter cultures are organisms that ferment lactose to lac- Types of Culture
tic acid and other products. These include streptococci, leu-
conostocs, lactobacilli, and streptococcus thermophilus. There are some impending changes in the nomenclature of
Starter cultures also include propionibacteria, brevibac- starter culture organisms; the nomenclature used here fol-
teria, and mold species of Penicillium. The latter organ- lows present standards (7). Mesophilic cultures are used
isms are used in conjunction with lactic acid bacteria for a for cheese types that do not exceed 4O0C during cheese
particular characteristic of cheese, eg, the holes in Swiss making (8). These starters are propagated at 21-230C and
cheese are due to propionibacteria, and the yellowish color include Streptococcus lactis ssp. lactis, S. lactis ssp. cre-
and typical flavor of brick cheese is due to brevibacterium moris, S. lactis ssp. diacetylactis andLeuconostoccremoris.
linens. Blue cheese and Brie derive their characteristics These are used for Cheddar, Gouda, brick, Muenster,
from the added blue and white molds, respectively. Lactic cream, cottage, and Quarg cheese types, leuconstoc and S.
acid-producing bacteria have several functions: lactis ssp. diacetylactis ferment citrate to produce carbon
dioxide and diacetyl to characterize Edam, Gouda, and Animal and microbial rennets are aspartic proteases
cream cheese. with optimum activity under acidic conditions. Their mo-
Thermophilic cultures are used in cheese types where lecular weights range from 30,000 to 38,000. The primary
curd is cooked to 45-560C. These starters are propagated stage of rennet coagulation involves partial hydrolysis of
at 40-450C and include 8. thermophilus, sometimes fecal jfiT-casein, the principal stabilizing factor of milk protein, at
streptococci, Lactobacillus helveticus, L. delbrueckii ssp. Phe-105 to Met-106 bond. Destabilization of the residual
lactis, and L. delbrueckii ssp. bulgaricus. These are used protein (para-casein) occurs in the presence of Ca2+ at
for Swiss, Emmentaler, Gruyere, Parmesan, Romano, moz- temperatures >18C in the secondary, nonenzymatic stage
zarella, and Gorgonzola cheeses (9). of rennet coagulation. About 30% of calf rennet is retained
in the curd before pressing and only 5-8% after pressing
Propagation (11). The amount of rennet retained is governed by the pH
of the curd. Microbial rennets are retained to a lesser ex-
Cultures are propagated in milk or a medium containing
tent (3-5%).
milk components and other nutrients and are heat treated
During coagulation, linkages between casein micelles
(85-90C for 45 min) to render milk free of contaminants.
are formed and many micelles are joined by bridges, but
The medium is then cooled to incubation temperature be-
later these appear to contract, bringing the micelles into
fore inoculation. This processing is accomplished in a jack-
contact and causing partial fusion. The firmness of curd is
eted stainless-steel vessel provided with agitation and sup-
due to an increase in both the number and strength of link-
plied with sterile air pressure. Culture inoculum is
ages between micelles. It is suggested that phosphoryl side
available from suppliers in frozen or freeze-dried form. It
chains of casein specially /?-casein are involved. These may
consists of appropriate mixture of culture strains and is
be linked by Ca2+ bridges. In cheese, os-1-casein plays a
free of contamination. After inoculation, culture is allowed
structural role (12).
to grow in quiescent state for 12-18 h. At the end of growth
Casein aggregation and fusion continues after coagu-
the medium is acidic with a pH of 4.5 or lower, depending
lum cutting and throughout cheese making and early
on the culture. Ripened culture cell population is about 109
stages of cheese ripening. This process of rennet coagula-
cfu/g. The ripened culture is cooled to at least 50C. This
tion of milk is fundamental to the conversion of milk to
form of propagation is called bulk-starter propagation. The
cheese curd and its manipulation is essential for the con-
culture may be used immediately or held for several days.
trol of cheese manufacture (Table 1). Casein aggregation
The growth medium may contain buffering salts or the acid
leads to curd formation and syneresis. Increase in acidity
produced may be neutralized and controlled by the addi-
and temperature and the addition of calcium chloride ac-
tion of ammonia, potassium hydroxide, or sodium hydrox-
celerates the rate of curd formation and its syneresis. On
ide under controlled conditions. The latter is called pH-
the other hand, cold storage of milk, homogenization,
controlled propagation.
higher pasteurization temperature, and increased fat con-
Starter cultures are susceptible to bacteriophages (vi-
tent impede the two processes. Acid coagulation of milk, as
ruses), which destroy the cultures and hamper cheese pro-
in cottage-cheese making results in less aggregation of ca-
duction. Cultures are also sensitive to antibiotics and bac-
sein than is seen with rennet. During cottage-cheese mak-
teriocins (proteinaceus bacterial inhibitors). Propagated
ing the pH of milk casein drops to its isoelectric point re-
cultures are used at 1-5% of cheese milk. Highly concen-
sulting in a soft, fragile gel, firm enough to be cut. For
trated (1010 cfu/g) frozen cultures are available for direct
large-curd cottage cheese, a very small amount of rennet
addition to cheese milk (350 g/5,000 Ib). These are called
is added. Essentially all added rennet is inactivated at the
direct vat set (DVS). This form is convenient, but expen-
cooking temperature of curd (57-6O0C).
sive.
themselves and with the microbial population to result in demineralized with respect to calcium and phosphorus.
a more flavorful and preserved milk. Both casein and milk The rate and extent of acid production governs the residual
fat hydrolysis is needed for cheese flavor development, but chymosin, minerals, moisture, and the cheese texture and
the rate and extent of such hydrolysis must be controlled structure. Higher acid in cheese reflects higher starter pop-
to maintain cheese identity. Different cheese types are dis- ulations, possibly resulting in bitter cheese due to total
cussed below with these comments in mind. proteinase activity from starter cells.
Lactic starter cultures are added to vat milk to give Cheddar-type curd is dry salted. Addition of salt to the
about 106-107 cfu/mL. The amount and type of starter may curd is the last step in the manufacture of cheese. It con-
vary significantly depending on the type of cheese and trols microbial growth and activity and the final pH of
characteristics desired. In most cheese types an overnight hooped cheese. At hooping Cheddar cheese may contain
pH range is 4.95-5.3. 0.6% lactose. Its fermentation to lactic acid depends on
SIS + M. Culture activity is inhibited by S/S + M of >5%
Cheddar-Type Cheese (13). Salt also helps to expel moisture. Proteolytic activity
of chymosin and pepsin on as-1-casein is stimulated by
In Cheddar, Caciocavallo, and Colby types of cheese, about salt, whereas ^-casein proteolysis is inhibited by S/S + M
30-40% of the added culture cells are lost in whey. The cells of 5%. Salt appears to affect physical changes in cheese
trapped in the rennet coagulum rapidly multiply and fer- protein, which influence cheese texture, protein solubility
ment lactose to lactic acid. The population of starter or- and probably protein conformation. Cheddar-type cheese
ganisms may reach in excess of 5 X 108 cfu/g in curd before is internally ripened by chymosin in concert with starter
salting. These bacterial numbers include a 10-fold increase proteinases and adventitious lactobacilli. For normal rip-
due to milk solids concentration. The cultures multiply ening a high starter population must lyse to release pro-
only slightly during coagulation and cooking, but growth teinases and peptidases affecting cheese flavor, body, and
and acid production accelerate after whey is removed and texture development. In most cheese types there is a shift
continues through cheddaring as the starter cells are con- in the population of starter organisms to lactobacilli and
centrated in the curd. Acid production will continue until in some cases pediococci. It has been demonstrated that in
the lactose is depleted. At the time of milling the curd may young cheese there are inhibitory and stimulatory factors
have a pH of 5.3 and titratable acidity of whey at 0.57% or for lactobacilli. As the cheese ripens, most of the inhibition
higher. vanishes. These stimulatory factors for lactobacilli appear
The milling operation involves cutting the curd into to originate primarily in os-casein (14). In Cheddar cheese,
small pieces to facilitate uniform salt distribution and /?-casein is not extensively degraded (15). Studies with
whey drainage. Enough salt is applied to the curd in two starters lacking proteinase indicate the importance of
or three applications to yield a salt-in-moisture phase starter proteinases (16). Proteolysis and increasing con-
(S/ S + M) of the cheese of about 4-5%. Due to steady acid centration of free amino acids add to the savory taste and
production throughout cheese making the casein curd is provide substrate for sulfur compounds. Many flavor com-
pounds are chemical interactions of microbially derived strains of lactobacilli and fecal streptococci, biogenic
substrates under conditions of low pH and low oxidation- amines are sometimes found in Swiss cheese.
reduction potential. Numerous compounds, such as hydro-
carbons, alcohols, aldehydes, ketones, acids, esters, lac- Camembert Cheese
tones, and sulfurs are important in cheese flavor.
This is a soft cheese with 48-52% moisture. Milk inocu-
Hydrogen sulfide and methanethiol along with phenyl-
lated with 1-5% mesophilic lactic starter is renneted at
acetaldehyde, phenylace tic acid, and phenethanol are con-
about 3O0C. When the acidity reaches 0.20-0.23% the curd
sidered key compounds of good Cheddar flavor (17). Lactic
is dipped, molded, and held at 210C in rooms with 85-90%
acid bacteria are not lipolytic but small increases in butyric
humidity until it reaches pH 4.5-4.6. During storage, yeast
and other fatty acids appear desirable.
and Geotrichum candidum appear on the surface. After
about a week at about 1O0C Penicillium camemberti covers
Swiss, Emmentaler, and Gruyere the surface and deacidifies the cheese in 15-20 days. This
These cheese types are made with thermophilic strepto- is followed by colonization of the cheese surface by B. linens
cocci and lactobacilli to which propionibacteria are added and micrococci. During ripening, the surface pH rises to
for eye formation. During the early phases of cheese mak- about 7.0. /?-Casein is not extensively degraded. Appear-
ing S. thermophilus multiplies rapidly and utilizes the glu- ance of some y-casein suggests plasmin activity. There is
cose moiety of lactose to produce L-lactate, leaving behind os-casein degradation but less compared to Cheddar
galactose. Lactobacilli start vigorous acid production after cheese. In Camembert, due to extensive deamination, am-
whey drainage when the curd temperature drops to 46- monia constitutes 7-9% of the total N. Free fatty acids
490C. Acid production and starter bacteria number are found in large quantities contribute to the basic flavor of
greater toward the periphery where the cheese has cooled cheese and serve as the precursors of methylketones and
down. Lactic acid fermentation in cheese is complete secondary alcohols. Aldehydes, methylketones, 1-alkanols,
within 24 h with no detectable sugars. 2-alkanols, esters (C2, 4, 6, 8, 10-ethyl 2-phenylethylace-
tate), phenol, p-cresol, lactones, hydrogen sulfide, metha-
Changes During Ripening. Increase in starter organisms nethiol, methyldisulfide and other sulfur compounds along
population and acidity are halted when the cheese is with anisoles, amines, and other compounds constitute the
brined. This is due to exhaustion of fermentable sugar and volatile compounds.
the low brine temperature. Cheese is cured in a hot room
(20-25C) for 18-40 days. During this period the added Blue Cheese
starter organisms disappear and the niche is occupied by Blue cheese and its relatives, Roquefort, Stilton, and Gor-
propionibacteria, adventitious lactobacilli, and fecal strep- gonzola are characterized by peppery, piquant flavors pro-
tococci. Propionibacteria ferment lactate to propionic acid duced by the mold Penicillium roqueforti. Milk for cheese
and other flavor compounds according to the reaction: making may be homogenized to promote lipolysis in
3CH3CHOHCOOH -> 2CH3CH2COOH + CH3COOH + cheese. An acid curd with pH 4.5-4.6 is produced with
CO2 + H2O. mesophilic lactic starter and sometimes include S. lactics
ssp. diacetylactis. Gorgonzola is made with S. thermophi-
Eye Formation. The quality of Swiss cheese is judged by lus and Lactobacillus bulgaricus. The blue mold is added
the size and distribution of eyes. Swiss cheese eyes are to the milk or curd. The molded curd is dry salted, and salt
essentially due to carbon dioxide production, diffusion, and is rubbed on cheese to attain 4-5% salt. After about a week
accumulation in the cheese body (18). The number and size the cheese heads are pierced with needles to aerate the
of eyes depend on carbon dioxide pressure, diffusion rate, cheese and let carbon dioxide escape and air enter. This
body texture, and temperature of cheese. The bulk of pro- promotes mold growth.
tein breakdown products are derived from os-casein. /?- Due to high acid and salt, starter population declines
Casein is not greatly proteolysed in Swiss cheese (15). Bac- rapidly and the blue mold grows throughout the cheese.
terial proteinases and plasmin (milk proteinase) are Salt-tolerant B. linens and micrococci appear on the cheese
considered important in Swiss cheese ripening. surface in two to three weeks. Due to deacidification of the
cheese and extensive proteolysis, the cheese pH rises from
Flavor. Cheese flavor is derived in part from cheese 4.5 to 4.7 at 24 h to a maximum of 6.0-6.25 in two to three
milk. However, the characteristic flavor of Swiss-type months.
cheese comes from the microbial transformation of milk Molds are both proteolytic and lipolytic, resulting in ex-
components. These contain water-soluble volatiles (acetic tensive proteolysis and lipolysis of cheese. In blue cheese
acid, propionic acid, butyric acid, and diacetyl), which give both as- and ^-casein are degraded. There is a large accu-
the basic sharpness and general cheesy notes (17). Water- mulation of free amino acids due to extracellular acidic and
soluble nonvolatile amino acids (especially proline), pep- alkaline endopeptidases (19). B. linens and micrococci are
tides, lactic acid, and salts provide mainly sweet notes. Oil- also proteolytic and contribute to the overall proteolysis.
soluble fractions (short-chain fatty acids) other than the Occurrence of citrulline, ornithine, y-aminobutylic acid,
water-soluble volatiles are important to flavor. Nutty fla- and biogenic amines reflect amino acid break-down prod-
vor is attributed to alkylpyrazines. Several compounds, eg, ucts. Other volatile compounds such as ammonia, alde-
ketones, aldehydes, esters, lactones, and sulfur-containing hydes, acids, alcohols, and methanethiol are also produced
compounds are important. Due to the activity of certain from amino acid metabolism.
Mold-ripened cheeses have a high free fatty acid con- cheese. Starter organism production of low molecular
tent, 27-45 meq of acid per 100 g of fat. Penicillium roque- weight peptide fractions and amino acids are stimulated
forti produces two lipases, one active at pH 7.5-8.0 or by rennet action.
higher and the acid lipase active at pH 6.0-6.5. The fatty Lipolysis occurs to a small degree mainly due to en-
acids produced are converted into methylketones via zymes of starter bacteria liberating free fatty acids from
ketoacyl-coenzyme A and the /?-keto acids (20). Thiohydro- monoglycerides and diglycerides formed by milk or micro-
lases are also present in cheese, resulting in the accumu- bial lipases. In well-made Edam and Gouda lactobacilli do
lation of 2-heptanone. The rate of fatty acid release gov- not exceed 105-106/g or certain defects in the cheese are
erns the rate of methylketone formation (21). noticed. Lactic acid, carbon dioxide, diacetyl, aldehydes,
ketones, alcohols, esters, and organic acids in proper bal-
Brick Cheese ance are important to flavor. Anethole and bismethyl-
thiomethane are important odor compounds of Gouda
Brick cheese is representative of a large group of cheeses
cheese (24).
(Limburger, Muenster, Tilsiter, Bel Paese, and Trappist)
ripened with the aid of surface flora made of yeast, micro-
Mozzarella and Provolone
cocci, and coryneform bacteria (B. linens). A culture of S.
lactis ssp. lactis, S. lactis ssp. cremoris, and sometimes in These cheese types may contain 45-60% moisture. S. ther-
combination with S. thermophilus is used to cause a cheese mophilus, thermophilic Lactobacillus sp. or mesophilic lac-
pH of 5.0-5.2. After brining for one or more days cheese is tics with S. thermophilus combination starters are used.
held at about 150C (6O0F) in rooms with a 90-95% RH Sometimes citric acid or other acids are used in place of
where yeast (Mycoderma) appear on the surface in two or lactic starters.
three days followed by micrococci and then B. linens. Or- The cultures used generally cleave the galactose moiety
ganisms from the genus Arthrobacter have also been iso- of lactose in cheese, which, if not utilized, result in dark
lated from the cheese surface. Cheese ripens in four to brown cheese color on baking. In fresh brined cheese there
eight weeks depending on the moisture and intensity of may be 108 cfu/g of starter organisms in 1:1 ratio of strep-
cheese flavor desired. Film-wrapped cheese has more tococci and lactobacilli. os-Casein is proteolysed to a lesser
rounded flavor than waxed cheese. degree by rennet enzymes compared to other cheese types,
Growth of yeast lowers the acidity on the surface, mak- while /?-casein is largely intact. This level of rennet pro-
ing it suitable for micrococci and B. linens colonization (22). teolysis of milk protein is sufficient to give the melt and
Sometimes G. candidum may also be present. os-Casein is stretch characteristics to cheese during hot water knead-
always hydrolyzed but ^-casein disappearance was seen in ing at about 570C. The molded cheese is brined. The pH of
Muenster and not in brick. Yeasts found on Limburger cheese should be 5.1-5.4. There is little lipolysis and fatty
cheese synthesize considerable amounts of pantothenic acids liberation in traditional mozzarella cheese (25).
acid, niacin, and riboflavin (23). Pantothenic acid and Cheese made with mesophilic starter and S. thermophilus
para-aminobenzoic acid are required by B. linens Thus ex- tends to have greater protein and fat hydrolysis during
plaining the population sequence. Liberated free amino ac- storage. Such cheese is difficult to shred and has atypical
ids are much higher on the surface than in the interior of flavor when aged.
cheese. Activities of micrococci appear essential to the de- Mozzarella and provolone are manufactured in a simi-
velopment of typical flavor of brick or Limburger cheese. lar manner. The former is consumed fresh while the latter
These proteolytic organisms are able to convert methio- may be ripened at 12.50C for three to four weeks and then
nine to methanethiol. Acetyl methyl disulfide is character- stored at 4.50C for 6-12 months for grating. The ripened
istic of Limburger flavor. cheese have mainly Lactobacillus casei and its subspecies.
Sometimes leuconstocs are detected in cheese, particularly
Edam and Gouda if no starter was used.
These Dutch cheese varieties are made with S. lactis ssp.
Parmesan and Romano
lactis, S. lactis ssp. cremoris, Leuconstoc cremoris and/or
L. lactis. Leuconstoc and S. lactis ssp. diacetylactis ferment Parmesan and Romano cheese are made with S. thermo-
citrate to produce carbon dioxide, diacetyl, and other com- philus, Lactobacillus bulgaricus, or other species of ther-
pounds. The starter organisms reach ~109 cfu/g in curd mophilic lactobacilli. In addition to rennet, pregastric es-
with a pH of about 5.7. The remaining lactose in curd is trases, or rennet paste may be added to cheese milk for
fermented in an uncoupled state to lower cheese pH to 5.2. their lipolytic activity. The curd is cooked to 51-540C, when
Molded cheese forms are placed in 14% brine at 140C for the whey acidity reaches about 0.2% it is hooped (packed)
three to seven days. After brief drying, the cheese is coated in round forms. Sometimes salt is added to the curd, which
with two to three coats of plastic emulsion, which permits slows the starter and regulates moisture. The cheese at pH
slow moisture evaporation. Carbon dioxide production is 5.1-5.3 is placed in 24% brine for several days.
essential to eye formation. Ripening changes involve pro- Compared to other cheese types, the starter populations
teolysis by rennet enzymes, enzymes of starter bacteria, in the fresh cheese is low. Throughout cheese ripening, 12-
and, to a small extent, native milk proteinase. Rennet is 24 months, cheese flora seldom exceeds 105 cfu/g. Fecal
responsible for extensive degradation of os-casein to large streptococci and salt-tolerant lactobacilli predominate. In
molecular weight water-soluble peptides. This proteolysis these hard grating cheeses as- and /?-caseins are not overly
is significant in determining the body characteristics of proteolysed compared to other cheese varieties. This is at-
tributed to high cooking temperatures of curd, which in- Moisture accumulation on the surface of hard cheeses per-
activates the coagulant, and the high salt in the moisture, mits rind rot due to yeasts, molds, and proteolytic bacteria
which discourages growth of adventitious flora. In ripened growth, sometimes accompanied by discoloration. Milk it-
cheeses quality varies from location to location. Volatile self can at times contribute weedy, feedy, cowy, barny, and
free fatty acid and nonvolatile free fatty acid (C4 through related flavors coming from the cow. Psychrotrophic organ-
C18) concentrations are high in these cheeses, particularly ism growth in milk can generate rancidity due to lipolysis
in Romano (25). Butyric acid and minor branched chain and bitterness due to proteases from these organisms. Spe-
fatty acids that occur in milk appear to contribute to the cific defects are discussed below.
piquant flavor of Parmesan. For a more balanced flavor a
concomitant increase in free amino acids (glutamic acid, Swiss Cheese
aspartic acid, valine, and alanine) has been noted. Too high
a free fatty acid level in cheese gives a strong, soapy, un- Swiss is graded by the size, number, and distribution of
desirable flavor. eyes; there are many defects of the eyes (18). Blind or
cheese with no eyes may be due to inhibition of carbon
dioxide production of proprionibacteria by pH of less than
Cottage Cheese and Cream Cheese
5.0, prolonged brining (high salt), and antibiotics or other
These are cultured to the isoelectric point of casein (pH inhibitors in milk or cheese.
4.6) followed by heating to separate the cheese solids. Overset (pinny or too many eyes) is generally caused by
Cottage cheese curd is blended with a cultured or uncul- improper acidity, high moisture, entrapment of air in curd,
tured cream to no more than 4% fat. Cream cheese is cul- and other factors that prevent knitting of curd before gas
tured with lactics and citrate-fermenting cultures. Diace- production. Early gas is caused by Enterobacter aerogenes.
tyl, ethanol, acetone, lactic acid, acetic acid, and other Flavor defects, such as stink spots, white spots (28), and
less-characterized compounds are responsible for the fla- excessive amine production, are caused by Clostridium ty-
vor of these products. robutyricum, S. faecalis ssp. liquefaciens, and strains of
Lactobacillus buchenerii, respectively.
ACCELERATED CHEESE RIPENING Cheddar Cheese
One of the major costs of cheese is the expense of curing Excessive acidity, below pH 5.0 at three or more days,
time before desired flavor develops. While some matura- causes short, crumbly body and a sour, often bitter flavor.
tion time is inevitable, there are systems available where Normal body and flavor development may not occur in this
ripening time is shortened by speeding up proteolysis and cheese. On the other hand, too little acid or pH above 5.3
lipolysis to generate flavor and modify texture. Elevated at three or four days may lead to corky, pasty body with
temperature (130C or higher) curing offers the simplest ap- off-flavor development. Open-texture defect may be caused
proach to speed up ripening of otherwise normal cheese. by lactobacillus fermentum, L. brevis, and leuconostocs.
Cheese intended for this type of curing must not contain Raw milk and rennet preparations have been linked to
measurable levels of heterofermentative lactobacilli or leu- these defects.
conostocs, because an open-texture defect and off-flavors
will develop (26). Edam and Gouda
Microbial proteinases and gastric esterases have been
Edam and Gouda are subject to spoilage similar to Ched-
used with little success to achieve acceptable cheese with
dar. In these cheeses, brine has been known to contami-
uniformity. Activity of these exogenous enzymes is unregu-
nate the cheese surface with gas-forming lactobacilli.
lated and may contribute to the detriment of cheese qual-
These may cause the occurrence of phenols, putrid odor,
ity. Several unproven systems are available from culture
and sulfidelike flavors and excessive production of carbon
houses.
dioxide. Butyric acid fermentation and carbon dioxide pro-
Additions of partially inactivated starter organisms
duction are due to C. tyrobutyricum. Growth of propioni-
have been used with mixed results. Presently, this is not
bacteria may cause a sweet taste and an open texture due
economical. Most of the proprietary systems investigated
to carbon dioxide.
cause a minor to major deviation from characteristic flavor,
body, and texture of cheese,
Brick Cheese
Excessive acidity is a major defect. Coliform bacteria can
CHEESE DEFECTS
grow during draining and salting, causing early gas, which
if excessive can yield a spongy condition. Sometimes, due
Cheese varieties exist because manufacturing and curing to lack of surface smear growth, typical flavor does not de-
are carried out to preserve characteristic flavor, body, and velop.
texture of a given cheese. Attributes of one cheese may
prove to be defects in another.
Blue Cheese
Even though certain molds are used for manufacturing
and curing of cheese, their growth on most cheeses is un- Blue cheese may not have sufficient mold growth, leading
desirable (27). Gas production with putrid, unclean odors to lack of flavor and general development of cheese attrib-
due to nonstarter bacteria constitute a defect in cheese. utes. Excessive growth of mold may cause mustiness and
loss of flavor. Mold-ripened cheeses are sensitive to bitter- vented process cheese. A patent issued to J. L. Kraft in
ness development due to excessive acidity in the curd fol- 1916 marked the origin of the process cheese industry in
lowed by abundant mycelium growth and proteases. Sur- America and describes the method of heating natural
face discoloration by other molds is not uncommon. cheese and its emulsification with alkaline salts.
Excessive slime and undesirable flavors occur due to ex- Process cheeses in the United States generally fall into
cessive humidity in curing rooms. one of the following categories (29).
Improved slicing properties without crumbling. Tripotassium citrate (used in reduced-sodium for-
Smooth melting without phase separation. mulations, promotes bitterness).
Flavor ranges depending on the cheese used. Calcium citrate (poor emulsification).
Can control organoleptic and physical properties.
Versatile in use attributes (cooking cheese, dips, Orthophosphates
sauces, snacks, etc).
Disodium phosphate and trisodium phosphate (most
Shelf stability (nonrefrigeration, fixed properties).
common, used for loaf and slices).
Can take on various shapes and forms.
Sodium aluminum phosphate (used in slices).
Basic Emulsification Systems for Cheese Processing Dicalcium phosphate and tricalcium phosphate (poor
Citrates emulsification, used for calcium ion fortification).
Trisodium citrate (most common, used for slices). Monosodium phosphate (acid taste, open texture).
Table 4. Manufacturers' Sales of Cheese Condensed Phosphates
Year Total ($, millions) Annual percent change Sodium tripolyphosphate (nonmelting).
Sodium hexametaphosphate (used to restrict melts).
Tetrasodium pyrophosphate and sodium acid pyro-
phosphate (minimal usage).
General Rules for Emulsifier Selection
Citrates. Used where firm-textured, close-knit products
are desired, such as slices, and when products are refrig-
erated.
Phosphates. Used where shelf stability is required, pH
is to be controlled for melting, and other physical proper-
ties.
Optional Dairy Ingredients
Milk fat.
Milk and skim milk.
Nonfat dry milk (NFDM).
Source: Ref. 31.
"Average annual growth.
Whey (lots of lactose, some sweetness).
^Estimate. Whey protein.
Buttermilk.
Skim-milk cheese.
Other Optional Ingredients
Acidifying agents.
Salt.
Casein Products
Vegetable Fats
The most critical component in cheese analogues is the pro-
tein. The cheese analogues that have had commercial suc- Fats are essential ingredients in cheese analogues, for they
cess are all based on casein, the protein in milk. In some are replacing butterfat in the products. The fats utilized
cases a soluble casein salt, or casemate, is used. One of become emulsified and intermixed with protein and water
three forms of casein is generally used. For each, the start- and, therefore, contribute to melting and textural charac-
ing material is skim milk (Table 7). teristics. The fats also must behave in the mouth some-
thing like butterfat, which does melt in a characteristic
Vegetable Proteins way and influences creaminess, flavor, and other factors.
Several patents have been issued for, and papers written Consequently, fats most often utilized in cheese analogues
about, the use of vegetable proteins such as soy or cotton- are partially hydrogenated or mixtures of hydrogenated
seed protein in place of caseins (16,32). However, these and unhydrogenated oils that stimulate butterfat. These
products have not been commercially successful to date be- fats are similar to vegetable shortenings and can be made
cause of many technical problems. These include such im- from soybean, corn, cottonseed, palm, or coconut oils or
portant characteristics as flavor, melting properties, gel blends of these oils. These blends often have a melting
strength, color, translucence, and mouth feel (such as point of about 35-470C (33).
so that
a = Ge + arje6 (14)
Figure 6. Compression of a cylinder: (a) ideal; (b) concave; (c) This is not so convenient to analyze but there is still an
barrel; and (d) complex. intercept on the F axis proportional to the viscous compo-
nent and the rate of compression. The solution for the Max- is often difficult to decide whether there is an intercept on
well body is more complicated. Making the same substi- the stress axis, ie, whether there is an instantaneous build-
tutions as before leads to an infinite series up of stress at the moment the compression begins or a
rapid development of stress rising from zero but in a finite
though brief time. Nevertheless, it is essential that the dis-
a - G^-fe + I (-'^l - ^] (16) tinction be made if the correct model is to be assigned. The
instrument itself necessarily has a finite, even if very
At the commencement of the compression the stress is zero rapid, acceleration from rest, and the response of the re-
and the initial slope is proportional to the elastic compo- cording mechanism also takes a finite time, so that even if
nent. Initially the curve is convex upward, but as the com- the stress were instantaneous, it would appear as a very
pression proceeds a point of inflexion is reached, depending steep rise (35).
on the ratio of the viscous to the elastic components and However, much more serious than any limitations in the
the rate of compression. Finally, the curve becomes asymp- instrument is the problem of attaining perfection in the
totic to a line through the origin, with a slope given by the shape of the sample. Usually the dimensions of the sample
elastic constant. and the rate of compression are chosen so that the strain
If the stress-strain curve obtained for a particular sam- rate at the commencement is of the order of 0.01 s"1. In a
ple can be recognized as being similar to one of these two sample, say 20 mm in height, a lack of parallelism of the
patterns, the appropriate model can be identified and the two end surfaces of only 0.2 mm means that for the whole
material constants evaluated. It is seldom that such a sim- of the first second of compression only part of the sample
ple fit occurs. A material as heterogeneous as cheese is is being compressed. This will inevitably appear on the rec-
unlikely to conform to the behavior of a two-element model. ord as a flow, whatever the real properties of the cheese.
More sophisticated models may give a better representa- Assuming that any doubts about the shortcomings of
tion, but adding further elements only makes the theory either sample or instrumentation may be satisfactorily al-
more complex and the analysis that much more difficult. layed, it is pertinent to consider the principal features of
One word of caution must be entered here. The Voigt body the compression curve. In the early stages, after the initial
is characterized by the finite intercept on the stress axis. rise there is a smooth increase of stress with the strain.
The converse is not necessarily true. A finite intercept also Should the compression be halted at this stage, the cheese
arises in the case of any material possessing a yield value, would recover either completely or in part and a repeat of
since this is the stress which must be overcome before any the curve could then be obtained, the new curve having the
deformation takes place. same general shape as the original, showing that the in-
In the usual way in which compression tests are carried ternal structure of the cheese had remained more or less
out, the compression is allowed to proceed to a point far intact, although there may have been some rearrange-
beyond that at which any simple theory may be expected ment. Eventually a point is reached, the point A in Figure
to apply. Often it reaches 80%, a true strain of 1.609. Long 7, where the structure begins to break down and the slope
before this is reached, any structure which may have been becomes noticeably less. The conventional view is that this
present in the original sample of cheese can be seen to have is the point at which cracks in the structure appear and
broken down. If it is carried to this extent, only the early the cracks then spread spontaneously (18,36). In the case
part of the test may be considered as measuring the rheo- of a hard cheese these cracks may be evident to the eye,
logical properties of the original sample, while the latter but they may at first be so small and so localized that they
part becomes a test of the mechanical strength of the struc- do not become visible until the compression has proceeded
ture. A typical compression curve is shown in Figure 7. It somewhat further. If the cheese has a very homogeneous
structure, it is to be expected that these cracks will develop
throughout the structure at about the same time and the
change of slope will be clearly defined. In a more hetero-
geneous cheese they may appear over a range of strains
and the change of slope will be much more diffuse. Once
this region has been passed, the cracks continue to develop
at an increasing rate and become more evident, until at
point B the rate at which the structure breaks down over-
takes the rate of build-up of stress through further com-
pression and a peak is reached. This value is obviously
dependent on a balance between the spontaneous failure
of the structure and the effect of increasing deformation
applied by the instrument to any residual structure. It is
a convenient parameter to determine and may be used as
a measure of firmness or hardness of the cheese (18). Be-
yond this point the stress may continue to fall if the failure
Compression (%) of the structure becomes catastrophic, until the fragments
become compacted into a new arrangement which can take
Figure 7. Typical force-compression curve. up the stress and this now rises again.
If the compression test is carried on beyond the point at
which it is reasonable to attempt to interpret it in terms
of an acceptable model, and hence to evaluate any of the
customary rheological parameters, it becomes purely em-
pirical. One of the points on the curve most frequently used
Recovery (%)
Figure 13. Relation between firmness and protein content in a Figure 14. Relation between recovery of cheese and previous
single cheese. SNF/F = ratio of nonfat to fat solids. compression: O, Cheddar; , Mozzarella; and , Muenster.
varieties. Above this region the proportion of solid de-
creases further until at around 350C almost all is liquid.
This is near the temperature that a small portion will rap-
idly attain if it is placed in the mouth and chewed. The
ratio of the solid to liquid fat components is the principal
factor influencing the rheological properties of the fat (61).
Although factors such as breed and species of animal, pas-
ture, and herd management have some effect on this ratio,
temperature is by far the most important. Fat also super-
cools readily, so that the thermal history is almost as im-
portant as the absolute value of the temperature itself.
During maturation and storage cheese is usually kept at a
lower temperature than that at which it was made. Orig-
inally most of the glycerides will have been liquid and at
Initial stress (KPa) the lower temperature these will slowly solidify. Most of
the change will take place in the first day or two, but so-
Figure 15. Amount of relaxation after previous stress. lidification will continue progressively, maybe for several
weeks before final equilibrium is reached.
Measurements made on Cheddar, Cheshire (39), Em-
one makes the assumption that the cheese behaves as a mentaler (62), Gouda (63), and Russian (64) cheeses at a
Voigt body, a modulus of rigidity can be calculated from the range of temperatures, using different instruments, all
inphase component of the signal received and a viscosity show the same general trend (Fig. 16). It may be men-
from the out-of-phase component. For a true Voigt body tioned that different instrumental methods give rise to
both of these should be independent of the frequency. In somewhat different results. In general, penetrometers ap-
fact, neither was constant with either Cheddar or Gouda pear to indicate a rather steeper dependence of firmness
cheese, even when the strain was as low as 0.04. The in- on temperature than compression tests. Nevertheless,
ference is that even at this strain some failure in the rigid bearing in mind the difference in origin of the cheeses and
structure had taken place. Either internal cracks or slip the limitations in accuracy of the individual measure-
planes had developed within the cheese (42). However, ments, already discussed, this curve shows clearly the in-
everyday experience suggests that cheese should have fluence of the (test) temperature on the firmness of the
some rigid structure. The stress on the lower layers of a cheeses.
large cheese, such as a Parmigiano or a Cheddar, is of the Differences in the glyceride composition of the original
order of 3 to 4 kPa; yet such a cheese retains its shape more milk fat are also reflected in the final cheese. Using the
or less indefinitely. iodine number as an indication of the ratio of solid to liquid
Summarizing the previous paragraphs, it appears that fat at any one temperature, the firmness of Swiss cheese
the rheological role of the casein is to provide a continuous was shown to vary seasonally with the solidity of the fat
elastic framework within the individual granules. It is (65) (Fig. 17). The lower the iodine number, the greater the
likely that where the casein chains lie in the granule sur- degree of saturation of the glycerides and the higher the
face and are contiguous with chains in neighboring gran-
ules they may be held together by physicochemical bonds
which develop during maturation and give rise to some
rigidity in the aggregation (54). However, these bonds will
be sparser than those within the original network, since
they form only where chance contacts occur. This results
in a weaker secondary structure. These bonds may be bro-
ken when a positive strain is applied, giving a Maxwell
Relative firmness
Recovery (%)
Iodine number Water content (%)
Figure 17. Variation of firmness with saturation of glycerides. Figure 18. Relation between elastic recovery and moisture con-
tent.
Water content (%) Figure 22. Relation between rate of casein breakdown and mois-
ture content.
Figure 20. Relation between quasi-modulus and moisture con-
tent in a single cheese variety.
pressed, may sometimes appear as crystals embedded in
the fat-protein mass. Then it is not usually present in
changes which take place in the casein network. An illus- large enough quantities to make any sensible contribution
tration of this is found in Meshanger cheese (56). This to the rheological properties of the whole. Almost all of the
cheese has the usual well-organized casein structure when salt is present only in solution in the water. There its effect
freshly made. As the ripening proceeds, the structure on the properties of the whole cheese is minimal. Any se-
breaks down until it becomes a more or less amorphous rious contribution of the salt to the rheological properties
loose mass of casein submicelles. Figure 21 shows the re- of the whole cheese is by indirect action (67). A high con-
lation found between an arbitrary measurement of the centration of salt increases the osmotic pressure, diverting
firmness and the water content of cheeses from some ten a significant quantity of water from the structural bonds
batches during ripening. In the same series of experiments of the casein network (68,69). This may be seen in the effect
the rate of degradation of the casein was determined for on the ripening of some samples of Mozzarella cheese (70).
some of the batches over the first few weeks of life. The When the salt content was low (0.27%) the modulus de-
rate of degradation, calculated as a first-order reaction, creased from 120 to 45 N/m2 in five weeks, but when salt
showed good agreement with the water content (Fig. 22). was present in excess of 1% no change was observed within
Although protein, fat, and water constitute by far the the same period.
greatest part of any cheese mass, other constituents can- In cheese where the salt is added by immersion in brine
not be ignored. Salt, when added dry before the cheese is there is a further consideration. The inward diffusion of
the brine results in a concentration gradient being set up
within the cheese. This has a twofold effect. First, the pres-
ence of the salt simply excludes some of the water; this in
turn reinforces the moisture gradient simultaneously aris-
ing from the evaporation of water from the surface layers.
Probably more important is the fact that the diffusion of
the salt into the cheese is a slow process (71). In the early
stages of ripening the salt concentration in the inner
regions is unlikely to be sufficient to limit the protein deg-
Firmness
probably account for a substantial amount of the observed Cheese (kN/m2) (kPa) ey (kPa) Ref.
scatter. In compression measurements they will give rise American loaf 70 25 0.72 46 58
to premature breakdown. They also account for the fact BelPaese 300 44 1.1 37
that difficulties are encountered when any attempt is Caerphilly 1100 92 0.16 67 36
made to assess the rheological properties of cheese by Cheddar 280 41 0.34 50 22
studying the propagation of ultrasound through it. The ve- Cheddar 53 0.25 39
locity of propagation is more influenced by the scattering Cheddar 63 0.24 47
at the discontinuities than by the properties of the cheese Cheddar (mild) 160 40 0.60 78 58
mass. Cheddar (strong) 400 58 0.22 65 58
Cheddar 320 45 0.21 64 73
Cheddar (green) 75 54 0.80 37 47
SOME EXPERIMENTAL RESULTS Cheddar (mature) 170 23 0.20 22 47
Double Gloucester 1600+ 139 0.24 75 36
Edam 660 214 0.60 36
Most of the rheological methods described earlier have German loaf 300 18 ca 1.1 33
been used at one time or another for the study of cheese. Gouda 240 98 0.72 52 36
Problems associated with penetrometers and tests on the Lancashire 2000+ 105 0.23 36
surface have already been indicated. The most satisfactory Leicester 400 56 0.31 38 32
tests are made on samples cut out specifically from the Montasio 40 85 0.80 37
cheese mass. In this case the sample can be inspected to Mozzarella 300 (no peak) 34
insure that there are at least no major cracks or other in- Mozzarella 80 14 0.57 58
Muenster 40 16 0.72 59 58
homogeneities in it and the dimensions can be precisely Parmigiano 700 132 0.28 37
determined. The force-compression test using small pre- Provolone 120 37 0.60 37
pared samples has been widely used for routine measure- Silano 230 26 ca 0.30 57
ments. However, in spite of its widespread use, there has Processed 195 57 0.39 30 36
been no consensus of opinion on the most suitable operat- Processed 440 71 0.27 37
ing conditions. Sample size and shape, rate of compression, Processed 60 9 0.21 37
and even temperature have all varied. A most interesting
feature is that, notwithstanding these differences and the
number of cheeses which have been examined, the force-
compression curves show a remarkably common pattern. into stressstrain curves. As previously mentioned, the
This underlines its general usefulness. instrument in its usual commercially available form pro-
There are several important considerations to be taken duces curves of force versus linear travel. While linear
into account when deciding on the operating conditions. In travel is easily converted to true strain (eq. 11), the stress
the first place, the sample should be large enough to be correction requires a knowledge of the actual shape at any
representative of the whole (72); the more heterogeneous instant during compression. Often this is unknown, or at
the cheese, the larger the sample. On the other hand, it least unreported. Unless special precautions have been
should not be so large that it may contain hidden cracks taken, the behavior of the sample will be intermediate be-
or irregularities. These two requirements are almost mu- tween that obtaining in the lubricated and in the bonded
tually exclusive. As a compromise most workers have situations. For the present purposes the simpler correction
taken samples with linear dimensions of 10 to 25 mm. The applying to the lubricated condition has been used
preferred shape has usually been a cylinder. It is easier to throughout, although it is realized that it will not quite
prepare a rectangular sample with precise dimensions but compensate for the barreling which occurs. The values
the symmetry of the cylindrical shape helps to minimize were then read from the transformed curves. The modulus
the development of irregular cracks during compression given in the column headed EQ is from the slope at the
(63). A wide range of compression rates has been used: origin, ie, it refers to the undeformed sample. The entries
from 2 mm/min up to 100 mm/min (3.33 X 10~5 to 1.66 X in the columns headed yield refer to the stress and strain
10 ~ 3 m/s). The faster rates tend to obscure the true be- at the peak of the curve.
havior at the onset of compression unless a recorder of very Table 2 summarizes a number of results which have
short response time is available. The strain rate at any been obtained by other methods where it has been possible
instant depends on both the rate of compression and the to calculate a modulus from the data. In order to compare
height of the sample at that instant. the two tables, it will be recalled that Table 1 lists the
Table 1 summarizes the principal measurements that values of an elastic modulus. It must be most nearly com-
have been reported on hard cheeses using the force- parable with any quasi-modulus determined by the punc-
compression test. In order to produce this table and make ture test or by simple compression. The yield stress mea-
the results from different workers comparable, the original sured by a cone penetrometer is more likely to be
curves from the references cited have been transformed comparable with the yield value in the forcecompression
Table 2. Modulus Measurements Using Various Methods
Cheese Modulus (kN/m2) Method Ref.
Brie 1.3 Extruder 74
Sbrinz 41 Extruder 74
Chanakh 58 Cone 69
Emmental 40 Cone 69
Stress (KPa)
Emmental 3.5 Cone 22
Gouda 44 Cone 69
Kostroma 54 Cone 69
Lori 40 Cone 69
Cheddar 195 Punch 29
Edam 340 Punch 29
Emmental 220 Punch 29
Gouda 270 Punch 29
Kachkaval 120 Punch 75
Mozzarella 170 Punch 29
Mozzarella 22 Punch 74
Muenster 120 Punch 29
Parmigiano 550 Punch 29 Strain
Provolone 130 Punch 29
Cheddar 27(MrOO Compression 76 Figure 23. Force-compression curves for young and mature
Mozzarella 80 Compression 70 cheeses: , Cheddar (mature); , Cheddar (young); , Gouda
Kachkaval 60-100 Ball Compressor 77 (young); and , Gouda (mature).
oratories.
to more than $840 million by 2001 (1); the current and Separate zones for raw receiving, preprocess prep-
future chilled-food market trend for Japan can be seen in aration, product assembly and cooking, pasteurization,
Figure 5. chilling, and packaging are usually identified and main-
Most of this market growth is due to the expanding tained in chilled-food operations (2). Physical separation of
presence of supermarkets, although much of the available different production zones is necessary to prevent cross-
chilled foods is distributed through neighborhood conven- contamination between raw and cooked or processed prod-
ience stores. The chilled-food market in Japan is seen as uct. Other aspects of hygienic process design, such as clean
relatively new and expanding by market research compa- rooms and air handling systems, may be incorporated into
nies, as chilled-food distribution systems have only re- chilled-food processing to reduce the risk of microbial con-
cently been opened to Western companies (1). Home deliv- tamination. For example, clean rooms may be maintained
ery of food to the elderly and the expanding presence of in the assembly and packaging of already-processed con-
automatic vending machines are expected to contribute stituents, and air handling systems may be used to filter
significantly to the Japanese chilled-food market growth. particles 0.5 jum or smaller from product assembly areas
Consumers in both Europe and Japan view the nutri- to minimize postprocess microbial contamination. A rig-
tional value and health benefits of chilled foods as being orous cleaning protocol for machines and the factory en-
superior to similar frozen or shelf-stable products. A de- vironment is also to be included as part of a good manu-
mand for superior quality is also evident in both Europe facturing practice for the manufacture of chilled-food
and Japan, as consumers are willing to pay a premium for products (3).
chilled foods with authentic home-cooked or restaurant-
quality taste. Convenient and functional packaging of Pasteurization
chilled foods is given as much accord by Japanese custom- Pasteurization involves heating food products to eliminate
ers as the nutritional quality of the food. Consumers in specific types of microorganisms. Chilled products can be
both Europe and Japan are also becoming more price con- pasteurized before packaging and clean-filled (hot fill hold)
scious in light of the 1990 European recession and the re- or filled and pasteurized in-pack (IPP). Cooking processes
cent economic troubles in Asia (1). may be considered as part of the pasteurization process,
but care must be taken to prevent contamination during
PROCESSING OF CHILLED FOODS latter processing steps. For chilled products having an ex-
pected shelf life of 10 to 14 days, a minimal heat process
Chilled-food processing lines are designed to produce qual- to eliminate infectious pathogens is recommended, espe-
ity finished products as well as to control the presence and cially if the product is ready to eat. An example of a typical
growth of microorganisms in finished products. A partic- process for these product types is 7O0C per 2-min hold,
ular production method may be used in concert with an- which will eliminate 106 Listeria monocytogenes per gram
other to produce a product of superior organoleptic and mi- of product. Chilled products having an expected shelf life
crobiological quality. The following procedures are common of more than two weeks generally require a more severe
throughout the industry in the production of chilled foods. process to eliminate spore-forming psychrotrophic patho-
gens. Typical processing conditions for these extended
Controlled Product Handling During Processing shelf-life products are at least 9O0C per 10-min hold to
eliminate 106 nonproteolytic, psychrotrophic Clostridium
Product handling during all phases of chilled-food produc- botulinum per gram of product.
tion is crucial from a microbiological safety and quality Pasteurization processes are defined in terms of P-
standpoint. A typical processing diagram for chilled foods value, which is the time a product is held at a certain pro-
indicating separation of production zones can be found in cessing temperature (typical value for nonproteolytic C.
Figure 6. botulinum would be written as P900C = 10). Conventional
Market size (in $billions)
Figure 5. Actual and predicted market for chilled
foods in Japan, 1992-2001. Year
Table 2. Commonly used Gas Mixtures in MAP for Microbial Stability in Chilled Products
Chilled product Target organisms CO2 (%) Nitrogen (%) Oxygen (%)
Pasta Molds, S. aureus >35 >20
Meats Spoilage organisms 100
Salads Spoilage organisms 20
Fish C. botulinum 50-60 25
Sandwiches Spoilage organisms 100
Pizza Molds, lactics 50 50 0-10
Poultry Spoilage organisms >40 60
Cottage cheese Listeria 35
Soft Cheeses Listeria, molds 100
Hard Cheeses Listeria, molds 100
Table 3. Advantages and Limitations of MAP in Chilled measure surface temperature, the actual temperature of a
Foods food product may need to be confirmed by other means.
Advantages Limitations Similarly the liquid crystal devices seen on the front sur-
faces of chill cabinets suffer the same problem since they
Shelf-life extension Does not inactivate pathogens or measure the surface temperature of the cabinet.
prevent growth
Restrict growth of aerobic Shelf-life extension depends on
These single-unit devices are now being replaced with
organisms initial population of more accurate remote systems. These systems can be
microorganisms linked to a computer for data storage and temperature con-
Delays growth of some trol. Such systems can give temperature displays from a
facultative organisms Requires more costly packaging number of sites at once and may be linked to an alarm
May improve flavor Can lead to lower line speeds device. The temperature-measuring devices in these units
Adjunct to other processes Does not control the growth of may be either thermocouples or thermistors. The accuracy
lactic acid bacteria of these sensors ranges between 0.3 and 1.50C. The therm-
istor, a device that measures changes in resistance with
temperature, is preferable to a thermocouple because of its
storage. Refrigerated display units may be configured in a accuracy.
variety of ways, and the most common types are freestand- Data loggers may also be used to monitor refrigerated
ing bins without doors and upright shelf units with pro- transport and storage of chilled foods. These units can be
tective glass doors. Several sources have noted that retail programmed to measure and record temperatures at reg-
display is the aspect of distribution in which a control of ular intervals over a period of time. When linked to a com-
storage conditions is most lacking (9). Proposed regula- puter, these data can then be retrieved, and the tempera-
tions in the United States are more stringent in that the ture history during storage is revealed. Current
temperature requirement has been lowered from 6 to 40C developments with these units have reduced the size of
for refrigerated storage of chilled products. The goal of this these loggers so that they can easily be placed inside small
regulation if to provide a greater margin of safety and qual- packages. Temperature monitoring and control is an im-
ity to chilled products, which should benefit both the con- portant issue, especially for chilled food where it remains
sumer and the processing company. the primary hurdle against spoilage and foodborne dis-
ease. An indication of this is that chilled-product mishan-
dling and abuse due to incorrect storage temperatures con-
TEMPERATURE CONTROL AND MONITORING tributed to 43% of foodborne disease outbreaks in the
United States in 1996. A temperature-monitoring ap-
In the production of chilled foods the focus of any produc- proach that has been successful in the pharmaceutical in-
tion strategy is either to eliminate or minimize the growth dustry is the use of time-temperature indicators (TTI).
of pathogens or spoilage organisms. However, this focus These indicators measure temperature or temperature
must be balanced with quality issues such as color, flavor, changes based on chemical or biological reactions. The re-
and the desired shelf life. A number of options will allow sults of these reactions are displayed in the form of color
such a balance, but all of these depend on temperature changes. In chilled foods the best type of TTI is the one
control. that integrates both time and temperature. Such a product
A key factor for successful production of chilled foods is is available on the market, but current costs for these units
the constant awareness of controlling the temperature prevent many companies from using them on individual
from the production and manufacturing site to the retail packs. Consumer preference with TTI, especially with
or food service markets and the consumer. The rate of qual- chilled products, is a "go/no-go" indicator. Systems indi-
ity loss for chilled products, for example, can increase up cating how much shelf life is remaining in a product are
to eight times for each 1O0C increase in temperature, and also preferred by consumers (10). Future developments
the penalty for mishandling of products can be severe both should be able to overcome cost and ease-of-use issues.
in terms of human illness and product loss (10).
A number of temperature-measuring devices are avail- Distribution and Storage Temperature Studies
able for monitoring products during production or trans-
porting or in the retail marketplace. An excellent overview Several studies on refrigeration temperatures maintained
of this area has been published in Reference 11. The most at retail outlets and homes of consumers revealed several
common types consist of single readout units, sensors such interesting facts (12). Studies carried out in the U.S. mar-
as semiconductors or thermocouples, recording charts, ket have shown that the temperature of storage of chilled
data loggers, and chemical indicators. The single-unit de- products varies within a store and by product type. Super-
vices such as the dial and stick thermometer, often seen in market surveys have shown that storage temperatures
supermarket chill cabinets, lack accuracy in determining and fluctuations within the raw meat cabinets are better
the air temperature. Changes to electronic readout ver- controlled than in the delicatessen areas. A summary of
sions of these bimetal units have not added significantly this information can be found in Figure 7.
to their accuracy. A much more accurate unit is the "point Comprehensive studies have observed that many re-
and shoot" infrared thermometers. These handheld guns frigerated foods both at the retail and consumer level ex-
measure radiation temperatures of a product surface, ceeded 1O0C (13). This was particularly true for delicates-
which is translated to a digital readout. Since the units sen items, where 13% of these items were above 120C.
num. Recent outbreaks in the United States of Listeria in
Low temp chilled meats emphasize the importance of controlling this
High temp pathogen in a chilled-food processing environment. Ready-
to-eat deli meats produced by one large company were as-
Temperature (0C)
Raw meats
Dairy
Delicatessen
meats
in ready-to-eat products. Some viruses such as the Nor- Nonmicrobial Issues Pertaining to Chilled-Product Safety
walk virus have been associated with oysters and have and Quality
caused foodborne outbreaks when the product has been Several toxicological issues relate to the safety of chilled
eaten raw. foods. Natural toxicants exist usually at low levels in sev-
eral types of raw products. These include biogenic amines,
Microbiological Spoilage glycoalkaloids, phytotoxins, nutritional inhibitors, antivi-
Many of the spoilage organisms associated with chilled tamins, and antigens that can stimulate anaphylactic
foods are adapted to their environment (17). At O0C, for shock in sensitive people. Fortunately, many such agents
example, the lag time for many organisms is usually about are modified during processing as a result of culling, wash-
two to three days before initiating growth. Once this oc- ing, and heating. Potatoes, for example, can produce gly-
curs, the generation time for these psychrotrophic bacteria coalkaloids such as solamine, which is a potent cholines-
at 40C is in the region of 10 to 12 h. For a chilled food terase that acts on the central nervous system and
product to achieve maximum shelf life with optimum qual- interferes with nerve impulses. These amines are pro-
ity, the initial level of these psychrotrophic spoilage micro- duced by stress conditions in the potato and accumulate
organisms must be minimized. The principal groups of close to the skin. The process of culling and peeling reduces
spoilage organisms associated with chilled foods are human exposure to this alkaloid. Lectins associated with
Pseudmonas spp., lactic acid bacteria, members of the co- legumes such as kidney beans have been associated with
liform group, yeast, and molds. These groups are widely toxicosis when eaten without prior treatment. When such
distributed in nature and therefore present both in raw products are soaked overnight and subsequently cooked,
ingredients and the factory environment. They are good the toxic lectins are inactivated. An important toxin asso-
competitors and capable of producing off-flavors or odors, ciated with fish products is caused by algal growth. The
especially when bacterial populations reach about 1 mil- algal toxins gain access to the food chain through ingestion
lion cells per gram of food. by shellfish. These toxins can accumulate in marine life at
Each of the microbial spoilage groups contributes cer- high levels without adverse effects. It is particularly dan-
tain attributes to a food product during growth. Pseudo- gerous to consume such shellfish during these periods of
monas species cause slime formation, color changes within high algal concentration in coastal waters when the nutri-
the pack, and, as a result of their proteolytic metabolism, ent levels and temperature reach an optimum level. De-
strong amine odors. These changes occur in an aerobic en- pending on the type of toxin present, consumption by hu-
vironment and can be controlled by removing the oxygen mans of contaminated shellfish causes a number of
from the food. Other Gram-negative groups contribute less symptoms including vomiting, disorientation, numbness,
drastic changes but will contribute to off-odors and acid and paralysis.
flavors. The lactic acid group has a unique role in spoilage Other chemicals arising from the environment can oc-
since lactic acid is produced as a result of their metabolism. cur at low levels in foods and should be accounted for when
In addition to lactic acid, other antimicrobial agents that considering safety of a product. The most common and
are capable of controlling the growth of certain pathogens closely monitored contaminants are heavy metals, pesti-
and competitive microflora may be produced. Lactic acid cides, antibiotic residues, and incidental additives from
bacteria are also one of the more persistent groups in packaging. Toxic metals are of a particular concern, as
chilled foods because they tend to be resistant to most of problems arise as a result of using sludge from sewage
the preservatives used and can grow under anaerobic con- farms and waste from settling pools for fertilizing crops.
ditions. Yeasts and molds are also a problem in chilled The dissemination of antibiotics from livestock into the
foods, and this type of spoilage is easily visible to the con- food chain has been demonstrated in milk and meats. Al-
sumer. Yeasts cause spoilage problems in chilled products though the levels are low, there is a concern with respect
because they are facultative with respect to oxygen re- to the development of resistant strains of bacteria entering
quirements, but they can be inhibited by a preservative the food chain. See Reference 18 for further information.
such as sorbic acid or growth delayed by high carbon di-
oxide levels in the pack. Molds require aerobic conditions Quality Control Plans
for growth and can be controlled by use of oxygen scaven- Control plans for chilled food include shelf-life testing and
gers in the pack or modified atmosphere packaging. the use of predictive microbiology, HACCP plans, and risk
assessment to ensure that all products meet local and na- issues likely to arise during the complete food chain (pro-
tional regulations. duction to consumer) and lists hazards that are deemed
critical. Such hazards are recognized as critical control
Shelf-Life Testing. The shelf life of a refrigerated product points (CCP), and control measures are put in place to con-
is, in a sense, a record of its production and applied pro- trol the identified hazard during the production, distribu-
cesses. Products with a long shelf life have to be prepared tion, and sale of the product. The system is science based,
with more stringent control over ingredients and environ- applying a systematic approach to the issue of safety (and
ment as well as the use of more severe heat treatment or sometimes quality) for food production. Briefly, the ap-
the application of multihurdle technology. Product shelf proach uses seven steps that include hazard identification,
life can be defined as the period in which the product, when setting of standards for CCPs, corrective action to be
stored under proper chilled conditions, is safe and whole- taken, and auditing. The application of a HACCP program
some to eat. In determining shelf life at chilled tempera- requires a team approach that draws on expertise in dis-
tures, both chemical and microbiological parameters have ciplines such as engineering, product development, micro-
to be considered. Likewise, there should be a balance be- biology, chemistry, and public health. The HACCP system
tween spoilage and safety with respect to microbiological can also provide other benefits such as reducing end prod-
issues. Chemical issues usually involve texture changes, uct testing, aid inspection programs and promote inter-
color degradation, syneresis or separation of water from national trade.
the product, and flavor changes. Texture changes usually
occur as a result of migration of water to or from an ingre- Risk Assessment. The decision on what is a hazard or
dient or as a result of enzymatic activity. Color degradation whether it is critical is sometimes unclear, and risk as-
of pigments such as chlorophyll or carotenes, for example, sessment can help link relevant steps in the HACCP plan
can occur from exposure to high temperatures or pH to public health concerns (20). Risk assessment is the sci-
changes. Sensory testing is an important part of shelf-life entific basis for the estimation of risks, either qualitative
evaluation for determining the optimum product quality or quantitative and has been used successfully for environ-
and how long it can be maintained during storage. mental issues for many years. When a person is exposed
Microbiological shelf life testing usually consists of test- to a hazard, it is possible to estimate the severity and like-
ing products at both standard chilled temperatures (4-50C) lihood of harm resulting from that exposure. One of the
and at abuse temperatures (10-150C) over the claimed steps in a HACCP study is the establishment of critical
shelf life. The abuse temperatures are used to determine limits for the CCPs. These critical limits would more mean-
the margin of safety built into the product by allowing for ingful if they were established by quantitative means. The
the growth of certain pathogens if present. Several sam- steps in risk assessment would allow this by determining
pling periods and storage trials are necessary to get a true (7) hazard identification, (2) assessment of the exposure to
picture of the microbiological profile of the product. Shelf the hazard, (3) dose response or negative effects of such
life is then designated based on data from these studies. exposure, and (4) estimation of the magnitude of the public
In some instances, challenge studies are incorporated in health problem.
shelf-life studies, especially if new formulations or tech- Thus, the overall objective is to generate and obtain
nology is used. The food is challenged with the pertinent quantitative information of the microbial risks associated
pathogens over the shelf-life standard and abuse tempera- with the manufacturing and distribution of the product.
tures (19). The data give some idea as to the ability of the This is achieved by assessing the frequency of pathogens
growth characteristics of the pathogen in that food. Math- in raw materials, the survival or growth patterns during
ematical modeling of data can be used for such studies as the process, storage, and distribution. This data, along
a basis for experimental design. These models may aid in with the dose response for the pathogen, will provide in-
predicting growth conditions of selected pathogens under formation for a risk assessment to be determined. For fur-
a given set of condition at different temperatures. Using ther reading see Reference 22.
such data can be timesaving and limit the number of tests
that need to be performed. Current predictive models also Legislation
include a number of variables associated with the intrinsic
properties of the food such as aw, pH, and preservative sys- Many countries have standards or guidelines that cover
tems. relevant legislation for chilled foods. The FDA in the
Needless to say, most of the data used in the establish- United States has requirements under Good Manufactur-
ment of predictive models has been derived from both stud- ing Practices for the production of chilled foods (CFR Part
ies and cannot completely replace standard challenge ex- 110). Included in this law is the requirement that raw ma-
periments. Both shelf-life and challenge experiments terials and ingredients be free from pathogenic microor-
require technical expertise and adequate resources to ganisms or be treated in such a way "so that they no longer
carry out the task successfully (20). contain levels that would cause the product to be adulter-
ated." This regulation also has provisions for maintaining
Hazard Analysis. Data from shelf-life and challenge the food at 7.20C or below "as appropriate for the food." It
studies focus on the safety and quality issues of the product also requires that chilled products be handled in such a
during storage. This information can be tied into the way as to protect the product from recontamination. The
HACCP plan during the manufacturing of the chilled prod- FDA has also developed the Food Code as a model to assist
ucts (21). In essence, this approach examines the safety other state agencies in the area of food service, retail, and
vending. It provides guidance for thawing, cold storage, 8. T. P. Labuza, B. Fu, and P S. Taokis, "Prediction of Shelf
and reheating of potentially hazardous foods. The Code Life and Safety of Minimally Processed CAP/MAP Chilled
also provides information on labeling requirements and Foods: A Review," Journal of Food Protection 55, 741-750
shelf life at specific temperatures for chilled foods. Al- (1992).
though this code was intended as a guideline, several 9. A. L. Brody, "Chilled Foods Distribution Needs Improvement,"
states have adopted it into legislation. The U.S. Depart- Food Technol. 51, 120 (1997).
ment of Agriculture (USDA) provides general processing 10. M. Sherlock and T. P. Labuza, "Consumer Perceptions of Con-
guidelines for meat and poultry products as well as re- sumer Time-Temperature Indicators for Use on Refrigerated
quirements related to the sanitation of the plant. It also Products," J. Dairy ScL 75, 3167-3176 (1992).
requires any manufacturer of chilled foods under its juris- 11. M. L. Woolfe, "Temperature Monitoring and Measurement,"
diction have a sanitation standard operating procedures in C. Dennis and M. Stringer, eds., Chilled Foods, A Compre-
(9CFR 416) and a HACCP plan for all processed products. hensive Guide, Ellis Horwood, Chichester, United Kingdom,
1992, pp. 77-109.
The Food Act of 1990 provides the main provisions in
the United Kingdom for the safety and hygiene controls 12. G. E. Skinner and J. W. Larkin, "Conservative Predictions of
of chilled foods (23). It introduces the concept of "due dil- Time to Clostridium botulinum Toxin Formation for Use With
Time-Temperature Indicators to Ensure the Safety of Foods,"
igence" by stating that all reasonable precautions and Journal of Food Protection 61, 1154-1160 (1998).
control measures (eg, HACCP plans) must be in place in
food preparation. As with other European countries the 13. R. W. Daniels, "Applying HACCP to New Generation Refrig-
erated Foods at Retail and Beyond," Food Technol. 45, 122-
European Community Directives on Food Hygiene (93/43/ 124 (1991).
EEC) are implemented as part of the regulations on hy-
14. S. J. Van Garde and M. J. Woodburn, "Food Discard Practices
giene.
of Households," Journal of American Dieticians Association
The Food Sanitation Law governs food regulations in 87, 322-327 (1987).
Japan and covers a full range of topics including additives
15. L. J. Cox et al., "Listeria species in Food Processing, Non-food
and labeling and matters pertaining to chilled foods.
Processing and Domestic Environments," Food Microbiol. 6,
Codes of practice or industrial guides for chilled foods 49-61 (1989).
also exist in many countries and these lay out guidelines
16. S. A. Rose, "Chilled Foods," in Y. H. Hui, ed., Encyclopedia of
for the manufacturing of refrigerated products (24). Typi-
Food Science and Technology, Vol. 1., John Wiley and Sons,
cal is the Chilled Foods Association (25) chilled-foods New York, 1992, pp. xx-xx.
guidelines, which covers hygiene requirements, HACCP
17. V. N. Scott, "Interaction of Factors to Control Microbial Spoil-
considerations, lethal rates for selected pathogens, and age of Refrigerated Foods," Journal of Food Protection 52,
other relevant codes of practice. The outstanding feature 431-435 (1989).
of any legislation for chilled products is the temperature
18. H. M. Brown, "Non-Microbiological Factors Affecting Quality
requirements for storage, and this often forms the only ba- and Safety," in C. Dennis and M. Stringer, eds., Chilled Foods,
sis for local or provincial legislation. A Comprehensive Guide, Ellis Horwood, Chichester, United
Kingdom, 1992, pp. 261-288.
19. S. Notermans et al., "A User's Guide to Microbial Challenge
BIBLIOGRAPHY Testing for Ensuring the Safety and Stability of Food Prod-
ucts," Food Microbiol. 10, 145-157(1993).
1. The International Market for Chilled Foods, Packaged Facts, 20. W. B. McNab, "A Literature Review Linking Microbial Risk
New York, 1996. Assessment, Predictive Microbiology and Dose-Response
2. M. H. Brown and G. W. Gould, "Processing," in C. Dennis and Modeling," Dairy, Food and Environmental Sanitation 17,
M. Stringer, eds., Chilled Foods, A Comprehensive Guide, El- 405-416 (1997).
lis Horwood Limited, Chichester, United Kingdom, 1992, pp. 21. A. C. Baird-Parker, "Use of HACCP by the Chilled Food In-
111-146. dustry," Food Control 5, 167-170 (1994).
3. M. Waite-Wright, "Paper 1 Chilled FoodsThe Manufac- 22. L. Jaykus, "The Application of Quantitative Risk Assessment
turer's Responsibility," Food Science and Technology Today 4, to Microbial Food Safety Risks," Crit. Rev. Microbiol. 22, 279-
223-227 (1990). 293 (1996).
4. B. M. McKay and C. M. Derrick, "Changes in Heat Resistance 23. Guidelines for the Handling of Chilled Food, 2nd ed., Institute
of Salmonella typhimurium During Heating at Rising Tem- of Food Science and Technology, London, United Kingdom,
peratures," Lett Appl. Microbiol. 3, 1316 (1987). 1990.
5. B. P. F. Day, "Chilled Food Packaging," in C. Dennis and M. 24. Guidelines for the Development, Production, Distribution and
Stringer, eds., Chilled Foods, A Comprehensive Guide, Ellis Handling of Refrigerated Foods, National Food Processors As-
Horwood Limited, Chichester, United Kingdom, 1992, pp. sociation, Washington, D.C., 1989.
147-163. 25. Technical Handbook for the Chilled Food Industry, Chilled
6. J. M. Farber, "Microbiological Aspects of Modified Atmo- Foods Association, Atlanta, Ga., 1990.
sphere Packaging TechnologyA Review," Journal of Food
Protection 54, 58-70 (1991).
7. C. D. Gill and G. Molin, "Modified Atmospheres and Vacuum DAVID COLLINS-THOMPSON
Packaging," in N. J. Russel and G. W. Gould, eds., Food Pre- JOHN M. SIDDLE
servatives, Blackie and Sons, London, United Kingdom, 1991, Nestle R&D Center, Inc.
pp. 172-199. New Milford, Connecticut
CHLOROPHYLL. See COLORANTS: CHLOROPHYLLS. Fermentation (Curing)
Prior to shipment from producing countries, most cocoa
beans undergo a process known as curing, fermenting, or
CHOCOLATE AND COCOA sweating. These terms are used rather loosely to describe
a procedure in which seeds are removed from the pods,
In the United States, chocolate and coca are standardized fermented, and dried. Unfermented beans, particularly
by the U.S. Food and Drug Administration under the Fed- from Haiti and the Dominican Republic, are used in the
eral Food, Drug, and Cosmetic Act. The current definitions United States.
and standards resulted from prolonged discussions be-
tween the U.S. chocolate industry and the Food and Drug Commercial Grades
Administration (FDA). The definitions and standards orig-
inally published in the Federal Register of December 6, Most cocoa beans imported into the United States are one
1944, have been revised only slightly. of about a dozen commercial varieties that can be generally
The FDA announced in the Federal Register of January classified as Criollo or Forastero. Criollo beans have a light
25, 1989 a proposal to amend the U.S. chocolate and cocoa color, a mild, nutty flavor, and an odor somewhat like sour
standards of identity. The proposed amendments respond wine. Forastero beans have a strong, somewhat bitter fla-
principally to a citizen petition submitted by the Chocolate vor and various degrees of astringency. The Forastero va-
Manufacturers Association (CMA) and, to the extent prac- rieties are more abundant and provide the basis for most
ticable, will achieve consistency with the Codex standards. chocolate and cocoa for formulations. The main varieties
The proposed amendments would allow for the use of nu- of cocoa beans imported into the United States, usually
named for the country or port of origin, are Ivory Coast,
tritive carbohydrate sweeteners, neutralizing agents, and
emulsifiers; reduce slightly the minimum milkfat content Accra (Ghana), Lagos, Nigeria, Fernando Po, and Sierra
and eliminate the nonfat milk solids-to-milkfat ratios in Leone (from Africa); Bahia (Brazil), Arriba (Ecuador), and
certain cocoa products including milk chocolate; update the Venezuelan (from South America); Malaysia, New Guinea,
language and format of the standards; and provide for op- Indonesia, and Samoa (in the Pacific); and Sanchez (Do-
tional ingredient labeling requirements. FDA has also re- minican Republic), Grenada, and Trinidad (in the West In-
ceived a proposal to establish a new standard of identity dies).
for white chocolate. Comments regarding the proposal
Blending
amendments are under review by FDA, and a final ruling
is expected to be issued in the near future. Most chocolate and cocoa products consist of blends of
beans chosen for flavor and color characteristics.
WHITE CHOCOLATE Production
There is at present no standard of identity in the United Worldwide cocoa bean production ranged from 2.3-2.5-
States for white chocolate. million t and cocoa bean production was stagnant between
White chocolate has been defined by the European Eco- 1988 and 1993. Indonesia was the only country signifi-
nomic Community (EEC) Directive 75/155/EEC as free of cantly expanding production. Production in Brazil and Ma-
coloring matter and consisting of cocoa butter (not less laysia actually dropped.
than 20%); sucrose (not more than 55%); milk or solids ob-
tained by partially or totally dehydrated whole milk, Consumption
skimmed milk, or cream (not less than 14%); and butter or Worldwide cocoa bean consumption increased by 14% be-
butter fat (not less than 3.5%). tween 1988 and 1993 from approximately 2.1 million t in
the 1988-1989 crop year to almost 2.4 million t today.
North America and Western Europe increased grind by ap-
COCOA BEANS proximately 26% over this time period, whereas in Russia
and Eastern Europe grind dropped by 46%.
The cocoa bean is the basic raw ingredient in the manu-
facture of all cocoa products. The beans are converted to Marketing
chocolate liquor, the primary ingredient from which all
chocolate and cocoa products are made. Figure 1 depicts Most of the cocoa beans and products imported into the
the conversion of cocoa beans to chocolate liquor, and in United States are done so by New York and London trade
turn to the chief chocolate and cocoa products manufac- houses. The New York Sugar, Coffee, and Cocoa Exchange
tured in the United States, ie, cocoa powder, cocoa butter, provides a mechanism by which both chocolate manufac-
and sweet and milk chocolate. turers and trade houses can hedge their cocoa bean trans-
Significant amounts of cocoa beans are produced in actions.
about 30 different localities. These areas are confined to
latitudes 20 north or south of the equator. Although cocoa CHOCOLATE LIQUOR
trees thrive in this very hot climate, young trees require
the shade of larger trees such as banana, coconut, and Chocolate liquor is the solid or semisolid food prepared by
palm for protection. finely grinding the kernel or nib of the cocoa bean. It is also
Alternate Traditional Alternate
Cocoa beans Cocoa beans Cocoa beans
Cocoa cake
Standardizing Standardizing
Cocoa powder
Enrobing Molding Molding Enrobing
Table 5. Average Composition of Green and Roasted and 5-caffeoylquinic acid (neochlorogenic acid)occur at
Coffee least in part on potassium-caffeine-chlorogenate com-
Green, Roasted, plexes. They decompose in direct relationship to the degree
percent percent of roast. Table 6 shows the changes that occur in these
Constituents dry basis dry basis" acids during roasting. Apparently, chlorogenic acids mod-
Hemicelluloses 23.0 24.0
ify and control reactions that occur during the roast and
Cellulose 12.7 13.2 are particularly important to the decomposition of sucrose.
Lignin 5.6 5.8 Glycerides of linoleic and palmitic acids, along with
Fat 11.4 11.9 some glycerides of stearic and oleic acids, make up the 7
Ash 3.8 4.0 to 16% fat content of coffee. Some cleavage of glycerides
Caffeine 1.2 1.3 and some loss of unsaponifiables occur during roasting. Ta-
Sucrose 7.3 0.3 ble 7 details these losses (7).
Chlorogenic acid 7.6 3.5
Protein (based on nonalkaloid nitrogen) 11.6 3.1 Aroma
Trigonelline 1.1 0.7
Reducing sugars 0.7 0.5 Combinations of advanced chromatography and mass
Unknown 14.0 31.7 spectra analytical techniques have advanced the identifi-
Total 100.0 100.0 cation of volatile flavor components in roasted coffee to
"Not corrected for dry-weight roasting loss. more than 800. Although present in minute quantities,
they are extremely significant to the balance of flavor in a
cup of coffee. A historical account of this work has been
aromatic nitrogen ring compounds, such as pyridine, found published (8). A partial summary of the volatile compo-
in roasted coffee aroma. However, pyrazines, oxazoles, and nents by chemical class is in Table 8.
thiazoles, also components of the coffee aroma, are proba- Freshly roasted ground coffee rapidly loses its fresh
bly products of protein breakdown. Caffeine is relatively character when exposed to air, and within a few weeks de-
stable, and only small amounts are lost by sublimation velops a noticeable stale flavor. The mechanism for the de-
during roasting. velopment of staling is not known but is believed to be
The chlorogenic acids3-caffeoylquinic acid (choloro- caused by an oxidation reaction that can be catalyzed by
genic acid), 4-caffeoylquinic acid (cryptochlorogenic acid), increasing levels of moisture (9).
WILLIAM D. PANDOLFE
APV Americas-Homogenizers
Wilmington, Massachusetts
Figure 2. (a) Flow rate of a mayonnaise through a colloid mill IMPORTANCE OF FOOD COLOR
increases with in-feed pressure. The gap between the rotor and
the stator was 0.010 inches (0.254 mm). Density was 920 g/L. The role that color plays in the reaction to food is so au-
(b) Viscosity is reduced when the in-feed pressure is increased, tomatic that it may be taken for granted. This does not
causing an increase in flow rate and reduction in residence make that role any less important it merely decreases
time. Source: From the research laboratory APV Americas- awareness. The color of a food has important considera-
Homogenizers. tions for both the consumer and the technologist. These
considerations are quite different yet they are interrelated
as shown in Figure 1.
The psychological effects of color have long been recog-
Mayonnaise contains 65% or more vegetable oil. The col- nized. A room decorated in red exudes warmth and may
loid mill produces the best combination of fluid processing increase pulse and respiration rates and even increase vi-
conditions to make a good emulsion at this oil level. If this vacity. Whereas a room decorated in blue or green is cool
high oil level emulsion is processed on a homogenizer, then and peaceful encouraging concentration and relaxation.
the results are poor. The homogenizer makes too small a But darkening that blue can turn it into a subdued and
droplet size, which leads to instability and separation of even depressing atmosphere. The color of food also has its
the emulsion because the natural emulsifier in mayon- psychological aspects but these are less of mood swings
naise cannot stabilize the large interfacial area generated. than they are of learned associations. The color of a food
The colloid mill produces a droplet size range that makes not only sends a message of expectation but can also pro-
a stable, viscous product. On the other hand, a salad dress- vide clues as to the condition of that food; a yellow peach
ing at 30% oil can be made on a homogenizer or a colloid is ripe, brown strawberry jam is old. Food of an unnatural
mill. Because of the high viscosity usually associated with color raises a barrier that most people have difficulty over-
a salad dressing, a small oil droplet size is not necessary, coming. Witness the red-fleshed potato that cooks up blue.
and the energy level of a colloid mill is adequate to make Most people given the chance will avoid tasting it even
this type of emulsion. when assured it tastes similar to the familiar white vari-
There are many other products made on the colloid mill. eties. In contrast a recently introduced yellow-fleshed va-
In the cosmetic industry colloid mills are used for making riety, reminiscent of buttery mashed potatoes, is gaining
creams and lotions. In the chemical industry they are used in popularity. In a very real sense the appearance of a food
for preparing bituminous emulsions, silicone oil emulsions, acts as a gate keeper and the old saying "We eat with our
grease, and pigment dispersions. In many of these appli- eyes" is not far off the mark. Experience and memory play
cations, the colloid mill works well because of high dis- important roles in food assessment. This is easily demon-
persed phase concentration in the product, high viscosity strated by mismatching gelatin samples for color and fla-
components, and moderate droplet size requirements. vor. Even a familiar flavor such as orange is difficult to
cherry red of oxymyoglobin because of the strong effect on
Color of consumer acceptability.
food product
For many new products the product developer must con-
sider the eye appeal of the product, and this should be
given serious consideration in consumer acceptability rat-
ings in any optimization procedure undertaken. The need
Consumer Technologist to be aware of dynamic consumer reactions in regard to
color and appearance is paramount. What is preferred in
Experience Process the color of a product is influenced by experience and avail-
Quality Consistency ability and changes over time. The replacement of nitrites
Maturity Stability for curing meat products is complicated by the fact that
Like/dislike Oxidation the nitrites contribute to the characteristic color of cured
meat. A satisfactory replacement has yet to be found. To
support the deletion of nitrites from the process, consum-
Expectation R&D ers must exhibit sufficient concern about their diets that
Visual cue Optimization they would be willing to accept brown cured meat products
Identification of appeal or at least products that appeared different from those to
Food image Natural which they are accustomed.
appearance
Additive free
COLOR THEORY
Product
preference/acceptabi I ity A thorough review of color theory is beyond the scope of
this article; however, several references have been pub-
lished (1-5). The portion of the electromagnetic spectrum
Figure 1. Food color considerations for the consumer and for the that comprises visible light falls between 380 and 750 nm,
food technologist. bordered by ultraviolet light on the low end and infrared
light on the high end. The visible spectrum is represented
by the colors seen in the rainbow with blue existing at
recognize when colored red. This is because red is associ- wavelengths less than 480 nm; green roughly 480-560 nm;
ated with red fruits, thus a red-colored orange gelatin yellow, 560-590; orange 590-630; and red, at wavelengths
sends the wrong visual cue. This is of such proportion that longer than 630 nm (1). Purple is achieved by mixing blue
it is difficult to rely on the messages sent by the taste buds and red and is considered to be a nonspectral color. If white
and olfactory receptor. light is dispersed by a prism a spectrum is obtained rep-
In practice consumers do not isolate their sensory per- resenting all the visible colors at appropriate wavelengths.
ceptions of a food but combine them in obtaining a total The relative power or energy (power multiplied by time)
assessment for a food. This association is sufficiently emitted at these wavelengths can be plotted to produce the
strong that when asked to separate them there may still spectral power distribution curve of the light source. A
be a strong influence of one sensory perception on another. group of light sources, black bodies, change from black
Yet the visual sense is both sophisticated and sensitive, it through red to white when heated, the color produced be-
is only that experience has confirmed what the eye sees, ing dependent on the temperature reached. This is referred
which has caused the interaction of the senses to become to as color temperature. Tungsten filaments are close ap-
unconscious. proximations of black bodies, although their color tem-
The technologist has an interest in the color of food for perature is not exactly equal to their actual temperatures.
several reasons. One is the need to maintain a uniformity Real daylight and fluorescent lights do not approximate
of color over production runs. A second is the avoidance of black bodies.
color changes brought about by chemical reactions occur- When light falls on an object it may be reflected, ab-
ring during processing or storage life of the product. A sorbed, or transmitted or a combination of these may occur.
third is the optimizing of color and appearance in relation When light passes through a material essentially un-
to consumer preference. A fourth is the maintenance of a changed it is transmitted. Wherever light is slowed down,
color in accordance with consumer experience and expec- as occurs at the boundary of two materials, the light
tations. The need to maintain color uniformity over pro- changes speed and the direction of the light beam changes
duction runs varies with the food and especially with the slightly (refractive index). The change in direction is de-
packaging used. For example, the need is greater for fruit pendant on the wavelength and accounts for the dispersion
juices packaged in clear containers than for those pack- of light into a spectrum by a prism. The change in refrac-
aged in individual drinking boxes where very little of the tive index results in some light being reflected from the
juice is actually seen. The color problems of processed object. Light that is absorbed by the material is lost as
green vegetables are examples of color changes arising visible light. If light is absorbed completely the object ap-
from unstable pigment reactions. The retailing practices of pears black and opaque. If some of the light is not absorbed
fresh meat, particularly beef, have been limited for many but transmitted the object appears colored and transpar-
years by the need to maintain meat pigments in the bright ent. Lambert's law, which states that the fraction of light
that is absorbed by a substance is independent of the in- The human eye is an incredibly sensitive and discrim-
tensity of the incident light, is always true in the absence inating sensor; it can detect up to 10,000,000 different col-
of light scattering. Beer's law states that the light absorp- ors (6). The basic units of sight are the eye, the nervous
tion is directly proportional to the number of molecules system, and the brain. The cone light receptors located in
through which the light passes. In practice, Beer's law is the fovea of the retina of the eye are responsible for the
often not exactly observed, possibly due to chemical ability to see color. It is generally agreed that there are
changes in some of the absorbing molecules. three types of cone receptor responding to red, green, or
When light interacts with matter it may travel in many blue and that these responses are converted in nerve-
directions. The sky is blue because of light scattered by signal-switching areas within the eye and the optic nerve
molecules of air. Scattering caused by larger particles pro- to opponent-color signals as proposed by Muller. Three
duces the white of clouds, smoke, etc. Scattering results in opponent-color systems, black-white, red-green, and
light being diffusely reflected from an object. Translucent yellow-blue, were first proposed by Hering (3). The other
materials transmit part of the light and scatter part of the type of light receptor, the rods, are also located in the ret-
light, if no transmittance occurs, the object is said to be ina; they increase in density as the distance from the fovea
opaque. The color of the object is dependent on the amount increases. The rods are responsible for black-and-white vi-
and kind of scattering and the absorption occurring. The sion, the ability to see in dim light. Rods do not contribute
amount of light that is scattered is dependent on the dif- to color vision. Approximately 8% of the population, pre-
ference between the refractive indexes of the two materi- dominately men, have abnormal color vision. For all hu-
als. The boundary between two materials having the same mans the mode of presentation including viewing angle,
refractive index cannot be seen because no light scattering source of illumination, and background, affect the color
occurs. Large particles scatter more light than small par- perceived by the viewer.
ticles until the particle size approaches the size of the
wavelength, at which point scattering decreases. Many COLOR MEASUREMENT
foods are not completely reflecting or transmitting mate-
rials, which introduces an element of empiricism into an Tristimulus Colorimetry
attempt to measure the color (6). With these foods absorp-
tion and scattering are factors affecting visual judgments. It is possible to match colors with a simple laboratory
The absorption coefficient K and the scatter coefficient S setup. Three projectors with a red, green, and blue filter,
in the Kubelka-Munk equations have been used in at- respectively, can be focused with the image superimposed
tempts to deal with this (7,8). on a screen. A color to be matched is projected on the screen
The chemist tends to think of color rather simplistically by a fourth projector. An operator can match the desired
color by determining the amounts of red, green, and blue
as being determined by the amount of light absorbed at a
required for a match. Unfortunately, not all colors can be
specified wavelength. But that is not how color is seen, for
matched by the red, green, and blue primary colors, so the
it is the light that is reflected from an object that deter- researchers were given free rein to choose other primaries.
mines color. The appearance of an object may vary over the They chose X (roughly corresponding to red), Y (roughly
entire object because of the angle of viewing and the light corresponding to green), and Z (roughly corresponding to
falling on the object. Appearance attributes have been di- blue). X Y and Z are unreal in that they cannot be produced
vided into two categories: color, and geometric or spatial directly in the laboratory, but they are very useful math-
attributes (3). Color refers to the light reflected from the ematically. This concept was accepted by the Commission
object to provide a portion of the spectrum as well as white, Internationale de Eclairage (CIE) and became known as
gray, black, or any intermediate. Geometric attributes re- the CIE system. These tristimulus (three-stimuli) values
sult from the spatial distribution of the light from the ob- for the equal-energy spectrum were used to define the 2
ject and are responsible for the variation in perceived light 1931 standard observer and were designated as x, y, and
over a surface of uniform color, such as gloss or texture. z, which are special cases of X, Y, and Z; the 2 refers to
The mode in which the eye is operating affects the visual the angle of observation. Later systems of measurement
evaluation. There are three modes: the illuminant mode, were developed with a 10 angle of viewing and are thus
in which the stimulus is seen as a source of light; the object called 10 1964 standard observers. The definition of the
mode, in which the stimulus is an illuminated object; and XYZ system offered a number of advantages. First, all col-
the aperture mode, in which the stimulus is seen as light. ors lie within the primary coordinates. Second, the Y value
The aperture mode may be thought of as a lighted window contained all the lightness, and third, many of the coordi-
where first the light is seen, but at a closer range the object nates for orange and red colors lie along a straight line,
mode takes over and the contents of the room can be seen. which is a great advantage in color formulation.
The aperture mode views an object through a smallish ap- The XYZ values, sometimes presented as Y,x,y or xyz as
erture removing the effects of spatial distribution of light. described below, provided a measure of the color of a sam-
This method is usually used for visual color-matching ex- ple when viewed under a standard source of illumination
periments. However, it is the object mode that is of prac- by a standard observer. The CIE organization defined a
tical importance in assessing the appearance of a food. The number of standard sources of illumination. CIE Source A
everyday evaluations of color, haze, clarity, gloss, and opac- represented incandescent light and a color temperature of
ity are made by observing what the object does to the light 2,854 K; CIE Source B simulated noon sunlight; and CIE
falling on it. Source C simulated overcast-sky daylight. These light
sources were supplemented by the CIE in 1965, and illu-
minant D65 with a color temperature of 6,500 K is now White
widely used. In 1931 the CIE adopted the standard ob- light
server as having color vision representative of the average
of that of the population having normal color vision. These
data were used to obtain CIE standard-observer curves for
the visible spectrum for the tristimulus values r, g, and 6, Photocell
for a set of red, green, and blue primaries. The red, green, Surface Meter
and blue data were transformed into XYZ values and pro- to be
vided the basis for the standard observer curves shown in measured
Figure 2 (1). The definition of the standard observer curves
made it possible to design a simple colorimeter. Figure 3 Tristimulus
shows white light falling on a sample to be measured. The filters
reflected light is passed through a glass filter to determine
Figure 3. A simple tristimulus colorimeter. The light reflected
the X component, the Y component, and the Z component, from the sample passes through the three tristimulus filters, X,
respectively. The signal from each filter is measured elec- Y, and Z, and the signals are recorded by the photocell. The com-
tronically and constitutes a tristimulus reading for the bined outputs from the filter/photocell combination duplicate the
sample. The accuracy of the reading depends on the ability standard observer curves x j, and z and represent the color of the
of the manufacturer to produce a filter/photocell combi- sample.
nation that duplicates the response of the human eye, that
is, the standard observer curves. They have been very suc-
cessful in this aspect, and several commercial colorimeters "50
available today are based on this principle. o
RExcfcc
/-75O
Y = REydy
Spectrophotometry J380
r750
The CIE values of a color can be calculated by multiplying Z = EEzdz
the energy spectrum of the illuminant by the reflectance, J380
or transmission, spectrum of the sample and the standard
observer curves. They can be mathematically represented
where R is the sample spectrum, E is the source light spec-
by the following integral equations:
trum, and X9 y9 z are the standard observer curves.
Many of the more expensive colorimeters available to-
day record a spectrum from the sample as the initial signal
and calculate CIE values from it. This approach allows con-
siderable flexibility because the signal can be programmed
to produce data for any illuminant, several types of sample
presentation, a number of mathematical color systems,
special color scales, and many types of color difference cal-
culations. Interestingly, the early spectrophotometers de-
signed for color measurement 70 years ago all used this
Tristimulus values
Data Presentation
Spectrophotometers usually present data in XYZ units but
there are other conventional ways. Chromaticity coordi-
Wavelength (nm) nates (xyz) calculated by the following equations are often
used to plot a chromaticity diagram (Fig. 4). The conven-
Figure 2. Curves for 2 standard observer expressed as tristi- tion Yxy is also used, where Y represents CIE Y expressed
mulus values X, Yt and Z. as a percent of X + Y + Z:
Complementary
dominant
wavelength
Dominant wavelength
COMMERCIAL PREPARATION
SYNTHETIC COMPOUNDS
Erythrolaccin Deoxyerythrolaccin
compound. More recently, purification methods including Carminic acid is usually available as an aqueous solu-
proteinase enzyme treatments have produced colorants tion with a colorant content about 2 to 5%. It may also be
sometimes known as the "carmines of cochineal." The word spray-dried. Formulations may also contain propylene gly-
carmine has been used a general term for this class of an- col citric acid, and sodium citrate. Carmine is usually sup-
thraquinones, but the more usual meaning of the term car- plied as an alkaline solution with a carminic acid content
mine (CAS Reg. No. 1390-65-4) denotes a magnesium or of 2 to 7%. Traditionally, ammonia was used as an alkan-
aluminum lake of carminic acid. Carminic acid (Fig. 1) is izing agent, but recently formulations with potassium hy-
the pigment in cochineal, and the lakes usually contain droxide, spray-dried with maltodextrin as a carrier, have
about 50% of carminic acid. The content of carminic acid become available. They may also contain sodium hydrox-
is usually the way of specifying the strength, but Schul (1) ide, ammonium hydroxide, and glycerol. The intensity of
suggested that the price of carmine should be based on its carmine lakes is almost twice that of carminic acid; thus,
color strength, not on the carminic acid content, and pro- they are more cost-effective as colorants.
vided details of a method. The FDA-approved procedures
Applications
are specified in the CFR Section 73.100 for Carmine.
Solutions of carminic acid at pH 4 show a pale yellow Carmine is considered to be technologically a very good
color and actually have little intrinsic color at pH values food colorant. Its only significant limitation is with prod-
below 7, but they do complex with metals to produce stable ucts at low pH values. It is ideally suited for comminuted
brilliant red hues. Complexes with tin and aluminum pro- meat products such a sausages, processed poultry prod-
duce the most desirable hues, and nearly all commercial ucts, surimi, and red marinades. Other important uses are
preparations contain aluminum. A range of hues from in jams and preserves, gelatin desserts, baked goods, con-
"strawberry" to "black currant" can be produced by adjust- fections, icings, toppings, dairy products and soft drinks.
ing the ratio of carminic acid to aluminum. The color is The level of usage varies with the product and is usually
essentially independent of the pH value, being red at pH 0.05 to 1.0%. Cochineal and carmine are permitted as food
4 and bluish-red at pH 10. Aluminum lakes are soluble in colorants in the United States.
alkaline media and insoluble in acids. Carmine is very sta-
KERMES
ble to heat and light, resistant to oxidation, and not af-
fected by sulfur dioxide. The presence of other metal ions Kermes is a well-known red colorant in eastern Europe. It
may shift the color slightly toward the blue. is derived from the insects Kermes ilicis or Kermococcus
vermilis, which are found in the aboveground portions of ents were issued in the 1963 to 1984 era (2), and a large
several species of oak, particularly Quercus coccifera, the number of new compounds in this class have been reported
"Kermes Oak." The pigment in kermes is kermisic acid, the (3). Interest as food colorants stems mainly from their sta-
aglycone of carminic acid (Fig. 1). It also occurs as an iso- bility and high tinctorial strength. They were the chro-
mer ceroalbolinic acid (Fig. 1). The pigment is obviously mophores of choice in the "linked polymer" concept of col-
closely related to carminic acid, and the properties are very orants pioneered by the Dynapol Company, but this
similar. Colorants from kermes are not permitted in the concept is no longer being commercialized (2).
United States.
LAC BIBLIOGRAPHY
Lac is a red colorant obtained from the insect Laccifera 1. I. J. Schul, Proceedings of the First International Symposium
lacca found on the trees Schleichera oleosa, Ziziphus maur- on Natural Colorants, Amherst, Mass., November 7-10, 1993,
itiana, and Butea monosperma, which grow in India and The Hereld Co, Norwalk, Conn.
Malaysia. The lac insects are better known as a source of 2. F. J. Francis, Handbook of Food Colorant Patents, Food ands
shellac. The lac pigments are a complex mixture of an- Nutrition Press, Westport, Conn., 1986.
thraquinones (Fig. 2). The mixture also contains the
3. F. J. Francis, Lesser Known Food Colorants, in G. A. F. Hendry
closely related pigments erythrolaccin and deoxyerythro- and J. D. Houghton, eds., Natural Food Colorants, Blackie Pub-
laccin (Fig. 2). The chemistry and applications of lac are lishing, Glasgow, Scotland, 1996, pp. 310-341.
similar to cochineal. Colorants from lac are not permitted
in the United States.
Laccaic acid D
Figure 2. Structures of the anthraquinone pigments in lac. Figure 1. The diazoheptamethin structure.
Figure 2. Betacyanin resonating structures.
PREPARATION
presence of geosmin. Fermentation withAspergillus niger, protein together with citric and/or ascorbic acid as a pre-
Candida utilis, and Saccharomyces oviformis has been re- servative. The tinctorial power is usually expressed as %
ported to produce a product with improved stability and betanin. Betanin is identified as EEC No. E 162 or CAS
also to remove the geosmin. Traditionally, hydraulic or ro- Reg. No. 7659-95-2.
tary presses have been used, but they recover only about
50% of the pigment. Recoveries as high as 90% can be ac-
complished by continuous diffusion processes. A number of APPLICATIONS
resin and other absorption processes such as Dowex 50 W
followed by polyamide column chromatography with meth- Betanin preparations are water soluble with high tincto-
anol as the eluent, polyacrylamide (Bio-Gel P-6), and nu- rial strength. They are relatively unchanged in color from
merous others (3) are available for purification of the pig- pH 3 to 7 but are violet at pH values below 3 and bluer at
ments, but they are not usually permitted by legislation. pH values above 7. The absorption spectra of betanin at
In vitro cell suspensions have been reported to yield high three pH values are shown in Figure 6 (4). A shift in dom-
levels of pigment production, and they have a number of inant wavelength toward the left would indicate a yellower
advantages. The high growth rates of cultures makes pig- color and to the right a bluer color. The spectrum at pH 9
ment production efficient. The characteristic odor of geos- does show a small shift in color toward the bluish-red. Both
min is not produced. A number of pigments can be pro- the red and yellow pigments are thermolabile with and
duced selectively as desired. Economic commercialization without the presence of oxygen and are also degraded by
of cell culture production systems has yet to be demon- light. Metal cations such as iron, copper, tin, and alumi-
strated. But there is a need for more highly purified and num accelerate the degradation. With these limitations,
concentrated colorants. beetroot preparations may be used ideally to color products
Commercial beet powders usually contain 0.4 to 1.0% with short shelf life, which are packaged to reduce expo-
pigment expressed as betanin, 80% sugar, 8% ash, and 10% sure to light, oxygen, and high humidity; do not receive
tion and precipitation in the food. These undesirable
effects result from colloidal interactions of charged mac-
romolecular components of caramel with a particular food.
Hence, the net ionic charge of the caramel color macro-
molecules at the pH of the product in which it is used is a
prime determinant of compatibility (1).
Caramel (CI Natural Brown 10, EEC No. E 150) is a
Absorbance
COMMERCIAL PREPARATION
APPLICATIONS
It is obvious that heating carbohydrates in the presence
of a reactant would produce a wide range of chemical com- Caramel color is freely soluble in water but insoluble in
pounds. Complete characterization is not feasible; thus, a most organic solvents. In concentrated form the colorant
series of profiles were developed using 157 samples from has a characteristic burnt taste, which is not detectable at
11 manufacturers in seven countries. Since Caramel Color the levels normally used in foods and beverages. Commer-
IV accounts for 70% of all caramel colors manufactured, it cial preparations vary from 50 to 70% total solids with a
was chosen as a prototype for this ambitious undertaking. range of pH values depending on the type of caramel. More
The profiles developed were HPLC screening, size fraction- than 80% of the caramel produced in the United States is
ation by ultrafiltration to provide low molecular weight, used to color soft drinks, particularly colas and root beers.
intermediate molecular weight and high molecular weight Type I is designed for use with distilled spirits, desserts,
groupings, and subfractionation by cellulose chromatog- and spice blends. Type II is used with liqueurs. Type III is
raphy. Each fraction was examined by a series of sophis- suitable for baked goods, beer, and gravies. Type IV is used
ticated analytical approaches. These data combined with in soft drinks, pet foods, and soups.
11 physical characteristics confirmed that the four group-
ings provided real and reproducible classifications (3).
Color is a physical parameter of interest to the formu- BIBLIOGRAPHY
lator. It could, of course, be specified in any of the conven-
tional tristimulus color scales, but it is possible to specify 1. D. V. Myers and J. C. Howell, "Characterization and Specifi-
the color accurately by a simpler method (4). The color of cations of Caramel Colours: An Overview," Food Chem. Toxicol.
caramel is due to a large number of chemical chromo- 30, 359-363 (1992).
phores; thus, different formulations do not show markedly 2. J. E. Kassner, "Modern Technologies in the Manufacturer of
different spectral curves and do not change shape with con- Certified Food Colors," Food Technol. 41, 74-76 (1987).
centration. Curves of different concentrations can be su- 3. B. H. Licht, J. Orr, and D. V. Myer, "Characterization of Car-
perimposed on each other by plotting log absorbency amel Color TV," Food Chem. Toxicol. 30, 365-373 (1992).
against concentration. This is the "optical signature" of a 4. R. T. Linner, "Caramel Coloring: A New Method of Determining
colorant. When log absorbency is plotted against wave- its Color Hue and Tinctorial Power," Amer. Soft Drink J., 26-
length for caramel solutions, the result is a straight line 30 (1971).
COLORANTS: CAROTENOIDS degradation. Annatto shows more stability to exposure to
air than other carotenoids and is moderately stable to heat.
The carotenoids are one of the largest group of pigments Little change in color occurs with pH changes, but products
produced in nature, second only to the chlorophylls. They with a low pH may show a pinkish tinge due to isomeri-
are very widespread with more than 100,000,000 tons pro- zation of the pigments.
duced annually in nature. Most of this amount is produced
in the form of fucoxanthin in algae in the ocean and the LYCOPENE
three main carotenoids of green leaves: lutein, violaxan-
thin, and neoxanthin (Fig. 1). Other pigments predominate Lycopene occurs as the major (85-90%) pigment (Fig. 1) in
in certain plants, such as lycopene in tomatoes (Fig. 1), red tomatoes, Lycopersicum esculentum. The other pig-
capsanthin and capsorubin (Fig. 2) in red peppers, and ments are /7-carotene (10-15%) with small quantities of
bixin in annatto (Fig. 2). Colorant preparations have been about 10 other carotenoids. In spite of the fact that large
made from all of these (1), and obviously the composition quantities of lycopene are available in the waste from the
of the colorant extracts reflects the profile of the starting tomato-processing industry, colorants containing lycopene
material. The chemistry and occurrence of the carotenoids were not commercially available. This was probably due to
is well described in the article entitled COLORANTS: CAROT- the belief that lycopene was susceptible to degradation by
ENOIDS. Carotenoids are probably the best known of the oxidation and light. But recently a combination of better
food colorants derived from natural sources (2). manufacturing practices, and the development of a tomato
cultivar particularly high in lycopene led to the commer-
ANNATTO cialization of lycopene as a food colorant. Preparation of
lycopene extracts from tomatoes is relatively simple, in-
volving an alkali saponification and extraction with a mix-
Annatto (CI Natural Orange 4, CI No. 75120, EEC No. E
ture of solvents such as acetone and hexane. The acetone
16Ob) is found in the outer layers of the seeds of the shrub
can be removed by washing with water and the hexane by
Bixa orellana, a tropical plant grown in South America,
vacuum treatment, leaving a relatively pure lycopene ex-
India, East Africa, the Philippines, and the Carribbean.
tract. The extract would, of course, contain the other ca-
Peru and Brazil are the dominant sources of supply. An-
rotenoids in the tomato. Commercialization probably was
natto is one of the oldest colorants and has been used in
also helped by the health aspects because it may be an
antiquity for coloring foods, cosmetics, and textiles. It has
efficient in vivo radical scavenger. Lycopene preparations
been used for more than a hundred years in the United
are being marketed as a neutraceutical and as a food col-
States and Europe primarily as a colorant for dairy prod-
orant. Colorant preparations containing lycopene are cur-
ucts. The colorant is prepared by leaching, with gentle me-
rently not allowed in the United States.
chanical friction, of the seeds with various solvents, in-
cluding vegetable oil, fats, and alkali aqueous and alcoholic
solutions. Depending on the application, the crude extract PAPRIKA
may be refined by precipitation with acids and/or recrys-
tallization. Spray-dried powders are also available in both Paprika is a deep red pungent powder prepared from the
water-soluble and oil-soluble forms. The Food and Drug ground dried pods of the sweet pepper Capsicum annum.
Administration (FDA) approved procedures for extraction Paprika is produced in many warm countries around the
are specified in the 21 CFR section 73.30 for Annatto Ex- world, and several areas have developed products with
tract. specific characteristics such as the Hungarian paprika and
The pigments in annatto are a mixture of bixin, the the Spanish paprika. The same peppers are used in salads
monomethyl ester of a dicarboxylic carotenoid, and nor- and as a source of pimento. The other principal type of red
bixin, the dicarboxylic derivative of the same carotenoid pepper (also C. annum), typically called cayenne pepper or
(Fig. 2). Both bixin and norbixin normally occur in the cis cayenne, is usually much more pungent in flavor. Both
form, but small amounts of the more stable trans form are types are highly pigmented. The red pepper C. frutescens
formed on heating. A yellow degradation product termed is the source of the highly colored and very pungent Ta-
C17 yellow pigment (Fig. 2) is also produced on heating. basco sauce.
The cis forms are redder than the trans forms or the C17 Paprika contains capsanthin and capsorubin (Fig. 2) oc-
compound; thus, a source of red and yellow pigments are curring mainly as the lauric acid esters. Smaller quantities
available. The carboxylic portion of the molecule contrib- of about 20 other carotenoids are also present. Specifica-
utes to the solubility in water, and the ester form contrib- tions do not attempt to describe the pigment profile but
utes to oil solubility. This has provided flexibility in appli- usually specify color strength by the American Spice Trade
cations, and annatto has been used in a wide variety of Association (ASTA) Color Value. This is essentially the ab-
applications. sorption at 460 nm in acetone measured against a cobalt
Annatto is available in both water-soluble and oil- solution or a glass standard used as a reference (3).
soluble liquids and powders. The oil-soluble form is some- Paprika oleoresin (EEC No. E 16Oc) is an orange-red oil-
what unstable under oxidative conditions, and degrada- soluble extract from C. annum. The FDA-approved proce-
tion is increased by exposure to light and is catalyzed by dures are specified in 21 CFR Section 73.345 for Paprika
metals. Addition of antioxidants, such as ascorbic acid, to- Oleoresin. The dried and ground red peppers are extracted
copherols, and polyphenols, helps to minimize oxidative with a volatile solvent, usually a chlorinated hydrocarbon
Lutein
Fucoxanthin
Zeaxanthin
Neoxanthin
Violaxanthin
Lycopene
Figure 1. Selected structures for the carotenoids in plants.
Capsanthin
Capsorubin
Crocetin
gentiobioside
gentiobioside
Crocin
Bixin
Trans-bixin
Norbixin
Figure 2. The carotenoids of paprika (capsanthin and capsorubin), saffron (crocetin and crocin),
and annatto (bixin, transbixin, norbixin, and C17 yellow pigment).
followed by removal of the solvent. Preparations can also dipalmitate, dimyristate, myristate-palmitate, palmitate-
be made by extraction with a vegetable oil to provide an stearate, and distearate esters. Because of the seasonality
oil-soluble colorant. Paprika and paprika oleoresin add of the crop, the mature marigold flowers are collected and
both color and flavor to a product; thus, the applications the petals separated prior to storage in large bins contain-
are usually limited to products in which both characteris- ing up to 80 tons. The petals are removed as needed,
tics are desirable. For example, the recent rise in demand pressed, and then dried to less than 10% moisture. They
for tomato products in the form of pizza, salsa, and so on can then be ground and sold as tagetes meal. The ground
has increased the demand for paprika. Most of the spice petals can also be extracted with a number of solvents, but
extract used in Europe is used to flavor meat products, hexane seems to be preferred. After removal of the solvent,
soups, and sauces. Smaller quantities are used in salad a brown oleoresin is obtained, which can be incorporated
dressings, snacks, processed cheese, confectionery, and directly into poultry feed. The resin can be further purified
baked goods. by saponification and sold as Saponified Marigold Extract.
This product is suitable for incorporation into poultry feed.
SAFFRON The product can be further purified to produce a dry pow-
der suitable for use as a food colorant.
Colorants from tagetes are available in a variety of
Saffron (CI Natural Yellow 6, CI No. 75100) is a very old
forms. Formulations for animal feeds are usually ground
colorant dating back to the twenty-third century B.C. It has
dried petals, oleoresins, or saponified oleoresins. Food col-
come to be known as the "gourmet spice" because of its high
orants are available in a number of forms such as purified
price, but it also provides both spice and colorant. Saffron
lutein esters in oil-soluble or water-soluble dispersible sys-
consists of the dried stigmas of the flowers of the crocus
tems, spray-dried emulsions, gum-based emulsions, and
bulb, Crocus sativus, grown primarily in North Africa,
emulsifier-based emulsions. They show good stability to
Spain, Switzerland, Austria, Greece, and France. The high
heat, light, pH changes, and sulfur dioxide. They are sus-
price is due to the fact that it takes about 150,000 flowers
ceptible to oxidation, which can be minimized through the
to produce 1 kg of colorant.
addition of antioxidants such as ethoxyquin, ascorbic acid,
The pigments in saffron are chemically similar to those
tocopherols, BHA and BHT, and encapsulation. The
in annatto (Fig. 2). They are crocetin, a dicarboxylic carot-
strength of tagetes extracts is usually measured as the ab-
enoid, together with its gentiobioside ester. Gentiobioside
sorption of a 1%/1 cm solution in an appropriate solvent
is a diglucoside with a /3 16 linkage. The sugar portion
and is often quantified by calculations using the specific
confers solubility in water and makes the colorant very
extinction coefficient of lutein or lutein esters.
flexible in its applications to a variety of food and phar-
Tagetes colorants provide yellow to orange colors suit-
maceutical products. The same pigments occur in a num-
able for use in pastas, vegetable oils, margarine, mayon-
ber of other plants but C. sativus is the only commercial
naise, salad dressings, baked goods, confectionery, dairy
source. The fruits of the Cape Jasmine, Gardenia jasmi-
products, ice cream, yogurts, citrus juices, and mustard.
noides, produce the same pigments and have been sug-
Tagetes meal and its extracts are approved only as color-
gested as an alternate source. But the gardenia fruits sup-
ants in poultry feed in the United States.
ply only the colorant, not the spice flavor, so the sources
are quite different. Saffron extracts also contain /?-
carotene, zeaxanthin, and traces of several other carote- SYNTHETIC CAROTENOIDS
noids.
Saffron preparations are fairly stable to light, oxidation,
Plant extracts of carotenoids have been used for centuries
microbiological attack, and changes in pH. Overall, tech-
as food and cosmetic colorants, so it was only natural that
nically it is a good colorant with high tinctorial strength.
synthetic carotenoids would become available as colorants.
Its strength is usually judged by its carotenoid content as
The original synthesis of ^-carotene was reported in 1950,
measured by the absorption of an aqueous extract at 440
and commercial production followed in 1954. It was fol-
nm, but Alonso et al. (4) suggested that tristimulus meth-
lowed by /?-apo-8'-carotenal in 1962 and canthaxanthin in
ods were more appropriate for classifying samples of saf-
1964. The methyl and ethyl esters of /?-apo-8'-carotenoic
fron.
acid, citranaxanthin, and astaxanthin followed (Fig. 3). All
carotenoids by virtue of their structure are susceptible to
TAGETES degradation by oxidation, light, and heat. In addition, they
are insoluble in water and almost insoluble in oil. But ap-
Tagetes erecta L. (Aztec marigold) is an annual herb that propriate commercial preparations are currently available
grows from 3 to 4 tall in temperate climates. Colorants are for almost any type of food in the yellow to red range.
available in three forms: dried ground flower petals, oleo- A variety of approaches are used to prepare appropriate
resin extracts, and purified oleoresin extracts. The first formulations. These involve reducing particle size for sus-
two are used primarily in the poultry industry and the pensions in oil and stabilization with antioxidants. Three
third in the food industry. The principal producers are approaches are used to develop water-soluble products.
Mexico, Peru, the United States, Spain, and India (5). These are formulation of colloidal suspensions, emulsifi-
Tagetes petals contain up to 80% lutein with smaller cation of oily solutions, and dispersion in suitable colloids.
amounts of zeaxanthin, cryptoxanthin, /?-carotene, and They can be stabilized by a wide variety of additives in the
about 14 other carotenoids. The lutein compounds exist as protein, carbohydrate, and lipid categories and stabilized
Canthaxanthin
p-apo-8'-carotenal
p-apo-8'-carotenoic acid
with antioxidants (6). Carotenoid colorants are appropri- pastes are well known in Europe and consist of extracts of
ate for margarines, oils, fats, shortenings, fruit juices, alfalfa (lucerne), nettles, or broccoli. Unless they are sa-
beverages, dry soups, canned soups, dairy products, milk ponified they will be green due to their high content of chlo-
substitutes, coffee whiteners, dessert mixes, preserves, rophyll. Many concentrated xanthophyll pastes contain as
syrups, confectionery, salad dressings, meat products, much as 30% carotene with the major pigments as lutein
pasta, egg products, baked goods, and many others. (45%), ^-carotene (25%), violaxanthin (15%), neoxanthin
(15%), and a number of minor pigments. Highly concen-
trated extracts from alfalfa became available some years
MISCELLANEOUS CAROTENOID EXTRACTS ago as by-products of the Pro-Xan process for preparing
protein concentrates from alfalfa. The carotenoid extracts
The red oil obtained from the fruit of the palm tree Elaeis were widely promoted as colorant additives for poultry
guineensis is very highly pigmented with about 500 mg feed, but the Pro-Xan process was never commercially suc-
carotenoids per kilogram of oil. The carotenoid mixture is cessful. Extracts from citrus peels have been suggested as
very complex, containing mainly /?-carotene and about 20 a means of augmenting the natural color of orange juice
other carotenoids. The oil can be used as an ingredient to since the more highly colored juices command a premium
color margarine and other oil-based products, but its chief price, but addition of colorants from citrus is not permitted
use is as a cooking oil due to its distinctive flavor or, after in the United States at the present time. Citrus peel ex-
refining, as a general purpose edible oil. Xanthophyll tracts contain /?-carotene, cryptoxanthin, antheroxanthin,
violaxanthin, lycopene and /?-apo-8'-carotenol together 7. G. C. Hinostoza et al., "Pigmentation of Rainbow Trout Oncor-
with a number of others. About 115 carotenoid pigments hynchus mykiss by Astaxanthin from Red Crab Pleuroncodes
have been reported in citrus. Colorants from carrots planipes in Comparison with Synthetic Astaxanthin and Phaf-
usually contain about 80% ^-carotene and up to 20% a- fia rhodozyma Yeast," Proc. 2nd Int. Symp. on Natural Color-
ants, Puerto de Acapulco, Mexico, January 23-26, 1996.
carotene plus small amounts of several others. Some of
the high pigment strains of carrots used for colorant ex- 8. F. J. Francis, Handbook of Food Colorant Patents, Food and
tracts also contain lycopene. Astaxanthin is a desirable Nutrition Press, Westport, Conn., 1986.
addition to the diet of salmon and trout in aquaculture
because of its ability to impart a desirable red color
to the flesh. The usual sources of astaxanthin are the
by-products of the lobster and shrimp processing in- See also CAROTENOID PIGMENTS.
dustry, but the demand exceeds the supply. This has
led to an interest in growing the red yeast Phaffia rhodo-
zyma as a raw material for a concentrated extract. But
unfortunately Phaffia produces the wrong optical isomer COLORANTS: CARTHAMIN
of astaxanthin for optimal accumulation in the flesh of
salmon. Hinostroza et al. (7) reported that carotenoids
from three sources, synthetic astaxanthin, crabs (Pleuro- Carthamin (CI Natural Red 26; CI 75140) is a very old
codesplaniples), and P. rhodozyma, were deposited in trout colorant. Its use as a textile colorant dates back to antiq-
muscle at the rate of 7.8%, 5.0%, and 4.0%, respectively. uity under a variety of names such as Spanish saffron, Af-
The FDA has approved the addition of Phaffia products to rican saffron, American saffron, thistle saffron, false saf-
fish food. There is an ongoing interest to develop other fron, bastard saffron, Dyer's saffron, and so on. More
plant sources to compete with the nature-like synthetic ca- modern names are carthemone, carthamic acid, and safflor
rotenoids. Several mutants of the carotogenic molds Blak- red. Carthamin is a yellow to red preparation from saf-
eslea trispora and Phycomyces blakesleeanus produce high flower flowers, Carthemus tinctorius, of the family Com-
concentrations of ^-carotene, but recent interest has positae, which is cultivated extensively in Europe and
shifted to the microalgae. Species ofDunaliella can accu- America.
mulate up to 10% dry weight of ^-carotene. Ponds in Aus- Carthamin is classified biochemically as a chalcone in
tralia originally developed to produce salt by evaporation the yellow flavonoid group of pigments. The flavonoids are
of salt water are now being used to grow Dunaliella. Other a very large group of plant pigments with more than 4000
installations are in Hawaii. Regardless, both sources com- compounds, but only carthamin has been suggested as a
mand a premium because of their "natural" association. colorant. Carthamin contains three chalcones: the red car-
Interestingly, the same ponds can be used to grow Hae- thamin, safflor Yellow A, and safflor Yellow B (Fig. 1).
matococcus species, which accumulate astaxanthin. A gene Fresh yellow flower petals contain precarthamin, which
from H. pluvialis has been transferred to tobacco plants to oxidizes to form the red carthamin. Carthamin, under
provide a plant source of astaxanthin. In view of the wide- acid conditions, equilibrates to two isomers: red car-
spread occurrence of the carotenoid pigments, it is not sur- thamin and yellow isocarthamin (1). The earlier patents
prising that other plants and animals would be suggested on carthamin involved simple aqueous extraction of the
as potential sources of colorants. These include krill, chlo- petals or crushing the petals prior to extraction to allow
rella, shrimp, algae, bacteria, molds, and a variety of plant for oxidation (2). The three main pigments can be purified
sources (8). by passage through a styrene resin bed. Purification and
stabilization can be greatly enhanced by absorption of the
pigments on cellulose powder. Apparently cellulose has a
BIBLIOGRAPHY great affinity for carthamin and this is known as the
"Saito effect." "The effect is so strong that the carthamin
may be retained for more than a thousand years without
1. J. C. Bauernfeind, Carotenoids as Colorants and Vitamin A appreciable change to the coloration" (3). No storage data
Precursors, Academic Press, New York, 1981. were provided to substantiate this claim. The cellulose ab-
2. F. J. Francis, Handbook of Food Colorants, Eagen Press. St. sorption method was adapted to large-scale production us-
Paul, Minn., 1999. ing a methanolic extract and a cellulose column in acid
3. D. M. Marmion, Handbook of US Colorants, John Wiley & media. Another method using a cellulose derivative dieth-
Sons, New York, 1991. ylaminoethylcellulose yielded pure precarthamin, car-
4. G. L. Alonzo et al., "Color Analysis of Saffron," Proc. 2nd Int. thamin, safflor Yellow A and safflor Yellow B. Tissue cul-
Symp. on Natural Colorants, Puerto de Acapulco, Mexico, Jan- ture approaches have been successful in producing the
uary 23-26, 1996. safflower pigments as well as some novel closely related
5. J. Verghese, "Focus on Xanthophylls from Tagetes erecta, L. pigments (4,5).
The Giant Natural Colour Complex," Proc. 2nd International Carthamin has been suggested as a colorant for pine-
Symposium on Natural Colorants, Puerto de Acapulco, Mexico, apple juice, yogurt, butter, liqueurs, confectionery and so
January 23-26, 1996. on. The yellow to red range of colors gives it some flexibil-
6. F. J. Francis, "Carotenoids as Colorants," World of Ingredients, ity. Currently it is not approved for use in foods in the
34-38 (1995). United States.
violaxanthin, lycopene and /?-apo-8'-carotenol together 7. G. C. Hinostoza et al., "Pigmentation of Rainbow Trout Oncor-
with a number of others. About 115 carotenoid pigments hynchus mykiss by Astaxanthin from Red Crab Pleuroncodes
have been reported in citrus. Colorants from carrots planipes in Comparison with Synthetic Astaxanthin and Phaf-
usually contain about 80% ^-carotene and up to 20% a- fia rhodozyma Yeast," Proc. 2nd Int. Symp. on Natural Color-
ants, Puerto de Acapulco, Mexico, January 23-26, 1996.
carotene plus small amounts of several others. Some of
the high pigment strains of carrots used for colorant ex- 8. F. J. Francis, Handbook of Food Colorant Patents, Food and
tracts also contain lycopene. Astaxanthin is a desirable Nutrition Press, Westport, Conn., 1986.
addition to the diet of salmon and trout in aquaculture
because of its ability to impart a desirable red color
to the flesh. The usual sources of astaxanthin are the
by-products of the lobster and shrimp processing in- See also CAROTENOID PIGMENTS.
dustry, but the demand exceeds the supply. This has
led to an interest in growing the red yeast Phaffia rhodo-
zyma as a raw material for a concentrated extract. But
unfortunately Phaffia produces the wrong optical isomer COLORANTS: CARTHAMIN
of astaxanthin for optimal accumulation in the flesh of
salmon. Hinostroza et al. (7) reported that carotenoids
from three sources, synthetic astaxanthin, crabs (Pleuro- Carthamin (CI Natural Red 26; CI 75140) is a very old
codesplaniples), and P. rhodozyma, were deposited in trout colorant. Its use as a textile colorant dates back to antiq-
muscle at the rate of 7.8%, 5.0%, and 4.0%, respectively. uity under a variety of names such as Spanish saffron, Af-
The FDA has approved the addition of Phaffia products to rican saffron, American saffron, thistle saffron, false saf-
fish food. There is an ongoing interest to develop other fron, bastard saffron, Dyer's saffron, and so on. More
plant sources to compete with the nature-like synthetic ca- modern names are carthemone, carthamic acid, and safflor
rotenoids. Several mutants of the carotogenic molds Blak- red. Carthamin is a yellow to red preparation from saf-
eslea trispora and Phycomyces blakesleeanus produce high flower flowers, Carthemus tinctorius, of the family Com-
concentrations of ^-carotene, but recent interest has positae, which is cultivated extensively in Europe and
shifted to the microalgae. Species ofDunaliella can accu- America.
mulate up to 10% dry weight of ^-carotene. Ponds in Aus- Carthamin is classified biochemically as a chalcone in
tralia originally developed to produce salt by evaporation the yellow flavonoid group of pigments. The flavonoids are
of salt water are now being used to grow Dunaliella. Other a very large group of plant pigments with more than 4000
installations are in Hawaii. Regardless, both sources com- compounds, but only carthamin has been suggested as a
mand a premium because of their "natural" association. colorant. Carthamin contains three chalcones: the red car-
Interestingly, the same ponds can be used to grow Hae- thamin, safflor Yellow A, and safflor Yellow B (Fig. 1).
matococcus species, which accumulate astaxanthin. A gene Fresh yellow flower petals contain precarthamin, which
from H. pluvialis has been transferred to tobacco plants to oxidizes to form the red carthamin. Carthamin, under
provide a plant source of astaxanthin. In view of the wide- acid conditions, equilibrates to two isomers: red car-
spread occurrence of the carotenoid pigments, it is not sur- thamin and yellow isocarthamin (1). The earlier patents
prising that other plants and animals would be suggested on carthamin involved simple aqueous extraction of the
as potential sources of colorants. These include krill, chlo- petals or crushing the petals prior to extraction to allow
rella, shrimp, algae, bacteria, molds, and a variety of plant for oxidation (2). The three main pigments can be purified
sources (8). by passage through a styrene resin bed. Purification and
stabilization can be greatly enhanced by absorption of the
pigments on cellulose powder. Apparently cellulose has a
BIBLIOGRAPHY great affinity for carthamin and this is known as the
"Saito effect." "The effect is so strong that the carthamin
may be retained for more than a thousand years without
1. J. C. Bauernfeind, Carotenoids as Colorants and Vitamin A appreciable change to the coloration" (3). No storage data
Precursors, Academic Press, New York, 1981. were provided to substantiate this claim. The cellulose ab-
2. F. J. Francis, Handbook of Food Colorants, Eagen Press. St. sorption method was adapted to large-scale production us-
Paul, Minn., 1999. ing a methanolic extract and a cellulose column in acid
3. D. M. Marmion, Handbook of US Colorants, John Wiley & media. Another method using a cellulose derivative dieth-
Sons, New York, 1991. ylaminoethylcellulose yielded pure precarthamin, car-
4. G. L. Alonzo et al., "Color Analysis of Saffron," Proc. 2nd Int. thamin, safflor Yellow A and safflor Yellow B. Tissue cul-
Symp. on Natural Colorants, Puerto de Acapulco, Mexico, Jan- ture approaches have been successful in producing the
uary 23-26, 1996. safflower pigments as well as some novel closely related
5. J. Verghese, "Focus on Xanthophylls from Tagetes erecta, L. pigments (4,5).
The Giant Natural Colour Complex," Proc. 2nd International Carthamin has been suggested as a colorant for pine-
Symposium on Natural Colorants, Puerto de Acapulco, Mexico, apple juice, yogurt, butter, liqueurs, confectionery and so
January 23-26, 1996. on. The yellow to red range of colors gives it some flexibil-
6. F. J. Francis, "Carotenoids as Colorants," World of Ingredients, ity. Currently it is not approved for use in foods in the
34-38 (1995). United States.
Figure 1. Pigments of carthamin (a) carthamin; (b) Safflor Yellow A; (c) Safflor Yellow B.
Orange B
Citrus red no 2
FD & C no. 40
FD & C red no. 3
Table 2. Regulatory Status of Colorants Exempt from Certification in the United States
E.G. JECFAADP
Name of color additive U.S. food use limit status (mg/kg/bw)
Annatto GMP6 ElGOb 0-0.065 (calculated
as bixin)
Dehydrated beets GMP E 162 Not evaluated
Ultramarine blue Salt for animal feed up to 0.5% by weight Not listed None
Canthaxanthin Not to exceed 30 mg/pd of solid/semisolid food E161g None
or pint of liquid food or 4.41 mg/kg of chicken
feed
Caramel GMP E 150 0-200
/?-apo-8 ' -carotenal Not to exceed 15 mg/pd of solid or semisolid food E 16Oa 0-5
or 15 mg/pt of liquid food
^-Carotene GMP E 16Oa 0-5
Cochineal extract or carmine GMP E 120 0-5
Toasted partially defatted cooked GMP Not listed Not evaluated
cottonseed flour
Ferrous gluconate GMP for ripe olives only Not listed Not evaluated
Grape color extract GMP for nonbeverage foods E 163 Not evaluated
Grape skin extract (Enocianina) GMP for beverages E 163 0-2.5
Synthetic iron oxide Pet food up to 0.25% E 172 0-2.5
Fruit juice GMP Not listed Not evaluated
Vegetable juice GMP Not listed Not evaluated
Dried algal meal GMP for chicken feed Not listed Not evaluated
Tagetes (Aztec marigold) meal GMP for chicken feed Not listed Not evaluated
and extract
Carrot oil GMP Not listed Not evaluated
Corn endosperm oil GMP for chicken feed Not listed Not evaluated
Paprika GMP E 16Oc None allocated
Paprika oleoresin GMP E 16Oc Self-limiting as spice
Riboflavin GMP ElOl 0-0.5
Saffron GMP Not listed Food ingredient
Titanium dioxide Not to exceed 1% by weight of food E 171 Not specified
Turmeric GMP E 100 (curcumm) Temporary ADI not
extended
Turmeric oleoresin GMP E 100 (curcumin) Temporary ADI not
extended
0
JECFA refers to the Joint Expert Committee on Food Additives set up by the World Health Organization and the Food and Agriculture Organization of the
United Nations. The term ADI refers to Acceptable Daily Intake as usually determined by the JECFA.
6
GMP = Good manufacturing practice.
colorants as discussed in COLOR AND FOOD. But each col- COLORANTS: HAEMS
orant probably will behave differently in each food system;
therefore prediction from a knowledge of each colorant is Haemoglobin from blood is the only commercially impor-
difficult. The blending will have to be done under actual tant colorant in the haem group. The term haem, or heme,
food conditions. The stability of the FD&C colorants under is used to describe iron derivatives of the cyclic tetrapyr-
acid, alkaline, light, heat, and oxidation/reduction condi- role protoporphin with the structure shown in Figure 1.
tions, and the presence of sugars, acids, diluents, solubility, The numbering system is similar to that for chlorophyll
and so on discussed by Francis (2). The FD&C colorants (see COLORANTS: CHLOROPHYLLS, Fig. 2). This structure is
are appropriate for a wide variety of foods, particularly basic to a number of compounds such as chlorophyll, im-
those requiring a water-soluble colorant. portant in photosynthesis; haemoglobin, in oxygen trans-
port; cytochrome, in energy transport; and a number of
other enzymes. Haemoglobin is probably the best known,
LAKES and it is composed of a haem group associated with a pro-
tein. Haemoglobin forms a loose association with oxygen
Lakes are colorants prepared by precipitating a soluble col- as the basis for oxygen transport and carbon dioxide re-
orant onto an insoluble base or substratum. A variety of moval and is remarkably stable in vivo but not in vitro.
bases such as titanium dioxide, zinc oxide, talc, calcium This introduces some difficulty in using haems as color-
carbonate, and aluminum benzoate are approved for D&C ants.
lakes, but only aluminum, magnesium, and calcium salts Free haem can be easily extracted from blood by treat-
are approved in the United States for manufacturing ment with acidified organic solvents. Preparation of haem
from blood has been known for centuries and can be accom-
FD&C lakes. The process of manufacture is fairly simple.
plished by the addition of whole blood to glacial acetic acid
First, a substratum is prepared by adding sodium carbon-
saturated with salt at 10O0C. Crystalline haem precipi-
ate to a solution of aluminum sulfate. Next a certified col-
orant is added to the slurry, then aluminum sulfate is tates out, but it is not stable enough to function as a food
added to convert the colorant to an aluminum salt, which colorant. More stable compounds can be produced by allow-
is absorbed onto the surface of the alumina. The slurry is ing other ligands such as carbon monoxide, nitrous oxide,
hydroxides, and cyanide to displace the oxygen from the
then washed, dried, and ground to a fine powder. The col-
ored powder can be marketed as is or mixed with a diluent central iron atom. A number of patents exist (1), and they
such as hydrogenated vegetable oil, coconut oil, propylene fall into three broad areas: (1) treatment of whole blood
glycol, glycerol, sugar syrup, or other media appropriate with a variety of reagents, (2) stabilization of the color with
for food consumption or for printing food wrappers. Dilu- a variety of ligands, and (3) purification of haem deriva-
ents for both pure colorants or lakes have to be either on tives. Treatment of whole blood to remove the haemoglobin
has considerable appeal because the iron is in a very nu-
the Generally Recognized As Safe (GRAS) list or on the list
approved by the FDA Code of Federal Regulations (1-3). tritionally available form as a dietary supplement and the
protein has a high biological value. It would be still another
Lake colorants have many advantages, primarily be-
advantage if the preparation could be made stable enough
cause they are insoluble in most solvents including water.
They have a high opacity, are easily incorporated into dry to act as a food colorant. A number of the patents claim
media, and have superior stability to light and heat. They
are effective colorants for candy and pill coatings since
they do not require removal of water prior to processing.
They are particularly effective for coloring hydrophobic
foods such as fats and oils, confectionery products, bakery
products, salad dressings, chocolate substitutes, and other
products in which the presence of water is undesirable.
Lakes made from some water-soluble FD&C colorants may
show some bleeding when formulated in foods outside the
pH range 3.5 to 9, but few foods are in this pH range. Lakes
have been used to color food packaging materials including
lacquers, plastic films, and inks from which straight water-
soluble colorants would be soon leached.
BIBLIOGRAPHY
gentiobiose
Figure 1. Structures of nine iridoid
pigments in G. jasminoides. Gl =
Geniposidic acid Genipingentiobioside Scandoside methylester glucose.
amino groups allow a range of colorants to be produced.
Several patents involve culturing extracts of gardenia with
microorganisms such as Bacillus subtilis, Aspergillus ja-
ponicus, or a species ofRhizopus. Several patents involve
hydrolysis of the iridoid glycoside geniposide by the action
of /?-glucosidase to produce genipin. The genipin can be re-
acted with taurine to produce a blue colorant. Other amino
acids such as glycine, alanine, leucine, phenylalanine, and
tyrosine can be reacted to produce brilliant blue colorants.
They are claimed to be stable for two weeks at 4O0C in 40%
Flavonoid compounds
ethanol. Four greens, two blues, and one red have been
commercialized in Japan.
Colorant preparations from gardenia have been sug-
Compound R1 R2 R3 R4 R5 R6 gested for use with candies, sweets, colored ices, noodles,
1 H H H O M e O M e O M e imitation crab, fish eggs, glazed chestnuts, beans, dried
2 OMe H H OH OMe OH fish substitutes, liqueurs, baked goods, and so on. In view
3 H H OMe OMe H OH of the wide range of colors and apparent stability, colorants
4 OMe H H OMe OMe OH from gardenia appear to have good potential. They are not
approved for use in the United States.
5 OMe OMe H H OH H
Rubropunctamine R = C sHn
Figure 1. Pigments of Monascus. Monascorubramine R = CyH 15
CHEMISTRY problem. Han and Mudgett (1992) concluded that M. pur-
pureus ATCC 16365 was the most appropriate organism
Monascus species produce six pigments with the struc- for solid-state fermentation and confirmed that it had no
tures shown in Figure 1. Monascin and ankaflavin are yel- antibiotic activity (5). Monascus produces a range of com-
low, rubropunctatin and monascorubin are red, and rub- pounds normal to growth metabolism such as alcohol, en-
ropunctamine and monascorubramine are purple. The red zymes, coenzymes, monascolins that modify fat metabo-
and yellow pigments are considered to be normal second- lism, antihypertensive agents, and flocculents. This is a
ary metabolites of fungal growth, and the purple pigments strain selection problem, growth optimization, and finally
may be formed by enzymatic modification of the red and a removal problem for a food colorant.
yellow pigments. The red pigments are very reactive and
readily react with amino groups via a ring opening and a
Schiff rearrangement to form water-soluble compounds APPLICATIONS
such as that in Figure 2(2). The Monascus pigments have
been reacted with amino groups, polyamino acids, amino Monascus colorants offer considerable advantages since
alcohols, chitin amines or hexamines, proteins, peptides they can be produced in any quantity on inexpensive sub-
and amino acids, sugar amino acids, browning reaction strates. Their range of colors from yellow to red and their
products, aminoacetic acid, and amino benzoic acid (3). Ob- stability in neutral media is a real advantage. Sweeny et
viously a number of derivatives are possible, and they have al. suggested Monascus colorants for processed meats, ma-
been shown to have greater water solubility, thermosta- rine products, jam, ice cream, and tomato ketchup (6).
bility, and photostability than the parent compounds. They should be appropriate for alcoholic beverages such as
The Monascus pigments are readily soluble in ethanol saki and also for koji, soy sauce, and kamboko. There is
and only slightly soluble in water. Ethanolic solutions are considerable interest in the Monascus group, with 38 pat-
orange at pH 3 to 4, red at 5 to 6 and purplish red at 7 to ents issued in the years 1969 to 1985 (3). Currently Mon-
9. The pigments fade under prolonged exposure to light, ascus colorants are not permitted in the United States.
but the pigments in 70% alcohol are more stable than in
water. The pigments are very stable to temperatures up to BIBLIOGRAPHY
10O0C in neutral or alkaline conditions.
1. H. C. Wong and P. E. Koehler, "Mutants for Monascus-pigment
COMMERCIAL PRODUCTION Production," J. Food ScL 46, 956-957 (1981).
2. U.S. Pat. 3,993,789, H. R. Moll and D. R. Farr.
Monacus colorants are currently being produced in Japan, 3. F. J. Francis, Handbook of Food Colorant Patents, Food and
China and Taiwon. Traditionally, Monascus has been Nutrition Press, Westport, Conn., 1986.
grown on solid cereal substrates such as rice and wheat 4. Jap. Pat. 81,006,263 (1981), H. Tadao et al.
and the entire mass used as a food or a food ingredient. 5. O. H. Han and R. E. Mudgett, "Effects of Oxygen and Carbon
But it became obvious that the fungus could be grown in Dioxide on Monascus Growth and Pigment Production in Solid
liquid or fluid solid state media and optimized for pigment State Fermentation," Biotechnol. Prog. 8, 5-12 (1992).
production. Much research has been devoted to the deter- 6. J. G. Sweeny et al., "Photoprotection of the Red Pigments of
mination of the optimal conditions for pigment production Monascus anka in Aqueous Media by 1.4,6-Trihydroxy-
on a wide variety of cereal substrates. It is possible to max- naphthalene/'Agric. Food Chem. 29, 1189-1193 (1981).
imize the production of either the red or yellow pigments
to produce a range of red to yellow colors. For example,
Tadao et al. reported that M. anka grown on bread pro- COLORANTS: PHYCOBILINS
duced only yellow pigments (4). Criticism was directed at
the earlier production methods because the fungus pro- Phycobilins are found in abundance as components of the
duced an antibiotic, and this is considered to be an unde- blue-green, red, and cryptomonad algae. They are colored,
sirable food ingredient. Recent strain selections and con- fluorescent, water-soluble pigment-protein complexes clas-
trol of growth conditions have eliminated the antibiotic sified into three major groups according to color: the phy-
coerythrins, which are red in color with a bright orange
fluorescence, and the phycocyanins and allophycocyanins,
which are both blue and fluorescent red. The range of color
and the apparent stability of the pigments appear to make
this group attractive as food colorants.
The structures for the two chromophores of the cyano-
bilins, termed phycocyanobilin and phycoerythrobilin, are
shown in Figure 1. Phycocyanins and allophycocyanins
share the same chromophore, and the differences in color
Figure 2. A red derivative of the monascin pigment. R represents are due to the different protein groups. Figure 1 shows a
an aliphatic radical and R' represents a compound of the formula bilin written in the conventional linear form and also in
HN-R, which represents an amino sugar, a polymer of an amino acyclic, possibly truer, form, showing its relationship to
sugar, or an amino alcohol. Source: Ref. 2. other pigments such as chlorophyll and haemoglobin. The
algal cells. The centrifugate is a brightly colored solution
of water-soluble protein of which 40% may be phycobilin.
Further purification by precipitation with ammonium sul-
phate and ion-exchange yields almost pure phycobilin. The
free chromophore can be obtained by extended refluxing in
methanol. An alternative to extensive purification would
be to grow an organism such as Cyanidium caldarium,
which, on addition of 5-aminolevulinic acid to the growth
medium, yields pure phycocyanobilin (1). Another ap-
proach is to use the existing technology for growth ofSpi-
rulina platensis in open ponds. This organism has been
used for eons in Africa and Mexico, probably because of its
high protein content and digestibility. It is important in
health food stores as a dietary supplement. The cells are
simply harvested and dried. Another unicellular organism,
the red algae Porphyridium cruentum can also be grown
in open ponds or in tubular reactors for production of phy-
cobilin and phycoerythrin. A number of patents (2) exist
for the extraction, stabilization, purification, and use of
phycocyanins from Spirulina and Aphanotheca nidulans,
and three firms are marketing the product.
The presence of a protein in the pigment suggests that
the colorant would be used for products requiring a mini-
mum of heat treatment. But the fact that it takes 16 hours
in boiling methanol to separate the protein from the chro-
mophore suggests that applications could include products
with mild heat treatment. Suggested applications for phy-
cocyanin colorants include chewing gums, frozen confec-
tions, soft drinks, dairy products, sweets, and ice cream.
No patents have been filed for the use of phycoerythrin,
but it seems like a good candidate for a red colorant.
There are several industrial applications for phyco-
bilins such as fluorescent tracers in biochemical research,
fluorescence-activated cell sorting, fluorescence micros-
copy, and so on (1). Existence of other markets will cer-
tainly help to obtain the critical volume necessary for pro-
duction of food colorants. Colorants containing phycobilins
are currently not permitted in the United States.
BIBLIOGRAPHY
COLORANTS: POLYPHENOLS
attachment of the bilin chromophore to its protein is very
The major brown food colorant is obviously caramel, but
stable due to covalent bonds between the ethylidene group
other sources are available. A brown colorant can be pre-
on position 3 (see COLORANTS: CHLOROPHYLLS, Fig. 2) of
pared from an appropriate mixture of FD&C colorants or
the bilin with a cysteine group in the protein. A second
from extracts of cacao or tea.
covalent bond may be on position 18. The major function
of the bilin pigments is to act as light absorbers in the
energy transport system. CACAO
Phycobilin preparations can be obtained by simply
freeze-drying an algal cell suspension, producing a highly Cacao, Theobroma cacao, has been suggested as a poten-
colored powder. The chlorophyll and carotenoid compo- tial source of brown colorants. The cocao, pods, beans,
nents can be removed by centrifuging after breaking the shells, cotyledons, husks, and stems all contain a complex
mixture of polyphenols such as cyanidin glycosides, leu-
coanthocyanins, (-)-epicatechins, quercitin glycosides, and
the acyl acids p-coumaric and gentisic. Colorants prepared
from cacao are likely to contain a complex mixture of leu-
coanthocyanins, flavonoid polymers, and catechin-type
polymers.
The suggested extraction methods involve hot acid or
alkaline water or ethanol followed by nitration and con-
centration. A more reddish extract can be obtained by prior
roasting of the beans followed by extraction with hot aque-
ous alkaline solutions. The colorant is suitable for most
foods where a brown color is desired. Cacao products are Curcumin RI = R2 = OCH3
permitted as food ingredients in the United States but not Demethoxycurcumin RI = H R2 = OCH3
as a source of colorants. Bisdemethoxycurcumin RI = R2 = H
Vegetables
Artichoke (Cynara scolymus) 2-3 2-3 O 32 1 mo CA decreases discoloration 51
Asparagus (Asparagus officinalis) Air 10-14 2 36 3wk High CO2 is beneficial 51
Bean, lima (Phaseolus limensis) >5 10-35 5-7 40-45 7-10 d Shelled only 52
Bean, snap (Phaseolus vulgaris) 2-3 4-7 8 46 2 wk CA reduces color loss 51
Broccoli (Brassica oleracea italica) 1-2 5-10 O 32 1 mo CA maintain green color 51
Brussels sprouts (Brassica oleracea gemmifera) 1-2 5-7 O 32 3-5 wk CA reduces yellowing 51
Cabbage (Brassica oleracea, capitata) 2-3 3-6 O 32 6-8 mo Large scale commercial use 51
Cantaloupe (Cucumis melo) 3-5 10-20 8 46 2-3 mo CA reduces ripening 51
Cauliflower (Brassica oleracea botrytis) 2-3 3-4 O 32 1 mo 51
Celery (Apium graveolens) 1-4 3-5 O 32 3 mo 51
Chinese cabbage (Brassica campestris) 1-2 0-5 O 32 4-5 mo CA reduces leaf abscission 51
Corn, sweet (Zea mays} 2-4 5-10 O 32 2 wk CA reduces sugar loss 51
Cucumber (Cucumis sativus) 1-4 O 12 54 3wk CA reduces yellowing 51
Leek (Allium porrum) 1-6 5-10 O 32 4 mo 51
Lettuce, head (Lactuca sativa) 1-3 O O 32 3-4 wk 51
Mushroom (Agaricus bisporus) Air 10-15 O 32 1-2 wk CO2 retards cap opening 51
Onion, dry (Allium cepa) 0-1 0-5 O 32 8 mo Tolerant to low O2 51
Onion, green (Allium cepa) 1 5 O 32 2 mo 53
Parsley (Petroselinum crispum) 8-10 8-10 O 32 3 mo 51
Pepper, sweet (Capsicum annuum) 2-5 O 12 54 3wk 51
Radish (Raphanus sativus) 1-2 2-3 O 32 4 mo 51
Spinach (Spinacia oleracea) 7-10 5-10 O 32 3wk 51
Tomato (Lycopersicon esculentum) 3-5 2-3 12 54 4-6 wk
Note: The approximate storage periods are compiled by the authors based on all the information available.
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50. J. S. Pruthi, "Physiology, Chemistry, and Technology of Pas- T. Palma et al., "Respiratory Behavior of Cherimoya (Annona cher-
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51. M. E. Saltveit, "A Summary of Requirements and Recommen- 647-649 (1993).
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of Harvested Vegetables," in Ref. 45. Term Controlled Atmospheres and Maturity on Ripening and
52. A. L. Ryall and W. J. Lipton, Handling, Transportation, and Eating Quality of Tomatoes," Postharvest Biology and Tech-
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GENERAL REFERENCES (1994).
J. Stow, "The Effects of Storage Atmosphere on the Keeping Qual-
D. Batram, "CA Storage Key to Growth of State's Apple Industry," ity of Idared Apples," Journal of Horticultural Science 70,587-
Good Fruit Grower 47, 44-46 (1996). 595 (1995).
T. K. Thomas and E. M. Sfakiotakis, "Effect of Low-Oxygen At- that were ductile both before and after welding were de-
mosphere on Storage Behaviour of Kiwifruit," Advances in veloped in Sheffield, England (then the heart of the British
Horticultural Science 11, 137-141 (1997).
A. B. Truter, J. C. Combrink, and S. A. Burger, "Control of Super- steel industry) exploiting scientific work undertaken in
ficial Scald in Granny Smith Apples by Ultra-Low Levels of Germany. This new group of steels was based on an 18%
Oxygen as an Alternative to Diphenylamine," Journal of Hor- chromium steel to which nickel was added as a second al-
ticultural Science 69, 581-587 (1994). loying element. These were termed the austenitic stainless
R. K. Voltz et al., "Prediction of Controlled Atmosphere-Induced steels. The general relationship between chromium and
Flesh Browning in Fuji Fruit," Postharvest Biology and Tech- nickel necessary to maintain a fully austenitic structure is
nology 13, 97-102 (1998). shown diagrammatically in Figure 1. It will be seen that
H. S. Yong and L. A. Kyung, "Physiological Characteristics of the optimum combination is 18% chromium, 8% nickel
Chilling Injury and CA Effect on its Reduction During Cold hence the terminology 18/8s.
Storage of Pepper Fruit," Journal of the Korean Society for Hor- Probably the next major advance in the development of
ticultural Sciences 38, 478-482 (1997).
H. S. Yong, I. I. Kim, and L. C. Jae, "Effects of Harvest Maturity stainless steels was the discovery that relatively small ad-
and Storage Environments on the Incidence of Watercore, ditions of molybdenum had a pronounced effect on the cor-
Flesh Browning, and Quality in Fuji Apples," Journal of the rosion resistance, greatly enhancing the ability to with-
Korean Society for Horticultural Sciences 39, 569-573 (1998). stand the effects of mineral acids and other corrodents
P. Younmoon et al., "Preharvest Factors Affecting the Incidence of such as chloride solutions. Needless to say, from these
Physiological Disorders During CA Storage of Fuji Apples," early developments, there has been tremendous growth in
Journal of the Korean Society for Horticultural Sciences 38, production facilities and the number of grades of stainless
725-729 (1997). steel available. Table 1 lists some of the more commonly
available grades, while Figure 2 illustrates how the basic
CHIEN Yi WANG 18/8 composition is modified to enhance specific physical
ALLEY E. WATADA or chemical properties.
USDA/ARS In spite of the plethora of stainless steels available,
Beltsville, Maryland grades 304 and 316 have, and continue to be, the work-
horses for fabrication of dairy and food processing equip-
ment.
See also PACKAGING: PART IVCONTROLLED/MODIFIED Although 316 stainless steel offers excellent resistance
ATMOSPHERE/VACUUM FOOD PACKAGING. to a wide range of chemical and nonchemical environ-
ments, it does not offer immunity to all. In the case of the
food industry, these are notably anything containing salt,
CORN. See CEREALS SCIENCE AND TECHNOLOGY. especially low-pH products. There was, therefore, a de-
mand by industry to develop more corrosion-resistant ma-
terials and these are finding increasing use in the food in-
CORROSION AND FOOD PROCESSING dustry for certain specific processing operations.
Nickel chromium
iron alloys
Add
sulfur to Duplex
selenium for stainless
machinability Increased
Add niobium Add chromium chromium steels (329)
and nickel (corrosion lower nickel
and titanium resistance
to reduce for strength for special
and oxidation reduced) properties
sensitization
resistance
Add copper,
Add titanium titanium, aluminum, Precipitation
to reduce lower nickel for hardening
sensitization precipitation stainless
hardening (corrosion steels
Add resistance reduced)
molybdenum for
pitting resistance Add
manganese and
Lower carbon nitrogen, lower
to reduce nickel for higher
sensitization strength (corrosion
Add more resistance reduced
molybdenum for
pitting
Add nickel, resistance Austenitic
Nickel, molybdenum, iron, nickel,
chromium, iron copper, niobium manganese
(molybdenum, for corrosion nitrogen,
copper, resistance stainless steels
niobium) alloys in reducing
environments
Figure 2. Outline of some compositional modifications of 18/8 austenitic stainless steel to produce
special properties. Source: Ref. 2.
Still further increases in the three aforementioned alloying minium Plant and Vessel Company (now APV pic) to ex-
elements result in the nickel alloys. (The classification of ploit the technique of welding this material for the fab-
an alloy is generally under the heading of the major con- rication of fermenting vessels in the brewing industry
stituent.) (5). Many of these original vessels are still in use in some
There are a large number of these alloys but those of of the smaller, privately owned breweries in the United
primary interest to the food industry are shown in Table 2 Kingdom.
together with their composition. In general terms, it will Although large fermenting vessels and storage tanks
be noted that the increase in nickel content is accompanied now tend to be fabricated from stainless steels, there is still
by an increase in chromium and molybdenum. As stated widespread use of aluminum for beer kegs, beer cans, and
previously, this element is particularly effective in pro- a miscellany of small-scale equipment where the resis-
moting corrosion resistance. tance of aluminum is such that it imparts no change or
Just like insurance, you get only what you pay for, and modification of flavor, even after prolonged storage.
generally speaking, the higher the corrosion resistance, While still used for holding vessels and some equipment
the more expensive the material. In fact, the differential when processing cider, wines, and perry, prolonged contact
between type 304 stainless steel and a high-nickel alloy is inadvisable because of the acidity of the sulfites em-
may be as much as 20 times, depending on the market ployed as preservatives for these productsinadvisable,
prices for the various alloying elements that fluctuate that is, unless the surface of the metal has been modified
widely with the supply and demand position. by anodizing or has been protected with a lacquer.
In the manufacture of preserves, aluminum is still em-
Aluminum ployed for boiling pans, the presence of sugar appearing to
inhibit any corrosion. In the field of apiculture, it has even
High-purity grades of aluminum (99.5%) and its alloys been used for making prefabricated honeycombs, which
still are preferred for some food and pharmaceutical ap- the bees readily accepted.
plications because of the reasonable corrosion resistance of Extensive use is made of aluminum and the alloys in
the metal. This resistance is attributable to the easy and the baking industry for baking tins, kneading troughs,
rapid formation of a thin, continuous, adherent oxide film handling equipment, etc.
on exposed surfaces. This oxide film, in turn, exhibits a In other areas of food manufacture and preparation, the
good corrosion resistance to many foodstuffs, and it is re- use of aluminum extends virtually over the whole field of
ported that fats, oils, sugar, and some colloids have an in- activitybutter, margarine, table oils, and edible fats,
hibitory or sealing effect on these films (3). meat and meat products, fish and shellfish, certain sorts
As aluminum salts formed by corrosion are colorless, of vinegar, mustards, spices; the list is almost endless.
tasteless, and claimed to be nontoxic, the metal is easy to No mention has so far been made of the application of
clean, inexpensive, and light and has a high thermal con- this metal in the dairy industry, and indeed it still has
ductivity. It still is used quite extensively in certain areas limited application mostly in the field of packaging, eg, bot-
of food manufacture and distribution. However, in recent tle caps, wrapping for cheese, butter, carton caps for yo-
years, the claim of nontoxicity is being questioned as a gurt, cream.
high dietary incidence has been implicated in Alzheimer's It will be appreciated that the uses of aluminum in the
disease (senile dementia) with compounds of aluminum food industry so far mentioned have tended to be for equip-
(aluminosilicates) being found in the brain tissue of suf- ment used in batch operation, hand utensils, and packag-
ferers (4). However, the case is far from proven, and it is ing. There are probably three major factors that have mit-
not clear if the increased levels of aluminosilicates are due igated against its more widespread use, not only in the
to a high intake of aluminum per se or other factors such dairy industry but in brewing and many other branches of
as a dietary deficiency of calcium. food processing.
For many years, aluminum was used extensively for
containment vessels in the diary and brewing industry, 1. Modern, highly automated plants operating on a con-
and it was Richard Seligman who founded the then Alu- tinuous or semicontinuous basis employ a wide va-
Table 2. Composition of Some of the More Commonly Used Wrought Super Stainless Steels and Nickel Alloys
Composition (%)
Alloy UNS no. Carbon Silicon Manganese Chromium Nickel Molybdenum Others
904L N08904 0.02 0.70 2.0 19.0-21.0 24.0-26.0 4.2-4.7 Cu 1.2-1.7
Avesta S31254 0.02 0.80 2.0 19.5-20.5 17.5-18.5 6.0-6.5 Cu 0.5-1.0, N 0.18-0.22
254 SMO
Incoloy825 N08825 0.05 0.50 1.0 19.5-23.5 38.0-46.0 2.5-3.5 Al 0.2, Ti 0.6-1.2
Hastelloy G-30 N06030 0.03 0.08 1.5 28.0-31.5 BaI. 4.0-6.0 Co 5.0, Cu 1.0-2.4, Cb + Ta 0.3-1.5,
Fe 13.0-17.0
Inconel625 N06625 0.10 0.50 0.50 23.0-28.0 BaI. 8.0-10.0 Co 1.0, Fe 5.0, Al 0.4, Ti 0.4
Hastelloy C-276 N10276 0.02 0.08 1.0 14.5-16.5 15.0-17.0 W 3.0-4.5, V 0.35
Note: Unless indicated otherwise, all values are maxima.
riety of materials of construction. Because of the po- a wide range of food acids makes it a material par excel-
sition in the electrochemical series (to be discussed lence for this purpose.
later), aluminum and its alloys are susceptible to Cadmium, used as a protective coating for carbon steel
galvanic corrosion when coupled with other metals. nuts and bolts, was favored at one time. However, the high
2. The commercial availability of stainless steels and toxicity of the cadmium compounds has come under in-
their ease of fabrication, strength, ease of mainte- creasing scrutiny from many health regulatory bodies and
nance, appearance, and proven track record of reli- now cadmium-plated bolting is not permitted in food fac-
ability. tories. Indeed, Denmark and Sweden have totally banned
3. The fact that since modern plants operate on a semi- the import of cadmium-plated components into their coun-
continuous basis with much higher levels of fouling, tries, and many other countries are likely to follow suit.
cleaning regimes require strongly alkaline deter- Lead and lead-containing products are generally not ac-
gents to which aluminum has virtually zero corro- ceptable for food contact surfaces, although some codes of
sion resistance. practice permit the use of lead-containing solder for cap-
illary pipeline joints on water supplies and service lines.
Copper and Tinned Copper
Copper and tinned copper were used extensively in former SELECTING MATERIALS OF CONSTRUCTION
times because of their excellent thermal conductivity (8
times that of stainless steel), ductility, ease of fabrication, Designing equipment is a multidiscipline exercise involv-
and reasonable level of corrosion resistance. However, the ing mechanical engineers, materials-corrosion engineers,
demise of copper as a material of construction is largely stressing experts, draftsmen, etc. The corrosion engineer
attributable to the toxic nature of the metal and its cata- has an important role in this team effort, namely, to ensure
lytic activity in the development of oxidative rancidity in the materials specified will offer a corrosion resistance that
fats and oils. Even at the sub-part-per-million level, copper is just adequate for all the environmental conditions likely
in vegetable oils and animal fats rapidly causes the devel- to be encountered during normal operation of the equip-
opment of off-flavors. In equipment where high levels of ment. A piece of equipment that prematurely fails by cor-
liquid turbulence are encountered (eg, plate heat ex- rosion is as badly designed as one in which the materials
changer or high-velocity pipe lines) copper is subject to ero- have been overspecified. Unfortunately, all too often the
sion. Nevertheless, there is an area of the beverage indus- functional requirements for a piece of equipment are an-
try where copper is still the only acceptable material of alyzed in a somewhat arbitrary manner and all too often,
construction, ie, pot stills for Scotch and Irish whiskey pro- the basic cost of the material tends to outweigh other
duction. It is also used in the distillation of the spirits such equally important considerations (6).
as rum and brandy. Much old copper brewing equipment Figure 3 shows the primary criteria that must be con-
such as fermenting vessels and wort boilers is still in use sidered in the initial selection process.
throughout the world, and an interesting observation is
that even though the wort boilers in modern breweries are Corrosion Resistance. For any processing operation,
fabricated from stainless steel, they are still known as there will be a range of materials that will offer a
"coppers" and UK craftsmen fabricating stainless steel are corrosion resistance that is adequate (or more than
still known as coppersmiths. adequate) for a particular job. When considering cor-
rosion resistance, the operational environment is the
Titanium obvious one, but the other point must be whether the
material will also offer corrosion resistance to the
There are certain areas of the food industry, especially in chemicals used for cleaning and sanitizing.
equipment involving heat transfer, where stainless steels Cost. Many of the materials originally considered will
are just not capable of withstanding the corrosive effects be eliminated on the grounds of their high cost. For
of salty, low-pH environments. Food processors are in- example, there is no point in considering a high-
creasingly accepting the use of titanium as an alternative, nickel alloy when a standard 300 series stainless
in the full knowledge that it offers corrosion immunity to steel at a lower cost will be perfectly satisfactory.
the more aggressive foodstuffs and provides a long-term
solution to what was an on-going problem with stainless
steels. Titanium is a light metal, the density of which is Cost
almost half that of stainless steels. Although relatively ex- Corrosion
resistance i Availability
pensive (6-7 times the cost of stainless steel), being a low-
density material offsets this price differential for the raw
material by almost half. It is ductile and fabricable using
\ * /
normal techniques, although welding it does require a high Maintenance >* Material ** Strength
degree of expertise.
Other Metals
/ \
Appearance Fabricability
Tin, in the form of tin plate, is used extensively in the can-
ning industry, where its long-term corrosion resistance to Figure 3. Materials selection criteria.
Availability. Availability is a less obvious feature of Ore Blast Rolling
the material selection process. Many steel producers mine furnace mill
will require a minimum order of, say, 3 tons for a
nonstandard material. Clearly, the equipment man-
ufacturer is not going to buy this large quantity when
the job that is to be done may only require the use of
one ton of material.
Strength. Strength is a factor that is taken into ac-
count at the design stage but, as with all the others,
cannot be considered in isolation. For example, many
of the new stronger stainless steels, although more Rain, snow Car
Rust and salt manufacturer
expensive on a ton-for-ton basis than conventional
stainless steels, are less expensive when considered
Figure 4. Extractive metallurgy in reverse.
on a strength/cost ratio.
Fabricability. There is little point in considering ma-
terials that are either unweldable (or unfabricable)
chemical process. It should be noted that the "aqueous"
or can be welded only under conditions more akin to
component of the system may be present in only trace
a surgical operating theater than a general engineer-
quantities (eg, present as moisture); the classical example
ing fabrication shop.
is the corrosion of steel by chlorine gas. In fact, steel is not
Appearance. Appearance may or may not be an im- corroded by chlorine since steel is the material used for
portant requirement. Equipment located outside storing liquid chlorine. However, in the presence of even
must be resistant to environmental weathering and trace quantities of moisture, chlorine rapidly attacks steel
therefore may require the application of protective and, for that matter, most metals.
sheathing, which could double the basic material The corrosion of metals involves a whole range of fac-
cost. tors. These may be chemical, electrochemical, biological,
Maintenance. Is the equipment to be essentially metallurgical, or mechanical, acting singly or conjointly.
maintenance-free or is some maintenance, such as Nevertheless, the main parameter governing corrosion of
periodic repainting, tolerable? How long will the metals is related to electrochemistry. Electrochemical prin-
equipment operate without the need for major ser- ciples therefore are the basis for a theoretical understand-
vicing? ing of the subject. In fact, electrochemical techniques are
now the standard method for investigating corrosion al-
When all these interrelated criteria have been consid- though the standard "weight loss" approach still provides
ered, the long list of possible starters will have been re- invaluable data. It is not proposed to discuss in depth the
duced to maybe one or two. Also, somewhere through the electrochemical nature of corrosion but should further in-
selection process some of those materials initially rejected formation be required, several excellent texts are available
because, for example, of their high cost, may have to be (7,8).
reconsidered because of other factors.
Forms of Corrosion
TYPES OF CORROSION Wet corrosion can be classified under any of eight head-
ings, namely:
Defining Corrosion
Before embarking on a discussion of the various forms of Galvanic or bimetallic corrosion
corrosion, it is worthwhile considering exactly what cor- Uniform or general attack
rosion is. There are several definitions of corrosion. For Crevice corrosion
example, Fontant (7) defines it as extractive metallurgy in Pitting corrosion
reverse using the diagram, shown in Figure 4, to illustrate Intergranular corrosion
the point.
Stress corrosion cracking
A more general and descriptive definition is "it is the
deterioration or destruction of a material through inter- Corrosion fatigue
action with its environment." This covers all materials of Selective corrosion (castings and free-matching
construction including rubber and plastics as well as stainless steels)
metal. However, the primary object of this article is to deal
with corrosion of metals, in particular stainless steels, and Galvanic Corrosion. When two dissimilar metals (or al-
how this corrosion can be classified. loys) are immersed in a corrosive or conductive solution,
There are two basic forms of corrosionwet corrosion an electrical potential or potential difference usually exists
and dry corrosion. Dry corrosion is concerned with the ox- between them. If the two metals are electrically connected,
idation of metals at high temperature and clearly outside then, because of this potential difference, a flow of current
the scope of this text. Wet corrosion occurs in aqueous so- occurs. As the corrosion process is an electrochemical phe-
lutions or in the presence of electrolytes and is an electro- nomenon and dissolution of a metal involves electron flow,
the corrosion rates for the two metals is affected. Gener- usually avoided in plant construction and in the author's
ally, the corrosion rate for the least corrosion resistant is experience, few cases have been encountered. Probably the
enhanced while that of the more corrosion resistant is di- most common form of unintentional galvanic corrosion is
minished. In simple electrochemical terms, the least resis- on service lines where brass fittings are used on steel
tant metal has become anodic and the more resistant cath- pipelinesthe steel suffering an increase in corrosion rate
odic. This, then, is galvanic or dissimilar metal corrosion. at the bimetallic junction.
The magnitude of the changes in corrosion rates de- One of the worst bimetallic combinations is aluminum
pends on the so-called electrode potentials of the two met- and copper. An example of this is in relation to aluminum
als; the greater the difference, the greater the enhance- milk churns used to transport whey from Gruyere cheese
ment or diminution of the corrosion rates. It is possible to manufacture (in Switzerland), where copper is used for the
draw up a table of some commercial alloys that ranks them cheesemaking vats and the whey picks up traces of this
in order of their electrochemical potential. Such a table is metal. The effect on the aluminum churns which are in-
known as the galvanic series. A typical one as shown in ternally protected with lacquer that gets worn away
Table 3 is based on work undertaken by the International through mechanical damage is pretty catastrophic.
Nickel Company (now INCO Ltd.) at their Harbor Island, Another, somewhat unique, example of galvanic corro-
NC, test facility. This galvanic series relates to tests in un- sion is related to a weld repair on a 304 stainless-steel
polluted seawater, although different environments could storage vessel. Welding consumables containing molybde-
produce different results and rankings. When coupled, in- num had been employed to effect the repair, and although
dividual metals and alloys from the same group are un- it is most unusual for the potential difference between mo-
likely to show galvanic effects that will cause any change lybdenum and nonmolybdenum containing stainless steels
in their corrosion rates. to be sufficient to initiate galvanic corrosion, the environ-
The problem of dissimilar metal corrosion, being rela- mental factors in this particular case were obviously such
tively well understood and appreciated by engineers, is that corrosion was initiated (Fig. 5). As stated, this is
somewhat unique and it is not uncommon for 316 welding
consumables to be used for welding 304 stainless steel with
no adverse effects. As a practice, however, it is to be dep-
Table 3. The Galvanic Series of Some Commercial Metals
and Alloys in Clean Seawater recated and the correct welding consumables should al-
ways be employed.
Platinum Not all galvanic corrosion is bad; indeed, galvanic cor-
Gold rosion is used extensively to protect metal and structures
Graphite
by the use of a sacrificial metal coating. A classic example
Titanium
Noble or Silver is the galvanizing of sheet steel and fittings, the zinc coat-
cathodic Chlorimet 3 (62 Ni, 18 Cr, 18 Mo) ing being applied not so much because it does not corrode,
Hastelloy C (62 Ni, 17 Cr, 15 Mo) but because it does. When the galvanizing film is damaged,
18/8 Mo stainless steel (passive) the zinc galvanically protects the exposed steel and inhib-
18/8 stainless steel (passive) its rusting. Similarly, sacrificial anodes are fitted to do-
Chromium stainless steel 11-30% Cr (passive) mestic hot water storage tanks to protect the tank.
Inconel (passive) (80 Ni, 13 Cr, 7 Fe)
Nickel (passive) Uniform or General Attack. As the name implies, this
Silver solder
form of corrosion occurs more or less uniformly over the
Monel (70 Ni, 30 Cu)
Cupronickels (60-90 Cu, 40-10 Ni) whole surface of the metal exposed to the corrosive envi-
Bronzes (Cu-Sn)
Copper
Brasses (Cu-Zn)
Chlorimet 2 (66 Ni, 32 Mo, 1 Fe)
Hastelloy B (60 Ni, 30 Mo, 6 Fe, 1 Mn)
Inconel (active)
Nickel (active)
Tin
Lead
Lead-tin solders
18/8 Mo stainless steel (active)
18/stainless steel (active)
Ni-resist (high-Ni cast iron)
Chromium stainless steel, 13% Cr (active)
Cast iron
Active or Steel or iron
anodic 2024 aluminum (4.5 Cu, 1.5 Mg, 0.6 Mn)
Cadmium
Commercially pure aluminum (1100)
Figure 5. Galvanic corrosion of 304 stainless steel initiated by a
Zinc
316 weld deposit. Note the large pit associated with the weld splat-
ter.
ronment. It is the most common form of corrosion encoun- surfaces exposed to service fluids such as services side hot/
tered with the majority of metals, a classic example being cold water, cooling brines, which tend to be overlooked dur-
the rusting of carbon steel. Insofar as the corrosion occurs ing plant cleaning operations.
uniformly, corrosion rates are predictable and the neces- Much research work has been done on the geometry of
sary corrosion allowances built into any equipment. In the crevices and the influence of this on the propensity for the
case of stainless steels, this form of corrosion is rarely en- initiation of crevice corrosion (9). However, in practical
countered. Corrodents likely to produce general attack of terms, crevice corrosion usually occurs in openings a few
stainless steel are certain mineral acids, some organic ac- tenths of a millimeter or less and rarely is encountered
ids, and high-strength caustic soda at concentrations and where the crevice is greater than 2 mm (0.08 in.).
temperatures well in excess of those ever likely to be found Until the 1950s, crevice corrosion was thought to be due
in the food industry. The same remark applies to cleaning to differences in metal ion or oxygen concentration within
acids such as nitric, phosphoric, and citric acids, but not the crevice and its surroundings. While these are factors
for sulfuric or hydrochloric acids, both of which can cause in the initiation and propagation of crevice corrosion, they
rapid, general corrosion of stainless steels. Hence, they are are not the primary cause. Current theory supports the
not recommended for use, especially where corrosion view that through a series of electrochemical reactions and
would result in a deterioration of the surface finish of pro- the geometrically restricted access into the crevice, migra-
cess equipment. tion of cations, chloride ions in particular, occurs. This al-
The behavior of both 304 and 316 stainless steels when ters the environment within, with a large reduction in pH
subjected to some of the more common acids that are en- and an increase in the cations by a factor of as much as 10.
countered in the food industry is graphically illustrated in The pH value can fall from a value of, say, 7 in the sur-
Figure 6. These isocorrosion graphs, ie, lines that define rounding solution to as low as pH 2 within the crevice. As
the conditions of temperature and acid concentration that corrosion is initiated, it proceeds in an autocatalytic man-
will produce a constant corrosion rate expressed in mils ner with all the damage and metal dissolution occurring
(0.001 in.) or mm loss of metal thickness per year, are used within the crevice and little or no metal loss outside. The
extensively by corrosion engineers in the material selec- confined and autocatalytic nature of crevice corrosion re-
tion process when the form of corrosion is general attack. sults in significant loss of metal under the surface of site
They are of no value whatsoever when the corrosion mode of initiation. As a result, deep and severe undercutting of
is one of the other forms that will be defined, such as pitting the metal occurs (see Fig. 8). The time scale for initiation
or crevice corrosion. of crevice corrosion can vary from a few hours to several
months and, once initiated, can progress very rapidly.
Crevice Corrosion. This form of corrosion is an intense Stopping the corrosion process can be extremely difficult
local attack within crevices or shielded areas on metal sur- as it is necessary to remove all the trapped reactants and
faces exposed to corrosive solutions. It is characteristically completely modify the occluded environment. The diffi-
encountered with metals and alloys that rely on a surface culty of attaining this will be appreciated by reference to
oxide film for corrosion protection, eg, stainless steels, ti- Figure 8, where the entrance to the corroded region is only
tanium, aluminum. 0.5 mm (0.020 in.).
The crevices can be inherent in the design of the equip- While methods for combating the onset of crevice cor-
ment (eg, plate heat exchangers) or inadvertently created rosion can be deduced from the foregoing text, a reiteration
by bad design. Although crevice corrosion can be initiated of some of the more important precautions is not out of
at metal-to-metal surfaces (see Fig. 7), it is frequently en- place, viz:
countered at metal to nonmetallic sealing faces. Any non-
metallic material that is porous and used, for example,as Good-quality, crevice-free welded joints are always
a gasket, is particularly good (or bad!) for initiating this preferable to bolted joints
form of attack. Fibrous materials that have a strong wick-
ing action are notorious in their ability to initiate crevice Good equipment design (well-designed gasket seal-
attack. Similarly, materials that have poor stress relaxa- ing faces) that avoids unintentional crevices and does
tion characteristics, ie, have little or no ability to recover not permit the development of stagnant regions
their original shape after being deformed, are also crevice Frequent inspection of equipment and removal of
creators, as are materials that tend to creep under the surface deposits
influence of applied loads and/or at elevated tempera- Use of good-quality rubber gaskets rather than ab-
tures. Although used for gasketing, PTFE suffers both sorbent packings
these deficiencies. On the other hand, elastomeric mate-
Good gasket maintenance; replacement when hard-
rials are particularly good insofar as they exhibit elastic
ened or damaged
recovery and have the ability to form a crevice-free seal.
However, at elevated temperatures, many rubbers harden
and in this condition, suffer the deficiencies of many non- However, certain pieces of equipment are by virtue of their
elastomeric gasketing materials. design highly creviced. In such cases, it is necessary to rec-
Artificial crevices can also be created by the deposition ognize the potential corrosion risk and select the materials
of scale from one of the process streams to which the metal of construction that will resist the initiation of crevice cor-
is exposed. It is necessary, therefore, to maintain food pro- rosion by the environment. Similarly, cleaning and sanitiz-
cessing equipment in a scale-free condition, especially on ing regimes must be developed to avoid the onset of attack.
Hydrochloric acid Type 304 Type 316
Temperature (0C)
In the case of stainless steels, although there are sev- Other environmental factors such as temperature and
eral ionic species that will initiate the attack, by far the the oxygen or dissolved air content of the process stream
most common are solutions containing chloride. The pres- all play a role in the corrosion process.
ence of salt in virtually all foodstuffs highlights the prob- Because the presence of oxygen is a prerequisite for the
lem. Low pH values also enhance the propensity for initi- onset of crevice corrosion (and many other forms of attack),
ation of attack. in theoretical terms complete removal of oxygen from a
small and sporadically distributed over the metal surface
(Fig. 9) or extremely close together, close enough, in fact,
to give the appearance of the metal having suffered from
general attack.
In the case of stainless steels, environments that will
initiate crevice corrosion will also induce pitting. As far as
the food industry is concerned, it is almost exclusively
caused by chloride containing media, particularly at low
pH values.
Many theories have been developed to explain the cause
of initiation of pitting corrosion (10), and the one feature
they have in common is that there is a breakdown in the
passive oxide film. This results in ionic migration and the
development of an electrochemical cell. There is, however,
no unified theory that explains the reason for the film
breakdown. Evans (11) for example, suggests that metal
dissolution at the onset of pitting may be due to a surface
Figure 7. Crevice corrosion at the interplate contact points of a scratch, an emerging dislocation or other defects, or ran-
heat-exchanger plate. dom variations in solution composition. However, propa-
gation of the pit proceeds by a mechanism similar to that
occurring with crevice corrosion. Like crevice corrosion, the
pits are often undercut and on vertical surfaces may as-
sume an elongated morphology due to gravitational effects
(Fig. 10).
The onset of pitting corrosion can occur in a matter of
days but frequently requires several months for the devel-
opment of recognizable pits. This makes the assessment of
the pitting propensity of a particular environment very dif-
ficult to determine, and there are no short-cut laboratory
testing techniques available. Methods and test solutions
are available to rank alloys; the best known and most fre-
quently quoted is ASTM Standard G48 (12), which em-
ploys 6% ferric chloride solution. Another chemical method
involving ferric chloride determines the temperature at
Figure 8. Photomicrograph of a section through a site of crevice
corrosion. Note the deep undercutting which is typical of chloride-
induced attack on stainless steel.
Type Minimum
cracking
time
Type
Type
Figure 13. Composite curves illustrating the relative resistance Figure 14. Stress corrosion cracking of iron, chromium, nickel
to stress corrosion cracking of some commercial stainless steel in alloysthe Copson curve. Data points have been omitted for clar-
a specific test solution. ity.
commercially viable proposition. Because of their low car- sient pressure peaks, frequent stop-start operations, dead-
bon content, typically 0.01-0.02%, the original problems ending of equipment linked to a filling machine, etc.
associated with welding ferritic stainless steels and chro- Generally speaking, fatigue cracks are straight, without
mium carbide precipitation have been overcome. The al- branching and without ductile metal distortion of the
loys are almost twice as strong as the austenitic stainless material adjacent to the crack. The one characteristic of
steels and are ductile and weldable. From a general cor- fatigue cracks is that the crack face frequently has a
rosion standpoint, they are comparable with, or marginally series of conchoidal markings that represent the stepwise
superior to, their 300 series equivalent; but from an SCC advance of the crack front (Fig. 16). Although, as stated,
standpoint in test work and from field experience, they of- corrosion fatigue cracks are generally straight and un-
fer a resistance orders of magnitude better. branched, where fatiguing conditions pertain in a poten-
Also now available are fully ferritic stainless steels such tially corrosive environment, the influence of the corrosive
as grade 444, which contains 18% chromium and 2% mo- component may be superimposed on the cracks. This can
lybdenum. This alloy contains carbon at the 0.001% level lead to branching of the cracks, and in the extreme case,
and therefore does not suffer the problems of welding that the crack may assume a highly branched morphology
were encountered with the original ferritic steels. Fur- which is almost indistinguishable from stress corrosion
thermore, stabilizing elements such as titanium and nio- cracking. It is only when the crack face is examined under
bium are also alloying additions that minimize the ten- high-power magnification that it is possible to categorize
dency for intergranular chromium carbide formation. The the failure mode. An example of this is shown in Figure
main disadvantage of these materials is their susceptibil- 17, which has all the features of stress corrosion cracking
ity to grain growth during welding (Fig. 15), which makes but the scanning electron micrograph (Fig. 18) clearly
them extremely sensitive to fracture even at room tem- shows the stepwise progression of the crack front.
perature. Welding sections thicker than 3 mm (1/8 in.) are The site for initiation of corrosion fatigue is frequently
not regarded as a practical proposition, and, therefore, a discontinuity in the metal section of the component. This
their use tends to be limited to tubing. may be, for example, a sharp change in diameter of a shaft
where inadequate radiusing of the diametric change re-
Corrosion Fatigue. Fatigue is not a form of corrosion in sults in a high cycle stress level through shaft rotation and
the accepted sense as there is no loss of metal, but can be thus an initiation point for fatigue. A corrosion pit, which
associated with other forms of localized attack. Because under cyclic loading will have a high stress-level associa-
pure fatigue is an in vacua phenomenon, a more correct tion, can also act as a nucleation site (epicenter) for fatigue
term is corrosion fatigue or environmental cracking, which failure. Because of the corrosive element, it is sometimes
is the modern expression and takes into account cracking difficult to establish whether the pit and associated cor-
where the corrosive factor has played a major role on the rosion were the initiating mechanism for the cracking or
crack morphology. the result of corrosion superimposed on a crack, the frac-
The primary cause of corrosion fatigue is the application
of fluctuating pressure loads to components that, while of
adequate design to withstand normal operating pressures
eventually fail under the influence of cyclic loading. The
components can be of extremely rigid construction such as
a homogenizer block or of relatively light construction such
as pipework. There are many potential sources of the fluc-
tuating pressure, the most common of which are positive-
displacement pumps (eg, homogenizer or metering
pumps), rapid-acting on-off valves that will produce tran-
Figure 15. Photomicrograph of a weld deposit on a ferritic stain- Figure 16. Fatigue cracking of a l-in.-diameter stainless steel
less steel. Compare the size of grains in the weld with those in the bolt showing the characteristic conchoidal striations on the crack
parent material on the left. face.
provision should be made to incorporate pulsation damp-
ers to smooth out the pressure peaks and minimize the risk
of fatigue failures.
Figure 20. Corroded pump impeller (above) and valve body (be- Figure 21. Free machining and nonfree machining bolts after im-
low) caused by tomato ketchup. Note the pocklike corrosion sites. mersion in a mildly acidic environment.
stress corrosion cracking. Therefore, this form of damage not be a continuous corrosion path. However, one of the
is frequently also present (Fig. 20). products of corrosion in acidic media will be hydrogen sul-
Depending on the method used to make the casting, the fide, which has a profound effect on the corrosivity of even
surface of the castings can be chemically modified, which dilute mineral acids, causing attack of the austenitic ma-
reduces the corrosion resistance. Small components are trix.
usually cast by either the shell molding process or pro- In the case of wrought materials, in particular bar
duced as investment castings. In the shell molding process, stock, the sulfide inclusions are present as semicontinuous
the sand forming the mold is bonded together with an or- stringers and can suffer so-called end-grain attack in
ganic resin that carbonizes when the hot metal is poured. mildly corrosive media.
This results in the metal adjacent to the mold having an Stainless-steel nuts and bolts, which are produced on
enhanced carbon level with the formation of intergranular automatic thread-cutting machines, are invariably made
carbide precipitates and hence, a susceptibility to inter- from free-cutting materials. Figure 21 illustrates the dif-
granular attack and other forms such as crevice, pitting, ference in corrosion resistance of a bolt made from this and
and stress corrosion cracking. Methods of overcoming this a nonfree machining 316. Both bolts were exposed to the
include solution annealing or machining off the carburized same mildly acidic environment.
skin of metal. When specifying materials of construction, quite clearly
With investment castings, the mold is made of zircon due cognizance of this difference must be recognized. Any
sand (zirconium silicate), and fired at a high temperature components turned from bar stock which are likely to come
to remove all traces of organic material and wax that is into contact with potentially corrosive environments
used as a core in the moldmaking process. They do not, should always be specified in 316 and not in the free ma-
therefore, have this carburized layer and offer a much bet- chining, sulfur-containing variant.
ter resistance to surface corrosion.
Free-Machining Stainless Steels. Stainless steels are no-
CORROSION OF SPECIFIC ENVIRONMENTS
toriously difficult to machine, especially turning, not so
much because they are hard, but because the swarf tends
to form as continuous lengths that clog the machine and From a corrosion standpoint, the environments likely to be
to weld to the tip of the machine tools. One method of over- encountered in the food industry that may cause prema-
coming this is to incorporate a small amount, typically ture equipment failure may be classified under main head-
0.2%, of sulfur or selenium in the alloy. These elements ings:
react with the manganese to form manganese sulfide or
selenide, which, being insoluble in the steel, forms as dis- Noncorrosive
crete pools in castings or as elongated, continuous string- Mildly corrosive
ers in, say, wrought bar. The effect of the sulfide inclusions Highly corrosive
is to cause the material to form chips rather than long Service fluids
strings of swarf when being machined. Both manganese Alkaline detergents
sulfide and selenide have virtually zero corrosion resis-
tance to dilute mineral acids or other corrosive media. Acidic detergents
Thus, the free-cutting variants have a much lower corro- Sanitizing agents
sion resistance than their designation would imply. Indeed,
some believe that the addition of sulfur to a type 316 ma- Noncorrosive Foodstuffs
terial will offset the beneficial effect of the alloying addi- In general terms, natural foodstuffs such as milk, cream,
tion of molybdenum. As stated, the sulfide inclusions will natural fruit juices, and whole egg do not cause corrosion
occur in castings as discrete pools, and therefore there will
Figure 20. Corroded pump impeller (above) and valve body (be- Figure 21. Free machining and nonfree machining bolts after im-
low) caused by tomato ketchup. Note the pocklike corrosion sites. mersion in a mildly acidic environment.
problems with 304 or 316 stainless steels. Prepared food- Highly Corrosive Foodstuffs
stuffs to which there is no added salt such as yogurt, beer, The list of foodstuffs falling in this category is almost
ice cream, wines, spirits, and coffee also fall within this endlessgravies, ketchups, pickles, salad dressings, but-
classification. For general storage vessels, pipelines, ter, and margarinein fact, anything to which salt has
pumps, fittings or valves, grade 304 is perfectly satisfac- been added at the 1-3% level or even higher. Also within
tory. However, for plate heat exchangers that are highly this category must be included cheese salting brine and
creviced and therefore prone to crevice corrosion, grade other brines used in the preservation of foodstuffs that
316 frequently is employed. This offers a higher degree of undergo pasteurization to minimize bacterial growth on
protection against some of the more acidic products such food residues remaining in the brine. Although these
as lemon juice, which may contain small quantities of salt brines are usually too strong to support the growth of com-
and also provides a higher level of integrity against cor- mon organisms, salt resistant strains (halophiles) are the
rosion by service liquids and sanitizing agents. major problem.
It is quite common to use sulfur dioxide or sodium bi- Low-pH products containing acetic acid are particularly
sulfite for the preservation of fruit juices and gelatin so- aggressive from a corrosion standpoint, but selection of
lutions and in such cases, storage vessels always should be materials for handling these products depends to a great
constructed from 316. Although the sulfur dioxide is non- extent on the duty involved.
corrosive at ambient temperature in the liquid phase, as a When trying to define the corrosion risk to a piece of
gas contained in significant quantities within the head equipment handling potential corrodents, several factors
space in a storage tank it tends to dissolve in water drop- come into play. While temperature, oxygen content, chlo-
lets on the tank wall. In the presence of air, the sulfurous ride content, and pH are the obvious ones, less obvious and
acid that forms is oxidized to sulfuric acid at a concentra- equally important is contact time. All three main forms of
tion high enough to cause corrosion of 304 but not of 316. corrosion induced in stainless steels (crevice, pitting, and
Mildly Corrosive Foodstuffs stress corrosion cracking) have an induction period before
the onset of corrosion. This can vary from a few hours to
This category of foodstuffs covers products containing rela- several months depending on the other operative factors.
tively low levels of salt and where pH values are below 7. In a hypothetical situation where stainless steel is exposed
Examples include glucose/fructose syrups and gelatin, the to a potentially corrosive environment, removal of the steel
production of which may involve the use of hydrochloric and removal of the corrodents will stop the induction and
acid. For storage vessels, pipelines, fittings, and pumps, the status quo is established. On repeating the exposure,
grade 316 has established a good track record, and boiling the induction period is the same. In other words, the in-
pans in this grade of steel are perfect for long and satis- dividual periods the steel spends in contact with the cor-
factory service. The corrosion hazards increase however in rodent are not cumulative and each period must be taken
processing operations involving high temperatures and in isolation.
where the configuration of the equipment is such as to con- When the contact period is short, temperatures are low
tain crevices, especially when the product contains dis- and a rigorous cleaning regime is implemented at the end
solved oxygen. For example, multistage evaporators oper- of each processing period, 316 stainless steel will give ex-
ating on glucose syrup will usually have the first stage, cellent service. However, where temperatures are high and
where temperatures may approach 10O0C (2120F), con- contact periods are long, the corrosion process may be ini-
structed in a super stainless steel such as 904L. Subse- tiated. This is especially so in crevices such as the inter-
quent effects where temperatures are lower and where the plate contact points on a plate heat exchanger where, al-
product has been deoxygenated may be fabricated in grade beit at a microscopic level, corrodents and corrosion
316 stainless steel. products are trapped in pits or cracks. Geometric factors
As previously indicated, it is common practice to use may prevent the complete removal of this debris during
sulfur dioxide as a preservative in dilute gelatin solutions cleaning and under such circumstances, the corrosion pro-
during storage prior to evaporation. In some cases, excess cess will be ongoing.
hydrogen peroxide will be added to neutralize the sulfur Because of the perishable nature of foodstuffs, storage
dioxide immediately before concentration. This can have a is rarely for prolonged periods or at high temperatures,
catastrophic effect on the 300 series stainless steels and and regular, thorough cleaning tends to be the norm. The
indeed on even more highly alloyed metals such as 904L, one exception to this is buffer storage vessels for holding
because of the combined effect of the chlorides present with "self-preserving" ketchup and sauces. For such duties, an
the excess hydrogen peroxide. Because of this, it is a more alloy such as 904L, Avesta 254 SMO, or even Inconel 625
acceptable practice to make the peroxide addition after may be required.
rather than before evaporation. While all the foregoing applies to general equipment,
Gelatin for pharmaceutical end use is subject to UHT the one exception is plate heat exchangers. Their highly
treatment to ensure sterility. This will involve heating the creviced configuration and the high temperatures em-
gelatin solutions to 1350C (2850F) and holding at that tem- ployed render them particularly susceptible. Plates made
perature for a short period of time. Plate heat exchangers from grade 316 have a poor track record on these types of
are used extensively for this duty. Although plates made duties. Even the more highly alloyed materials do not offer
from 316 stainless steel give a reasonable life of typically complete immunity. The only reasonably priced material
2-3 years, a corrosion resistant alloy with an enhanced- that is finding increased usage in certain areas of food pro-
level molybdenum is to be preferred. cessing is titanium.
The fact that butter and margarine have been included the regulatory factor. Even then, it is virtually impossible
in this group of corrodents requires comment. Both these to define the composition of a "safe" water, but as a general
foodstuffs are emulsions containing typically 16% water guideline, water with less than 100 ppm chloride is un-
and 2% salt. A fact not often appreciated is that the salt is likely to initiate crevice corrosion of type 316 stainless
dissolved in the water phase, being insoluble in the oil. steel while a maximum level of 50 ppm should be used with
From a corrosion standpoint, therefore, the margarine or type 304.
butter may be regarded as a suspension of 12% salt solu- Cooling tower water systems are frequently overlooked
tion and as such is very corrosive to 316 stainless steel at as a potential source of corrodents. It must be appreciated
the higher processing temperatures. The only mitigating that a cooling tower is an evaporator, and although the
feature that partly offsets their corrosivity is the fact that supply of makeup water may contain only 25 ppm chloride,
the aqueous salty phase is dispersed in an oil rather than over a period of operation this can increase by a factor of
the reverse and that the oil does tend to preferentially wet 10 unless there is a routine bleed on the pond.
the steel surface and provide some degree of protection. Water scale deposits formed on heat-transfer surfaces
However, the pasteurizing heat exchanger in margarine should always be removed as part of the routine mainte-
rework systems invariably has titanium plates as the life nance schedule. Water scale deposits can accumulate chlo-
of 316 stainless steel is limited and has been known to be ride and other soluble salts that tend to concentrate, pro-
as little as 6 weeks. ducing higher levels in contact with the metal than
indicated by the water composition. Furthermore, water
Corrosion by Service Fluids scale formed on a stainless-steel surface provides an ideal
base for the onset of crevice corrosion.
Steam. Because it is a vapor and free from dissolved As stated previously, potable water supplies usually
salts, steam is not corrosive to stainless steels. Although have a residual free chlorine content of 0.2 ppm. Where
sometimes contaminated with traces of rust from carbon installations have their own private wells, chlorination is
steel steam lines, in the author's experience no case of cor- undertaken on site. In general terms, the levels employed
rosion due to industrial boiler steam ever has been en- by the local water authorities should be followed and over-
countered. chlorination avoided. Levels in excess of 2 ppm could ini-
tiate crevice corrosion.
Water. The quality and dissolved solids content of water
supplies varies tremendously, with the aggressive ionic Cooling Brines. Depending on the industry, these can be
species, chloride ions, being present at levels varying be- anything from glycol solutions, sodium nitrate/carbonate,
tween zero, as found in the lakeland area of England, to or calcium chloride. It is the latter which are used as a 25%
several hundred parts per million, as encountered in solution that can give rise to corrosion of stainless steel
coastal regions of Holland. It is also normal practice to unless maintained in the ideal condition, especially when
chlorinate potable water supplies to kill pathogenic bac- employed in the final chilling section of plate heat exchang-
teria with the amount added dependent on other factors ers for milk and beer processing. However, by observing
such as the amount of organic matter present. However, certain precautions, damage can be avoided.
most water supply authorities aim to provide water with The corrosion of stainless steels by brine can best be
a residual chlorine content of 0.2 ppm at the point of use. represented as shown in Figure 22. It will be noted that
Well waters also vary in composition depending on the geo- an exponential rise in corrosion rate with reducing pH oc-
graphical location, especially in coastal regions where the curs in the range pH 12-7. The diminution in number of
chloride content can fluctuate with the rise and fall of the pits occurring in the range pH 6-4 corresponds with the
tide. change in mode of attack, ie, from pitting to general cor-
What constitutes a "good" water? From a general user rosion. It will be seen that ideally the pH of the solution
viewpoint, the important factor is hardness, either tem- should be maintained in the region 14-11. However, cal-
porary hardness caused by calcium and magnesium bicar- cium chloride brine undergoes decomposition at pH values
bonates that can be removed by boiling, or permanent higher than 10.6:
hardness caused by calcium sulfate that can be removed
by chemical treatment. While hardness is a factor, chloride
content and pH probably are the most important from a CaCl2 + 2NaOH -> Ca(OH)2I + 2NaCl
corrosion standpoint.
What can be classed as a noncorrosive water supply Scale deposition occurs and heat-transfer surfaces become
from a stainless-steel equipment user? Unfortunately, fouled with calcium hydroxide scale. Furthermore, the
there are no hard-and-fast rules that will determine scale that forms traps quantities of chloride salts that can-
whether corrosion of equipment will occur. As has been re- not be effectively removed and remain in contact with the
peatedly stated throughout this article, so many factors equipment during shutdown periods. This is particularly
come into play. The type of equipment, temperatures, con- important in equipment such as plate heat exchangers
tact times, etc all play a role in the overall corrosion pro- that are subjected to cleaning and possibly hot-water ster-
cess. Again, as has been stated before, the most critical ilization cycles at temperatures of 8O0C (1760F) or higher.
items of equipment are those with inherent crevices The other aspect, nonaeration, is equally important. Air
evaporators and plate heat exchangers among others. De- contains small quantities of carbon dioxide that form a
fining conditions of use for this type of equipment will be slightly acidic solution when dissolved in water. This has
Weight loss (mg/dm2/day)
Number of pits/sq dm
Temperature (0C)
Figure 22. The effect of pH and temperature on the pitting of stainless steel by brine.
the effect of neutralizing the buffering action of any alka- cate solution to ensure that any brine residues are
line components in the brine: rendered alkaline.
In plate heat exchangers and similar equipment,
2NaOH + CO2 -> Na2CO3 + H2O make sure that stainless-steel brine section compo-
Na2CO3 + CaCl2 - 2NaCl + CaCO3I nents remain free of scale.
When shutting down the plant after a cleaning run,
or it is advisable to leave the section full with a dilute
(1/4%) caustic solution. Before startup, this should be
Ca(OH)2 + CO2 - CaCO3I + H2O drained and residues flushed out prior to reintro-
ducing brine.
Therefore, the pH of the brine decreases and assumes
a value of about pH 6.5, which is the region where pitting When operating conditions prevailing in a plant do not
incidence is highest. Furthermore, scale deposits of cal- permit such a disciplined cleaning, operating, and shut-
cium carbonate are laid down on heat-transfer surfaces, down procedure, only two materials can be considered for
creating the problems referred to above. the brine section of a plate heat exchanger. These are Has-
The precautions to be observed when using brine cir- telloy C-276 or titanium. The corrosion resistance of both
cuits are of these materials is such that cleaning and sanitizing of
the product side of the heat exchanger can be carried out
Ensure correct pH control and maintain in the range without removing the brine. Although both are more ex-
pH 9.5-10. pensive than stainless steels, especially Hastelloy C-276,
Eliminate aeration. In particular, make certain that the flexibility of plant operation which their use permits
the brine return discharge line is below the surface could offset their premium price.
in the storage tank during running and that the
method of feeding brine from the tank does not cause Alkaline Detergents
vortexing with resultant air entrainment. Baudelot
type evaporators cause aeration of the chilling liquor Supplied to food processing plants either as bulk ship-
and should never be used on brine circuits. ments of separate chemicals or as carefully preformulated
When cleaning and sterilizing the brine section of a mixtures, the composition of alkaline detergent formula-
pasteurizer, flush out all brine residues until the tions can vary widely in accordance with individual pref-
rinse water is free of chloride. As an added precau- erence or the cleaning job to be done. The detergents do,
tion, it is advisable to form a closed circuit and cir- however, generally include some or all of the following com-
culate a 1/4-1/2% caustic soda or sodium metasili- pounds:
Sodium hydroxide It is always preferable to use alkaline cleaning before
Sodium polyphosphate the acid cycle to minimize the risk of interacting the
acid with any chloride salts and, therefore, minimize
Sodium metasilicate
the formation of hydrochloric acid.
Sodium carbonate
It is inadvisable to introduce an acid into a UHT ster-
ilizing plant when it is at full operating temperature
Additionally, it is not uncommon to find that a selection (14O0C/2850F) as part of a "clean-on-the-run" regime.
of sequestering agents such as EDTA and any of the many Nitric acid, which is a strong oxidizing agent, will
available wetting agents also may be present in the for- attack certain types of rubber used as gaskets and
mulations. seals. As a general guideline, concentrations should
None of these compounds are corrosive to stainless not exceed 1% and temperature 650C (15O0F), al-
steels at the concentrations and temperatures used by the though at lower concentrations, the upper recom-
food industry for cleaning. Indeed, 316 stainless steel is mended temperature is 9O0C (1950F).
unaffected by concentrations of sodium hydroxide as high
as 20% at temperatures up to 16O0C (32O0F). They can,
therefore, be used with impunity at their usual maximum Another acid that is finding increasing use in the food in-
concentration of 5%, even in ultra-high-temperature dustry for removing water scale and other acid-soluble
(UHT) operation where temperatures can rise to 14O0C scales is sulfamic acid. Freshly prepared solutions of up to
(2840F). 5% concentration are relatively innocuous to stainless
Companies have reported that some of these prefor- steels but problems may arise when CIP systems incor-
mulated alkaline detergents cause discoloration of the porating recovery of detergents and acids are employed.
equipment. Sulfamic acid will undergo hydrolysis at elevated tempera-
The discoloration starts as a golden yellow, darkening tures to produce ammonium hydrogen sulfate
to blue through mauve and eventually black. It has been
established that this discoloration is caused by the EDTA NH2SO2OH + H2O -> NH4HSO4
sequestering agent, which complexes with traces of iron in
the water. It then decomposes under certain conditions of which behaves in much the same way as sulfuric acid. In
pH and temperature to form an extremely fine film of hy- situations where the use of this acid is contemplated, pro-
drated iron oxide, the coloration being interference colors longed storage of dilute solutions at elevated temperature
that darken as the film thickness increases. Although the is inadvisable, although at room temperature the hydro-
film is not aesthetically pleasing, it is in no way deleterious lysis is at a low rate.
and removing it by conventional cleaning agents is virtu-
ally impossible. Sanitizing Agents
Some alkaline detergents are compounded with chlo-
rine release agents such as sodium hypochlorite, salts of Terminology for the process of killing pathogenic bacteria
di- or trichlorocyanuric acid that form a solution contain- varies from country to country. In Europe, disinfection is
ing 200-300 ppm available chlorine at their usage preferred; in America, sanitizing. Regardless, the term
strength. Although the high alkalinity reduces the corro- should not be confused with sterilization, which is the pro-
sivity of these additives, generally speaking they should cess of rendering equipment free from all live food spoilage
not be employed on a regular basis at temperatures ex- organisms including yeasts, mold, thermophilic bacteria,
ceeding 7O0C (16O0F). and most importantly, spores. Sterilization with chemicals
is not considered to be feasible and the only recommended
Acidic Detergents procedure involves the circulation of pressurized hot water
at a temperature of not less than 14O0C (2850F).
Alkaline detergents will not remove the inorganic salts For sanitization, while hot water (or steam) is pre-
such as milkstone and beer-stone deposits frequently ferred, chemical sanitizers are extensively used. These
found in pasteurizers. For this, an acidic detergent is re- include noncorrosive compounds such as quaternary am-
quired and selection must be made with regard to their monium salts, anionic compounds, aldehydes, amphoter-
interaction with the metal. As was shown earlier, sulfuric ics, and potentially corrosive groups of compounds that
and hydrochloric acids will cause general corrosion of rely on the release of halogens for their efficacy. By far, the
stainless steels. Although it could be argued that sulfuric most popular sanitizer is sodium hypochlorite (chloros),
acid can be employed under strictly controlled conditions and this is probably the one material that has caused more
because stainless steels, especially grade 316, have a very corrosion in food plants than any other cleaning agent. For
low corrosion rate, its use could result in a deterioration of a detailed explanation of the corrosion mechanism, the
surface finish. This, in corrosion terms, is an extremely low reader is referred to an article by Boulton and Sorenson
rate but from an aesthetic viewpoint, is undesirable. (17) that describes a study of the corrosion of 304 and 316
Acids such as phosphoric, nitric, and citric, when used stainless steels by sodium hypochlorite solutions. It is im-
at any concentration likely to be employed in a plant clean- portant, therefore, if corrosion is to be avoided, that the
ing operation, have no effect on stainless steels and can be conditions under which it is used are strictly controlled.
used with impunity. Three cautionary notes are worthy of For equipment manufactured from grade 316 stainless
mention: steel, the recommended conditions are:
Maximum concentration150 ppm available chlo- and crevice corrosion. Furthermore, in storage vessels that
rine have been partially filled with iodophor solutions and al-
Maximum contact time20 min lowed to stand overnight, pitting corrosion in the head
Maximum temperatureroom temperature that is space has been observed as a result of iodine vaporizing
well in excess of the minimum conditions established from the solution and condensing as pure crystals on the
by Tastayre and Holley to kill Pseudomonas aerugi- tank wall above the liquid line. Another factor is that io-
nosa (18). dine can be absorbed by some rubbers. During subsequent
processing operations at elevated temperatures, the iodine
In addition, several other precautions must be observed: is released in the form of organic iodine compounds, es-
pecially into fatty foods, which can cause an antiseptic
Before introducing hypochlorite, equipment should taint. The author knows of one dairy that used an iodophor
be thoroughly clean and free of scale deposits. Or- solution to sanitize a plate pasteurizer to kill an infection
ganic residues reduce the bactericidal efficiency of of a heat resistant spore-forming organism. The following
the disinfectant and offer an artificial crevice in day, there were over 2000 complaints of tainted milk. CIP
which stagnant pools of hypochlorite can accumulate. cleaning cycles did not remove the antiseptic smell from
the rubber seals, and complete replacement with new seals
It is imperative that acidic residues be removed by was the only method of resolving the problem.
adequate rinsing before introducing hypochlorite so- Another sanitizing agent that is assuming increasing
lutions. Acid solutions will react with hypochlorite to popularity, especially in the brewing industry because of
release elementary chlorine, which is extremely cor- its efficacy against yeasts, is peracetic acid. As such, per-
rosive to all stainless steels. acetic acid will not cause corrosion of 304 or 316 stainless
The equipment must be cooled to room temperature steels, and the only precautionary measure to be taken is
before introducing hypochlorite. In detergent clean- to use a good quality water containing less than 50 ppm of
ing runs, equipment temperature is raised to 80- chloride ions for making up the solutions to their usage
850C (176-1850F), and unless it is cooled during the concentration. Because of the strongly oxidizing nature of
rinsing cycle, a substantial increase in temperature some types of peracetic acid solutions, deterioration of
of the disinfectant can occur. An important point, fre- some types of rubber may occur. A recent survey under-
quently overlooked, is that a leaking steam valve can taken by the IDF for the use of peracetic acid in the dairy
cause a rise in the temperature of equipment even industry (19) found few corrosion problems reported. The
though it theoretically is shut off. general consensus of opinion was that it permitted greater
After sanitizing, the solution should be drained and flexibility in the conditions of use, compared with sodium
the system flushed with water of an acceptable bac- hypochlorite, without running the risk of damage to equip-
teriological standard. This normally is done by using ment.
a high rinse rate, preferably greater than that used For comprehensive information on the cleaning of food
in the processing run. processing equipment, albeit primarily written for the
dairy industry, the reader is referred to the British Stan-
While these comments relate specifically to the sanitizing dards Institute publication BS 5305 (20).
of plate heat exchangers, similar precautions must be
taken with other creviced equipment. Examples include
CORROSION BY INSULATING MATERIALS
manually operated valves that should be slackened and
the plug raised to permit flushing of the seating surface.
Energy conservation now is widely practiced by all
Pipeline gaskets also should be checked frequently to make
branches of industry, and the food industry is no exception.
sure that they are in good condition and not excessively
For example, in the brewing industry, wort from the wort
hardened. Otherwise they will fail to form a crevice-free
boilers is cooled to fermentation temperature, and the hot
seal over their entire diameter. Where it is not possible to
water generated in the process is stored in insulated ves-
completely remove hypochlorite residues such as in ab-
sels (hot-liquor tanks) for making up the next batch of
sorbent gland packing materials, hot water is preferred.
wort. An area of corrosion science that is receiving in-
All the foregoing relate specifically to sodium hypochlo-
creased attention is the subject of corrosion initiated in
rite solutions but other sanitizing agents that rely on hal-
stainless steels by insulating materials. At temperatures
ogen release, such as di- and trichlorocyanuric acid, should
in excess of 6O0C (14O0F) these can act as a source of chlo-
also be used under strictly controlled conditions, including
rides that will induce stress corrosion cracking and pitting
such factors as pH.
corrosion of austenitic stainless steels.
Iodophors also are used for sanitizing equipment. These
Among the insulating materials that have been used for
are solutions of iodine in nonionic detergents and contain
tanks and pipework are
an acid such as phosphoric to adjust the pH into the range
at which they exhibit bactericidal efficacy. This group of
Foamed plasticspolyurethane, polyisocyanurate, phe-
sanitizers is employed where hot cleaning is not necessary
nolic resins, etc
or on lightly soiled surfaces such as milk road tankers, and
farm tanks. Extreme caution should be exercised with this Cellular and foamed glass
group for, although used at low concentrations (50 ppm), Mineral fiberglass wool, rock wool
prolonged contact with stainless steel can cause pitting Calcium silicate
Magnesia mechanism, the net effect is that cork has an extremely
Cork good "track record." Unfortunately, due to the cost, cork is
now rarely used.
All insulating materials contain chlorides to a lesser (10 No hard-and-fast rules can be laid down for specifying
ppm) or greater (1.5%) extent. The mineral based insulants the acceptable maximum tolerable chloride content of an
such as asbestos may contain them as naturally occurring insulating material. Any specification must take into ac-
water soluble salts such as sodium or calcium chloride. The count what is commercially available as well as all the
organic foams, on the other hand, may contain hydrolys- other factors such as price, flammability, and ease of ap-
able organochlorine materials used as blowing agents (to plication. To specify zero chloride is obviously impractical
form the foam), fire retardants such as chlorinated organ- and even a figure of 10 ppm may be difficult to achieve in
ophosphates, or chlorine containing materials present as commercially available products. As a general compro-
impurities. Insulation manufacturers are becoming in- mise, 25 ppm maximum is considered to be technically and
creasingly aware of the potential risk of chlorides in con- commercially feasible while minimizing the potential
tact with stainless steels and are making serious efforts to source level of chloride corrodent.
market a range of materials that are essentially chloride- The primary function of the insulant is to provide a
free. thermal barrier between the outside of the vessel and the
A point not frequently appreciated is that even though environment. It does not provide a vapor or moisture bar-
many of the insulating materials contain high levels of rier, and provision of such protection must be regarded as
chloride, in isolation they are not corrosive. equally important in the insulating process. As mentioned
Corrosion, which is an electrochemical process, involves previously, the use of bitumen as an adhesive for cork in-
ionic species, and in the absence of a solvent (water) the sulation must provide an extremely good water barrier, al-
chloride or salts present in the insulation cannot undergo though there are a wide range of products marketed spe-
ionization to give chloride ions. Therefore, they are essen- cifically for this purpose. These include specially developed
tially noncorrosive. Similarly, where organochlorine com- paints of undefined composition and zinc free silicone
pounds are present, water is necessary for hydrolysis to alkyd paints as well as silicone lacquer. These silicone
occur with the formation of hydrochloric acid or other ion- based products are particularly appropriate because of
isable chloride compounds. their inherent low water permeability and also their sta-
The main problem, therefore, is not so much the insu- bility at elevated temperatures. Aluminum foil has also
lant but the interaction of the insulant with potential con- been successfully used as a water-vapor barrier between
taminants to release corrosive species. Under ideal condi- the stainless steel and the insulant. There is little doubt
tions, that is, if the insulating material could be that the foil provides an extremely good barrier but at laps
maintained perfectly dry, the chloride content would not between the sheets of foil, ingression of water can occur
be a critical factor in the material specification process. unless sealing is complete, the achievement of which is
Unfortunately, it must be acknowledged that even in the most unlikely. Furthermore, it is likely that there will be
best regulated installation, this ideal is rarely (if ever) tears in the foil, providing yet another ingression path for
achieved and therefore, thought must be given to recom- water. However, it is believed that aluminum foil has a role
mended guidelines. additional to that of a barrier. As it is, from an electro-
Any material that is capable of absorbing water must chemical aspect, "anodic" to stainless steel, it will provide
be regarded as a potential source of chloride. Although the galvanic protection of the steel in areas where there is a
chloride content of the insulant may be extremely low (25 "holiday" in the foil, thus inhibiting corrosion mechanisms.
ppm), under extractive conditions when the insulation be- When insulation material becomes wet, the insulating
comes wet and concentration effects come into play, even efficiency shows a dramatic fall-off. In fact, the thermal
this material may cause the initiation of stress corrosion conductivity of wet insulation will approach that of the
cracking. The chloride content of the contaminating water wetting medium, and it is ironic that the thermal conduc-
cannot be ignored. Even a "good-quality" water with a low tivity of water is among the highest known for liquids. It
chloride content (30 ppm), if being continuously absorbed is imperative that from the standpoint of preventing mois-
by the insulant, forms a potential source of chlorides that, ture ingression to minimize corrosion risks and maintain
through evaporation, can reach very significant levels and insulation efficiency, the insulation is externally protected
initiate the corrosion mechanism. from rain and water. There is a variety of materials avail-
The more absorptive the insulant, the greater the risk, able for this such as aluminum sheeting, plastic-coated
and materials such as calcium silicate and certain types of mild steel, and spray applied polyurethane coatings. Much
foams must be regarded as least desirable. It is interesting of the value of the protection will be lost unless particular
to note that one of the least absorptive insulants from attention is taken to maintaining a weather-tight seal at
those listed is cork, and in the experience of the author, the overlaps in individuals sheets of cladding. There are
there have been no reported cases of this insulant causing many semiflexible caulking agents that can be employed
problems with stress corrosion cracking of stainless steels. for this. One that is particularly effective is the RTV silicon
Of course, it could be argued that the bitumen used as an rubber, which exhibits extremely good weather resistance
adhesive to stick the cork to the vessel walls has to be ap- and long-term reliability. Nevertheless, maintenance is re-
plied so thickly that the bitumen forms an impermeable quired, especially around areas of discontinuity such as
barrier preventing contact of the contaminated water with flanged connections and manway doors. Operators are be-
the stainless-steel substrate. Irrespective of the protection ginning to realize that routine maintenance work on in-
Table 5. Some Synthetic Rubbers information, an excellent publication by the American So-
Common ciety for Testing Materials (21) is essential reading.
Rubber trade names Basic structure
Polychloroprene Neoprene Poly (2-chlor-l,8 butadiene) CORROSION OF RUBBERS
Perbunan C
Butachlor
Nairit Many involved in the field of corrosion would not regard
SBR (styrene Buna S Copolymer of styrene and the deterioration of rubber as a corrosion process. The au-
butadiene Plioflex 1,4 butadiene thor's opinion differs from this viewpoint as "rubber un-
rubber) Intol dergoes deterioration by interaction with its environment."
Krylene
Nitrile Buna N Copolymer of acrylonitrile
Chemigum N and 1,4 butadiene General
Paracril
Perbunan
Rubber and rubber components form an essential part of
Hycar food processing equipmentjoint rings on pipelines, gas-
EPDM (ethylene Nordel Copolymer of ethylene and kets on heat exchangers, and plate evaporators. Although
propylene diene Royalene propylene with a third natural rubber was the first material to be used for manu-
methylene) Vistalon monomer such as facturing these components, nowadays they are made al-
Dutral ethylidene norbonene, most exclusively from one of the synthetic rubbers listed
Keltan cyclopentadiene in Table 5.
Intolan Unlike metals and alloys, which have a strictly defined
Butyl GR-I Copolymer of isobutylene composition, the constituents used in the formulation of
Bucar and isoprene rubbers are rarely stipulated. More often, they will reflect
Socabutyl
Silicone Silastic Poly( dimethyl siloxane),
the views and idiosyncrasies of the formulator on how to
Silastomer poly(methyl vinyl achieve the desired end product. The important constitu-
Sil-O-Flex siloxane), etc. ents of a rubber are
Fluoroelastomer Viton Copolymer of
Technoflon hexafluoropropylene and Basic Polymer. Largely determines the general chem-
Fluorel vinylidene fluoride ical properties of the finished product.
Reinforcing Fillers. These are added to improve the
mechanical properties and will invariably be one of
the grades of carbon blackor if a white rubber is
required, mineral fillers such as clays or calcium sil-
icate.
Vulcanizing Agents. These cross-link the basic poly-
mer and impart rubberlike properties that are main-
tained at elevated temperatures.
Antioxidants. To stabilize the rubber against oxida-
tive degradation, hardening or softening, after pro-
longed operating periods at elevated temperatures.
Processing Aids. Which facilitate the molding of the
rubber.
Plasticizers. To modify the mechanical properties.
Cleaning Agents
Sodium hydroxide0 G E G G E E E
Sodium carbonate^ E E E E E E E
Sodium hypochlorite^ G G G G E E E
Nitric acid'1 F F P F G G G
Phosphoric acid1 E E E E E E E
Quaternary ammonium compounds6 E E E E G G G
"Depending on the type of basic polymer.
^Depending on the fat/oil content.
c
Used as an aqueous 1% solution.
d
The performance of a rubber will be affected by the presence of essential oils.
6
AIl strengths up to 5% at maximum operating temperatures of the rubber.
^Sodium carbonate and other detergent/additives, eg, sodium phosphate, silicate.
^Sodium hypochlorite as used at normal sterilizing concentration150 mg/L.
^Nitric acid as used at normal cleaning strength of 1/2-1%.
'Up to 5% strength.
Table 7. Suggested Limits of Concentration and Temperature for Peracetic Acid in Contact with Rubber
Peracetic acid concentration
(active ingredient) Temp. (0C) Medium nitrile Butyl (resin-cured) EPDM Silicon Fluoro-elastomer
0.05% (500 mg/L) 20 Ra R R R R
60 R R R R R
85 (?) R R R (?)6
0.10% (1 g/L) 20 R R R R R
60 NRC R R NR R
85 NR (?) R NR NR
0.25% (2.5 g/L) 20 R R R (?) R
60 NR R R NR R
85 NR NR R NR NR
0.5% (5 g/L) 20 R R NR R
60 NR R R NR R
85 NR NR R NR NR
0
RLittle effect on the rubber.
6
(?)Possibly some degradation.
C
NRNot recommended as significant degradation may occur.
Corrosion by Rubber many of the rubber adhesives are produced from one of
these polymers. That is the reason why manufacturers of
The majority of rubbers and formulating ingredients have heat exchangers and other equipment, which necessitates
no effect on stainless steels even under conditions of high sticking the rubber onto metal, specify what type of ad-
temperature and moisture. There are two notable excep- hesive should be used. Many DIY adhesives and contact
tions, namely, polychloroprene and chlorosulfonated poly- adhesives are formulated from polychloroprene, and it is
ethylene. Both of these contain chlorine, which under the not unknown for a maintenance engineer having to stick
influence of temperature and moisture, undergo hydrolysis gaskets in a heat exchanger to get the supply of rubber
to produce small quantities of hydrochloric acid. In contact cement from the local hardware shop. The results can be
with stainless steel, this represents a serious corrosion catastrophic, as shown in Figure 23. Similarly, many self
hazard causing the three main forms of attack. adhesive tapes used as a polychloroprene-based adhesive
When specifying a rubber component, it is easy to avoid and direct contact of these with stainless steels should be
these two polymers but a fact not often appreciated is that avoided.
Corrosion of Rubber by Environments 10. J. W. Oldfield, Test Techniques for Pitting and Crevice Corro-
sion of Stainless Steels and Nickel Based Alloys in Chloride-
From the standpoint of food processing, the environments Containing Environments, NiDi Technical Series 10 016,
likely to interact with rubber are classified under the fol- 1987.
lowing headings: 11. U. R. Evans, Corrosion 7, 238 (1981).
12. ASTM G48-76, Standard Methods for Pitting and Crevice Cor-
Foodstuffs containing no fat or a low level of fat, eg, rosion Resistance of Stainless Steels and Related Alloys by Use
milk of Ferric Chloride Solution, American Society for Testing Ma-
Fatty products: butter, cream, cooking oils, shorten- terials, Philadelphia.
ings 13. R. J. Brigham, Materials Performance 13, 29 (Nov. 1974).
Alkaline detergents 14. N. D. Greene and M. G. Fontana, Corrosion 15, 25t (1959).
Acid detergents 15. M. Woelful and R. Mulhall, Metal Progress, 57-59 Sept. 1982.
Sanitizing agents 16. M. R. Copson, "Effect of Composition on SCC of Some Alloys
Containing Nickel," in T. Rhodin, ed., Physical Metallurgy of
Unlike the corrosion of metals, which is associated with Stress Corrosion Fracture, Interscience Publishers, New York,
oxidation and loss of metal, rubber deterioration usually 1989.
takes other forms. When a rubber is immersed in a liquid, 17. L. H. Boulton and M. M. Sorensen, New Zealand Journal of
it absorbs that liquid or substances present in it to a Dairy Science & Technology 23, 37-49 (1988).
greater or lesser degree. The amount of absorption deter- 18. G. M. Tastayre and R. A. Holley, Publication 1806/B. Agricul-
mines whether the rubber is compatible with the environ- ture Canada, Ottawa, 1986.
ment. The absorption will be accompanied by changes in 19. IDF Bulletin 236, Corrosion by Peracetic Acid Solutions, In-
mass, volume, hardness, and tensile strength. For exam- ternational Dairy Federation, 41 Square Vergote, 1040 Brus-
ple, immersing and oil resistant rubber in vegetable oil sels, Belgium.
may produce a change in volume of only 2-3%, whereas a 20. BS 5305 Code of practice for cleaning and disinfecting of plant
non-oil-resistant rubber may swell by 150% or more. Such and equipment used in the dairying industry, British Stan-
a volumetric change will be accompanied by a large reduc- dards Institute, London.
tion in the tensile strength and a high degree of softening. 21. ASTM Special Technical Publication 880. Corrosion of Metals
Broadly, speaking, a rubber should not exhibit a volu- under Thermal Insulation. American Society for Testing Ma-
metric or weight change greater than 10% nor a hardness terials, Philadelphia.
change of more than 10 degrees (International Rubber 22. Sonderdruck aus Bundesgesundheitsblatt, 22.1,79, West Ger-
Hardness DegreesIRHD or Shore A) to be classed as many.
compatible. For general guidance, data presented in Tables 23. USA Code of Federal Regulations. Title 21. Food and Drugs
6 and 7 (19) indicate the compatibility of rubbers with Section 177.2600. Rubber Articles Intended for Repeated Use.
some food industry environments. But for more informa- 24. BS 903 Part A16, Resistance of Vulcanized Rubbers to Liq-
tion, the reader should refer to one of the national or in- uids, British Standards Institution, London.
ternational test procedures (24-26). 25. ASTM D. 471, Testing of Rubbers and Elastomers. Determi-
nation of Resistance to Liquids, Vapors, and Gases, American
Society for Testing Materials, Philadelphia.
BIBLIOGRAPHY
26. ISO 1817, Vulcanized RubbersResistance to Liquids
Adapted from: C. T. Cowan, "Materials Science and Corrosion Pre- Methods of Test.
vention for Food Processing Equipment," APF Corrosion Hand-
book, March 1990, 44 pp.
Copyrighted APV Crepaco, Inc. Used with permission. APV CREPACO, INC.
Lake Mills, Wisconsin
1. N. Warren, Metal Corrosion in Boats, London Stanford Mari-
time, 1980.
2. A. J. Sedricks, Corrosion of Stainless Steels, Wiley, New York,
1979. CRABS AND CRAB PROCESSING
3. The British Aluminium Co., Ltd., Aluminium in the Chemical
and Food Industries, 1951. (London: The British Aluminium Crabs play an important part in the U.S. fishing industry.
Co., Ltd.) Ex-vessel landings and values usually rank low in quantity
4. G. Ferry, New Scientist, 27 Feb. 1986, 23. (Fig. 1) and high in value (Fig. 2). The quantity and value
5. G. A. Dummett, From Little Acorns, A History of the APV of the major crab fishes in the United States in 1996 are
Company, Hutchison Benham, London, 1981. shown in Table 1 (1). Variations in processing methods for
6. C. T. Cowan, "Corrosion Engineering with New Materials," crabs are related to the species and the seasonal charac-
The Brewer 163-168 (1985). teristics that affect yield, ease of meat removal, and color.
7. M. G. Fontana, Corrosion Engineering, McGraw-Hill, New Speed in handling the product from time of harvesting to
York, 1986. freezing or canning is a most important process require-
8. L. L. Shrier, Corrosion, Newnes-Butterworth, London, 1976. ment (2,3). Quality control procedures generally empha-
9. J. W. Oldfield and B. Todd, Transactions of the Institute of size sanitation, food regulatory requirements, and compli-
Marine Engineering (C), 1984, Conference 1, 139. ance with end-product specifications of the processor (4).
Corrosion of Rubber by Environments 10. J. W. Oldfield, Test Techniques for Pitting and Crevice Corro-
sion of Stainless Steels and Nickel Based Alloys in Chloride-
From the standpoint of food processing, the environments Containing Environments, NiDi Technical Series 10 016,
likely to interact with rubber are classified under the fol- 1987.
lowing headings: 11. U. R. Evans, Corrosion 7, 238 (1981).
12. ASTM G48-76, Standard Methods for Pitting and Crevice Cor-
Foodstuffs containing no fat or a low level of fat, eg, rosion Resistance of Stainless Steels and Related Alloys by Use
milk of Ferric Chloride Solution, American Society for Testing Ma-
Fatty products: butter, cream, cooking oils, shorten- terials, Philadelphia.
ings 13. R. J. Brigham, Materials Performance 13, 29 (Nov. 1974).
Alkaline detergents 14. N. D. Greene and M. G. Fontana, Corrosion 15, 25t (1959).
Acid detergents 15. M. Woelful and R. Mulhall, Metal Progress, 57-59 Sept. 1982.
Sanitizing agents 16. M. R. Copson, "Effect of Composition on SCC of Some Alloys
Containing Nickel," in T. Rhodin, ed., Physical Metallurgy of
Unlike the corrosion of metals, which is associated with Stress Corrosion Fracture, Interscience Publishers, New York,
oxidation and loss of metal, rubber deterioration usually 1989.
takes other forms. When a rubber is immersed in a liquid, 17. L. H. Boulton and M. M. Sorensen, New Zealand Journal of
it absorbs that liquid or substances present in it to a Dairy Science & Technology 23, 37-49 (1988).
greater or lesser degree. The amount of absorption deter- 18. G. M. Tastayre and R. A. Holley, Publication 1806/B. Agricul-
mines whether the rubber is compatible with the environ- ture Canada, Ottawa, 1986.
ment. The absorption will be accompanied by changes in 19. IDF Bulletin 236, Corrosion by Peracetic Acid Solutions, In-
mass, volume, hardness, and tensile strength. For exam- ternational Dairy Federation, 41 Square Vergote, 1040 Brus-
ple, immersing and oil resistant rubber in vegetable oil sels, Belgium.
may produce a change in volume of only 2-3%, whereas a 20. BS 5305 Code of practice for cleaning and disinfecting of plant
non-oil-resistant rubber may swell by 150% or more. Such and equipment used in the dairying industry, British Stan-
a volumetric change will be accompanied by a large reduc- dards Institute, London.
tion in the tensile strength and a high degree of softening. 21. ASTM Special Technical Publication 880. Corrosion of Metals
Broadly, speaking, a rubber should not exhibit a volu- under Thermal Insulation. American Society for Testing Ma-
metric or weight change greater than 10% nor a hardness terials, Philadelphia.
change of more than 10 degrees (International Rubber 22. Sonderdruck aus Bundesgesundheitsblatt, 22.1,79, West Ger-
Hardness DegreesIRHD or Shore A) to be classed as many.
compatible. For general guidance, data presented in Tables 23. USA Code of Federal Regulations. Title 21. Food and Drugs
6 and 7 (19) indicate the compatibility of rubbers with Section 177.2600. Rubber Articles Intended for Repeated Use.
some food industry environments. But for more informa- 24. BS 903 Part A16, Resistance of Vulcanized Rubbers to Liq-
tion, the reader should refer to one of the national or in- uids, British Standards Institution, London.
ternational test procedures (24-26). 25. ASTM D. 471, Testing of Rubbers and Elastomers. Determi-
nation of Resistance to Liquids, Vapors, and Gases, American
Society for Testing Materials, Philadelphia.
BIBLIOGRAPHY
26. ISO 1817, Vulcanized RubbersResistance to Liquids
Adapted from: C. T. Cowan, "Materials Science and Corrosion Pre- Methods of Test.
vention for Food Processing Equipment," APF Corrosion Hand-
book, March 1990, 44 pp.
Copyrighted APV Crepaco, Inc. Used with permission. APV CREPACO, INC.
Lake Mills, Wisconsin
1. N. Warren, Metal Corrosion in Boats, London Stanford Mari-
time, 1980.
2. A. J. Sedricks, Corrosion of Stainless Steels, Wiley, New York,
1979. CRABS AND CRAB PROCESSING
3. The British Aluminium Co., Ltd., Aluminium in the Chemical
and Food Industries, 1951. (London: The British Aluminium Crabs play an important part in the U.S. fishing industry.
Co., Ltd.) Ex-vessel landings and values usually rank low in quantity
4. G. Ferry, New Scientist, 27 Feb. 1986, 23. (Fig. 1) and high in value (Fig. 2). The quantity and value
5. G. A. Dummett, From Little Acorns, A History of the APV of the major crab fishes in the United States in 1996 are
Company, Hutchison Benham, London, 1981. shown in Table 1 (1). Variations in processing methods for
6. C. T. Cowan, "Corrosion Engineering with New Materials," crabs are related to the species and the seasonal charac-
The Brewer 163-168 (1985). teristics that affect yield, ease of meat removal, and color.
7. M. G. Fontana, Corrosion Engineering, McGraw-Hill, New Speed in handling the product from time of harvesting to
York, 1986. freezing or canning is a most important process require-
8. L. L. Shrier, Corrosion, Newnes-Butterworth, London, 1976. ment (2,3). Quality control procedures generally empha-
9. J. W. Oldfield and B. Todd, Transactions of the Institute of size sanitation, food regulatory requirements, and compli-
Marine Engineering (C), 1984, Conference 1, 139. ance with end-product specifications of the processor (4).
tica). Blue king crab (P. platypus) is caught in commercial
quantities primarily near the Pribilof Islands. Brown or
golden king crab (Lithodes aequispina) are found in deeper
Quantity (million Ib)
which are cooked and made into scrapple. Frying, stewing, not observe dietary regulations. The country of origin can
and barbecuing are the favored methods of preparation. further influence a Jewish family's dietary practices.
Sweets such as molasses, pastries, cakes, and candy are Foods used according to strict Jewish laws are referred
especially popular. to as Kosher. Those who follow those dietary laws eat only
Milk consumption, which is often low, should be en- animals that are designated as clean and are killed in a
couraged, especially among children. Buttermilk and ice ritualistic manner. The method of slaughter minimizes
cream are well liked by black Americans, although there pain and maximizes blood drainage. Blood, the symbol of
is little use of cheeses. The use of more citrus fruits should life, is strictly avoided by soaking the meat in cold water,
be encouraged. draining it, salting it, and rinsing it three times. Permitted
As the economic status of black people improves, they meats include poultry, fish with fins and scales, and quad-
eat more meat and their diet improves generally. Because ruped animals that chew the cud and have divided hooves.
their typical diet is high in fat and carbohydrate and low (Thus, pork cannot be eaten.) The hindquarter of quadru-
in protein, iron, and vitamin C, an increase in consumption ped animals must have the hip sinew or the thigh vein
of lean meat, milk, and citrus fruits will help balance their removed.
nutrient intake. Kosher laws additionally require separation of meat
It is in preparation that the essence of the term soul and milk. Milk and its products must be excluded from
food can be found. It is not necessarily the unique foods but meals involving meat but can be consumed before the meat
rather the care in preparation that is emphasized. Food meal. If a milk meal is to be consumed, meat and its prod-
preparation offers the opportunity to minister to the physi- ucts are excluded from the milk meal and for 6 hours there-
cal health and well-being of those who will consume the after. Usually two milk meals and one meat meal are eaten
food. The opportunity to bring happiness, health, and love each day. A Kosher household will maintain two sets of
through food preparation lies at the figurative and literal dishes, utensils, and cooking supplies, one for meat meals
heart of the customary black dietary habits. and one for milk meals.
Certain foods, viewed as neutral, are referred to as
Jews pareve. Fruits, uncooked vegetables, eggs, and clean fish,
because they are recognized as neutral, can be consumed
Orthodox Jews follow Old Testament and rabbinical die- with either meat or milk meals.
tary laws. Conservative Jews distinguish between meals No food can be cooked or heated on Saturday, the Sab-
served in the home and those outside it. Reformed Jews do bath, so the evening meal preceding the Sabbath tends to
the most substantial of the week. Both chicken and fish recommended in taco fillings, dark green and yellow vege-
are served at that meal. Any foods eaten on the Sabbath tables, fruits, and milkdried if fresh milk is too
must be cooked on a preceding day. expensiveare also recommended. The milk is especially
On Jewish holidays, symbolic foods are eaten. For ex- important for children. One Mexican dietary practice that
ample, Passover, a spring festival, commemorates the is particularly encouraged is the practice of limiting the
flight of the Jews from Egypt. Passover celebration lasts 8 amount of sweets consumed (Table 2).
days, and only unleavened bread, called matzo, is permit-
ted. An Orthodox household will, therefore, use separate Puerto Ricans
utensils for preparing unleavened bread to avoid any con-
tact with leavening. Other holidays include Rosh Has- The Puerto Rican diet has similarities to the dietary pat-
hanah (Jewish New Year), Sukkoth (fall harvest), Chanuk- terns of other Caribbean Islands but is noteworthy because
kah (the festival of lights), Purim (the arrival of spring), so many Puerto Ricans emigrate to the United States.
and Yom Kippur (the day of atonement) when fasting oc- Traditional emphasis is on beans, rice, and starchy root
curs. vegetables (and plantains) known as viandas. Rice and
beans eaten together are a high-quality, complementary
Mexican-Americans protein combination. The beans are often boiled and then
cooked with sofrito, a mixture made from tomatoes, green
People of Mexican descent make up a large part of the peppers, onions, garlic, salt pork, lard, and herbs. Viandas
population of the Southwest. They therefore reside close to are good sources of B vitamins, iron calories, and, in some
their native country and maintain a close tie to traditional cases, vitamin C. Salt codfish is more popular than fresh
Mexican foods. A lack of refrigeration in such warmer cli- fish. Chicken, beef, and pork are favored. Coffee with 2 to
mates creates a scarcity of meat, milk, eggs, vegetables, 5 oz of milk per cupcafe con lecheis drunk several
and fruits. For lower-income families, the expense of these times a day, contributing to an otherwise low consumption
nutrient-rich foods can be prohibitive. of milk. Fruits prove an especially popular food owing to
Items basic to the Mexican diet include dry beans, chili availability, with such native fruits as papaya, mango, and
peppers, tomatoes, and corn. The corn is ground, soaked acerola (the West Indian cherry, which is extremely high
in lime water, and baked on a griddle to make tortillas, the in vitamin C) being joined by bananas, oranges, and pine-
popular flat breads that can be rolled and filled with apple.
ground beef and vegetables to make tacos. Tacos provide The mainstays of the Puerto Rican diet may be hard to
nutrients from all four food groups, although the user of find or expensive in the United States. And because Puerto
wheat tortillas reduces the calcium obtained from lime- Ricans come from an agrarian background and thus often
soaked corn tortillas. Many foods are fried, and beans are lack the job skills for a highly industrialized society, they
even refried until they absort all the fat. often find themselves in the lowest socioeconomic classes
Nutritionists encourage retention of the basic Mexican in the United States, living in crowded urban conditions
diet with only minor modifications. Because of iron, vita- with poor cooking and refrigeration facilities and unable
min A, and calcium deficiencies, use of lean meat is to feed their families as well as they did in Puerto Rico.
NUTRITION Yeast
Saccharomyces cerevisiae Ethanol, CO2
Candida (Torula) kefir Ethanol, CO2
The primary nutritional benefits of cultured milk products Kluveromyces fragilis Acetaldehyde, CO2
are due to their compositional makeup. All milk products
are excellent sources of high-quality proteins (casein and Note: Lc. Lactococcus, Leuc. = Leuconostoc, Lb. = Lactobacillus, Str. =
Streptococcus.
whey), calcium, and vitamins (especially riboflavin and Source: Ref. 3.
other B vitamins). Early in the twentieth century Eli
Metchnikoff (1908) proposed in his book, Prolongation of
Life Optimistic Studies, that the consumption of cultured
milk products such as yogurt result in the prolongation of BIBLIOGRAPHY
life. Metchnikoff based his claims on the ability of lactic 1. M. Kroger, J. A. Kurmann, and J. L. Rasic, "Fermented Milks
bacteria to prevent putrefactive processes in the digestive Past, Present, and Future," Food Technol. 43, 92-99 (1989).
tract (4). Although lactic cultures do produce antimicrobial 2. G. Campbell-Platt, Fermented Foods of the World, Butter-
effects from the production of acids, hydrogen peroxide, worth, Kent, United Kingdom, 1987.
and antibiotics such as nisin, scientific evidence does not 3. B. A. Law, Microbiology and Biochemistry of Cheese and Fer-
support Metchnikoff's claims of prolonged life due to the mented Milk, Blackie Academic and Professional, London,
consumption of cultured products. However, there is grow- United Kingdom, 1997.
ing scientific evidence that the addition of alternative or- 4. E. Metchnikoff, The Prolongation of Life Optimistic Studies,
ganisms to cultured products such as Lactobacillus aci- G. P. Putnam's Sons, New York, 1908.
dophilus and Bifidobacterium sp. may have therapeutic 5. K. Kailasapathy and S. Rybka, "L. acidophilus and Bifidobac-
effects in the lower digestive system (5). Many of these terium spp.Their Therapeutic Potential and Survival in
organisms are believed to be able to pass through the up- Yogurt," Aust. J. Dairy Tech. 52, 28-35 (1997).
per digestive system and then produce beneficial effects in
the lower intestine. Recent research suggest that the con- JOHN U. MCGREGOR
sumption of these probiotic cultures in cultured milk prod- Louisiana State University Agricultural Center
Baton Rouge, Louisiana
ucts could aid in the prevention of intestinal infections,
diarrheal diseases, hypercholesterolaemia, lactose diges-
tion, and cancer. CVCtOSPORA. See FOODBORNE DISEASES.
D
DAIRY FLAVORS of milk, including the cow, water buffalo, goat, and sheep,
that are commonly used sources.
Dairy products are very ancient foods and are one of the In the 10 year period from 1987 to 1997, the production
most important classes of foods in our diet. The basic dairy of milk has increased by approximately 15 billion Ib to 155
product, milk, is not a very stable food. Today's practice billion Ib, with 60% of the milk used to create other dairy
allows us to heat process it to keep it stable from micro- products. The percent use of milk products to make other
biological attack for various periods of time depending on dairy products increased by 2% during that period. Total
the nature of the processing conditions to which the milk cheese production, excluding cottage cheese, was 7.33 bil-
is subjected. The commercial practice of heat processing lion Ib in 1997, an annual increase of 2%. Wisconsin was
(pasteurization) has only been in place for the last 60 or so the leading state for cheese product, with 29% of the total
years. In ancient times milk was allowed to spoil in a con- production. By far the most popular types of cheese are the
trolled way so that it would remain eatable. American varieties, which include mainly cheddar. Cot-
The development of ghee (butter) from buffalo milk, an tage cheese is produced by far more plants in the United
early practice of controlling the spoilage of milk, has been States (332) and represents production of 1.2 billion Ib.
traced to India of perhaps about 4,000 years ago. The Butter production has been declining; in 1997 production
method of butter making was to appear in Europe at a was recorded at 1.2 billion Ib, a decrease of 2% from 1996.
much later date. The first commercial creamery in the California, at 27% of butter production, was slightly ahead
United States was built by Alanson Slaughter in 1881 in of Wisconsin, at 26%. Table 1 represents the statistics for
Orange County, New York. production of various dairy products in the United States
Cheese from milk also has a prehistoric origin. Cheese during 1997.
was an excellent way to preserve the important nutrients In discussing the nature of the flavors of these products
of milk. Because of the many ways of stabilizing milk into it is natural to organize the discussion based on the types
cheese, many forms of cheese with a variety of flavor and of products manufactured. Based on the major groups of
taste profiles have been developed. Recently, a USDA bul- products, there are four distinct areas that will be dis-
letin indicated over 800 varieties and the (United States cussed. They are fluid milk and milk products (dried and
Food and Drug Administration) U.S. FDA has established canned), milk-derived products (yogurt and similar types
standards of identity for 30 different type of cheeses. Typ- of fermented milk products and ice cream), butter, and
ically, cheeses are named after the immediate region where cheeses.
they were originally produced.
At first the manufacture of dairy products, including Milk and Milk Products
milk, milk products, butter, and cheese, was based on his-
torical practice and the art of the producers. It took the These products are minimally processed. Typically they
great scientific revelation of Louis Pasteur working in may be reduced in fat, have the fat suspended (homoge-
France between 1857 and 1876 to relate the manufactur- nized), or be heat treated. The heat-processing step may
ing process to the new world of the microorganism and fer- vary in its time/temperature relationship to assure a safe
mentation. The use of pure culture techniques began
around 1870, and the dairy and cheese industry was trans-
formed from an industry of inconsistent product quality Table 1. Dairy Product Production in the United States
and quantity. The various organisms responsible for the for 1997
development of the flavor, taste, and texture of dairy and Total volume
cheese products were discovered and used in day-to-day in 1997 Growth rate
operation of the manufacturing plants. More recent sci- Products Plants (in 1,000 pounds) (%)
entific advances in the area of organic, analytic, and bio-
Butter 91 1,151,250 2.0
chemistry have allowed for the identification of those Cheeses 2.0
chemical components that develop during the manufactur- American 215 3,285,203
ing steps and contribute to the flavor profiles that we as- Swiss 42 207,583
sociate with these products. Muenster 42 100,191
Besides the well-known nutritional properties of these Brick 21 8,535
products, they are very popular owing to their unique fla- Limburger 1 746
vor, taste, and textual attributes. Italian types 156 2,880,404
Cream & Neufchatel 32 614,921
Cottage Cheese 332 1,164,172
OVERVIEW OF DAIRY PRODUCTS Canned milk 9 580,965
Skim milk 51 997,802
Dairy products may be defined as food products based on Dry Milk (nonfat) 47 1,217,562 15.0
milk developed through a variety of manufacturing meth- Yogurt 104 1,574,050
ods and fluid milk itself. There are several animal sources Source: Ref. 1.
product. Although the heat treatment can have some influ- Reaction between the sugars and proteins (Maillard
ence on the taste and flavor of fresh milk, there is a much reactions).
greater relationship to the time of year, nature of the ani- The release or formation of sulfur-containing com-
mals' feed, and the species of animal from which the milk ponents.
is derived.
Milk is a very complex substance based on fats, sugars Degradation of Precursors. The triglycerides (lipids) in
(mainly lactose), proteins (such as lactalbumin), and salts milk fat are formed from complex as well as simple fatty
(such as calcium phosphate). The taste of milk is mainly acids of many types, including substituted acids such /?-
affected by the change in this mixture and the degree to keto acids and hydroxy acids. These acids originate in the
which the fat is emulsified (homogenized) in a continuous diet of the animal and also may be the result of normal
phase with the aqueous phase. The sensory perception de- metabolism. Methyl ketones are formed from the /?-keto
termines the physical nature of the emulsion, with a acids (5). Although they are formed in fresh milk, maxi-
slightly salty/sweet taste from the salts and lactose. Al- mum yield occurs at prolonged elevated heating (14O0C for
though some slight flavor changes can be detected in even 3 h). The liberation of methyl ketones is generally below
the mildest of heat-treated milk, the flavor defects are gen- their individual odor thresholds, yet they contribute to the
erally considered to be notes associated with good quality, aroma of milk because of their synergistic interaction due
pasteurized milk. to their combined concentration (6). Methyl ketones are
Of the various constituents of the milk, the lipid (fat) formed from the decarboxylation of the /?-keto acids,
fraction has the greatest effect on milk's flavor. It is also whereas ring closure of d- and r-hydroxy acids form the
the precursor of many chemical components considered im- corresponding lactones.
portant in all types of dairy flavors. The fatty acid com-
position of the milk lipids is also very complex and unique The Maillard Reaction. Reaction between the lactose
among food products. More than 60 fatty acids have been and the milk protein can lead to many different compounds
reported in cow's milk (2). Quantities of butyric acid and of flavor significance. These reactions are referred to as
caproic, caprilic, decanoic (fatty acids with 6, 8, and 10 car- Maillard reactions. Discussion of the Maillard reaction is
bon atoms) acids are unique to milk and of great impor- complex and outside the scope of this article, but its basic
tance in the development of flavors in products based on chemical pathway is the reaction between aldose and ke-
milk. Oxidation of these lipids gives rise to some key flavor tone sugars and a-amino acids resulting in the formation
components. For example, the oxidation of unsaturated oc- of aldosylamines or ketosylamines. These materials then
tadecadienoic acid leads to the formation of 4-cis-heptenal, undergo further rearrangement, resulting in the creation
which has been identified as the cream-like flavor compo- of many key flavoring materials, such as acetyls, furans,
nent in milk and butter (3). The free fatty acid distribution pyrroles, aldols, and pyrones. The normal heat treatment
of milk and butter is shown in Table 2. of milk does not appear to produce enough of the Maillard
The heat treatment of milk is divided into two types of reaction product to be a flavor contributor. However, the
cooked flavor of milk is noted when it is heated to above
processing: pasteurization in which the milk is heated for
750C (7). At that point many Maillard reaction products
15 s at 720C and ultra high-temperature treatment (uht),
start to contribute to the flavor of the milk. Further heat-
where it is heated at 135-15O0C for a few seconds. The
ing above the cooked-flavor range produces a carameliza-
flavor changes that occur during the heat treatment may
tion flavor, due to the intense amount of Maillard reaction
be formed from three distinct chemical mechanisms:
products being formed and the liberation of many sulfur-
containing chemicals.
Degradation of thermally labile precursor found in
milk. Formation of Sulfur-Containing Compounds. Dimethyl
sulfide is produced from the S-methyl methionine sulfo-
nium salt (from the vegetable matter in the animal's diet)
that is decomposed on heating (8). At high concentrations
Table 2. Free Fatty Acids in Milk
this chemical produces a malty or cowy flavor defect in the
Fatty acid Fat (%
> milk (9). The flavor from the caramelization of milk has
(carbon no.: unsaturation) Fresh milk Rancid milk Butter found great use in various culinary schools of fine food
preparation.
4:0 7.23 6.03 1.32
6:0 3.40 3.42 0.65
8:0 1.37 2.07 0.83 Flavor Defects in Milk. Caramelization is a wanted de-
10:0 5.16 3.98 1.41 fect in many food applications; yet, there are some defects
12:0 4.89 3.98 4.22 that are not wanted. Extended storage of dry milk causes
14:0 10.02 9.58 11.02 the stale off-flavor where the release to the fatty acid con-
16:0 23.61 26.09 22.69 tributes to the further development of methyl ketones
18:0 9.98 13.65 12.04 above their threshold value, but below the quantity seen
18:1 29.78 27.05 38.40 in certain cheeses; for example, the family of blue cheeses
18:2 4.55 4.14 4.66 (10).
18:3 2.69 The oxidation of milk causes the cardboardy or cappy
Source: Ref. 4. defect that is evaluated as the milk being metallic, tallowy,
oily, or fishy. The oxidation of the unsaturated fatty acids Table 4. Cultured Milk Products
leads to the methyl ketones and series of aldehydes. Very Product type Fermentation Organism
low levels of cis-4-heptenal, hexenal, and 1,3 octenone con-
tribute to the oxidized flavor defect (11). Yogurt (U.S.) Moderate acid Streptococcus thermophilus
The lipolysis of the milk by Upases remaining active af- Lactobacillus bulgaricus
Buttermilk Moderate acid Streptococcus cremoris
ter the heat treatment can cause rancidity of the milk. This (U.S.) Streptococcus lactis
is due to the increase of both the short-chain fatty acids Acidophilus milk
and the increased acidity of the milk. In normal milk the (U.S.) High acid Lactobacillus acidophilus
total free acid content is about 360 mg/kg, but in rancid Bulgarican milk
milk it rises to 500-1500 mg/kg (4). (EUR) High acid Lactabacillus bulgaricus
One final major flavor defect is known as the sunlight Yakult (Japan) Moderate acid
defect. It is believed to be produced from the degradation Dahi (India) Moderate acid Streptococcus diacetyllactic
of methional (a common amino acid found in milk) to sev- Leben (Egypt) High acid Streptococci, Lactobacilli,
eral sulfur-containing compounds, including mathane- yeast
thiol, dimethyl sulfide, and dimethyl disulfide. These con- Kifur (USSR) High alcohol Lactobacillus caucascus
Leuconostoc spp
tribute to a flavor characterized as burnt or cabbagey. The
extent of the flavor defect is related to the length and
strength of exposure to light (12).
Milk's Basic Flavor. Milk's basic flavor, then, is due increase over the 1966 figure. This, no doubt, reflects the
mainly to the taste components found in the milk as noted healthy eating trend in the United States prompted by
in Table 3. The fats, sugars, salts, and protein all contrib- television commercials and magazine ads listing the
ute to give milk a subtle, but enjoyable, flavor and taste. health benefits of cultured milk products.
Unless the milk has been mistreated or subjected to high The basic fermentation is due to lactic acid bacteria.
temperature for prolonged time, no significantly predomi- Historically, this was fermentation done by a mixed or un-
nate flavor is noted. In contrast, products made from milk known culture or back-slop, but modern technology has de-
have characteristic and, in some cases, strongly predomi- veloped the pure culture with its predictable performance
nate aroma and tastes. potentials.
The major flavor and taste component in these products
Cultured Dairy Products is the lactic acid produced by the fermentation of the sug-
ars by the bacteria. Although this flavor is considered ac-
Among the first products of milk to be developed were cul- ceptable in many societies, it is rejected completely in oth-
tured products. Cultured products are produced through- ers. To increase the commercialization of these products,
out the world, as seen in Table 4. Originally, fermentation manufacturers have introduced products that contain
occurred naturally to milk set aside for later use. The spoil- added sugars, fruit preserves, and flavors. These innova-
age organisms in the milk produced the proper conditions tions have also contributed to increased consumption, par-
for the preservation of the cultured product. The lowering ticularly in the United States.
of the pH of the milk by the organisms allows for the pres- During the fermentation the lactose in the milk is trans-
ervation of the product and contributes to its characteristic formed via pyruvic acid to lactic acid. The small amount of
aroma and taste. lactose or its hydrolysis products galactose and glucose is
The preparation of these cultured products became an below the threshold for detecting sweetness, but the lactic
art that survives today. The consumption of these products acid may account for more than 2% of the mass of the prod-
varies around the world, with the northern European uct and, by that, contribute a significant flavor and taste
countries consuming the greatest amount (20 kg/y/ effect. The fermentation pathway may favor both enanti-
person); and the United States consuming the least (1.2 mer formation (L( +) and D( ) lactic acid), as depicted in
kg/y/person) (14). However, the United States is a 300-fold Figure 1. The preferred metabolite, in flavor terms, is the
L( +) or a harsh off-flavor will be observed (15).
The basic microorganisms used are the lactobacilli,
Table 3. Fat Content of Cow's Milk streptococci, and leuconostocs. The major difference in
Type of fats Range of occurrence (%) their flavor is the amount of lactic acid produced and the
perception of the acid taste. One exception is the product
Triglycerides 97.0-98.0
Diglycerides 0.25-0.48
from the USSR called Kifur, which undergoes a secondary
Monoglycerides 0.015-0.038 fermentation to create ethyl alcohol. This product is also
Keto acid glycerides 0.85-1.28 known as the champagne of milk (16).
Aldehydo glycerides 0.011-0.015
Glyceryl ethers 0.011-0.023 Yogurt Flavor. Yogurt flavor is also influenced by acet-
Free Fatty Acids 0.10-0.44 aldehyde, another product of lactose from the fermentation
Phospholipids 0.2-1.0 of pyruvic acid by Lactobacillus bulgaricus. In yogurt the
Cerebrosides 0.013-0.066 acetaldehyde level differs greatly with the type of micro-
Sterols 0.12-0.4 organism^) used (17). There is no agreement on the acet-
Source: Ref. 13. aldehyde values that give an optimum flavor effect (18).
erated from the small amount of J-hydroxy acids occurring
in milk fat. On hydrolysis these compounds may sponta-
neously lactonize to form the corresponding J-lactones. The
r-lactones also may be formed from unsaturated CIS fatty
Lactose Pyruvic IX+) Lactic acids via hydration and ^-oxidation. The amount of lac-
acid tones formed is related to the type of feed, the season, the
type of breed, and the stage of lactation of the animal (25).
Estimates of the amount of lactone that can create a flavor
effect is reported at 7-85 ppm (26,27).
Butter and Cream Ice Cream. One other product produced from milk and
We have discussed the nature of milk flavor and the cul- butter is ice cream. Ice cream represents a congealed prod-
tured products derived from milk. The production of butter uct produced from cream, milk, skim milk, condensed milk,
from milk involves the concentration of the milk fat in the butter, or a combination of these ingredients, plus the ad-
milk by mechanical separation. The resultant product is a dition of sugar, flavorings, fruits, stabilizers and colors.
water in oil emulsion that has a mild characteristic flavor. Again, the basic contribution of the dairy ingredients to
During this process the exogenous enzymes (those en- the flavor is the fat and lactose, with those aromatic com-
zymes existing outside the cell) can break down the tri- ponents mentioned in the foregoing discussion and asso-
glycerides to free fatty acids; with improper handling this ciated with butter or cream flavor. Typically, the aromatic
may occur at a high level, leading to a flavor effect known portion of the flavor is greatly modified by the addition of
as rancidity. It is the short-chain free fatty acids (eg, bu- flavors and extracts.
tyric acid) that are responsible for the development of ran- Most of these basic dairy products, like butter, have fla-
cidity in butter. The role of other free fatty acids directly vor profiles that are simple. The real flavor masterpieces
on flavor seems small, except the deca- and dodecanoic of the dairy industry are the many varieties of cheese, with
acids, which appear in sweet cream butter at levels ex- their extremes in flavor types and intensities.
ceeding their flavor threshold (23). Because the Upases re-
sponsible for the hydrolysis of the triglycerides are very Cheese
heat stable, their activity continues even at low tempera- The many varieties of cheese represent many centuries of
ture during refrigerated or frozen storage. the cultivation of the art of cheese-making. Many different,
Rancidity. Rancidity is the major flavor defect in butter. probably accidentally developed, flavors, tastes, and tex-
The most useful index of rancidity is related to the amount tures have been developed. The products of cheese-making
of butyric acid found in the butter. A rancidity score de- are the result of many types of microorganisms (yeast, bac-
veloped by the University of Wisconsin correlates sensory teria, and mold) working together with the basic milk
data with individual free fatty acids concentration by step- source (typically cow's, goat's or sheep's milk) and the
wise regression and discriminatory analysis to index the knowledge of the control of fermentation. The variety of
relative rancid flavor intensities in butter (24). This is a methods is great and, so too, as has been noted, are the
very useful flavor index for the evaluation of butter. varieties of cheese produced throughout the world. We will
not attempt to discuss all the types known, but focus our
Lactone Formation. Lactones have also been considered flavor discussion on those well-known cheeses and the ba-
a major flavor attribute in butter and cream. They are gen- sic science of their formation.
Chemistry. The basic chemistry or biochemistry of The initial coagulation is achieved by using an added en-
cheese-making is the slow degradation of the macromole- zyme, rennin, or by lactic acid fermentation, or both, de-
cules (protein and lipid material) to small components of pending on the desired character of the final product. The
flavor (aroma and taste) value. Proteolysis (breakdown of green cheese is then ripened via the addition of certain
the protein by enzymes) during cheese ripening and aging microorganisms that will accomplish the breakdown of the
has a major influence on peptide formation. Peptides have protein, lipids, and sugars to the small molecular weight
various taste characteristics based on their polarity. The components that contribute to the cheesey flavors found in
basic taste sensations of sour/sweet and salt/bitter and the the final product.
flavor-enhancing property known as umami (the flavor-
enhancer taste associated with monosodium glutamate, Flavor Attributes of Cheese by Families. The less cheesey
MSG) are all taste attributes of peptides and amino acids. flavored cheeses are those with the least amount of rip-
It has been observed that the acid- (sour), hydrophobic- ening: fresh soft low-fat, higher fat cream/Neufchatel, and
(bitter), and glutamic/aspartic-rich (umami) peptides are the whey/ricotta type. Their flavors are primarily due to
the key taste peptides and amino acids in aged cheese (29). the components contributing to milk, cream, and butter
The hydrophilic (sweet) and salt-based peptides contribute flavor. They should be low in flavor intensity or they would
very little, as they are overwhelmed by the basic taste at- be considered to have a flavor defect.
tributes of the cheese. The natural sweetness from lactose The next group in terms of flavor strength consist of the
and the saltiness due to the salt (sodium chloride) added Swiss (Emmentaler), German (Muenster), and Dutch
to all cheese to produce a selective environment and the (Gouda) cheeses. The importance of peptides was recog-
chemistry needed to develop the specific cheese character nized in studies with Swiss cheese (30). Results indicated
play a more significant flavor role than do the peptides that that the small peptide that interacted with calcium and
have salty or sweet taste character. magnesium gives the cheese a sweet flavor, with the small
The salt content of selected cheeses is listed in Table 5. free peptides and amino acid contributing a slight brothy-
Note that the Roquefort or blue-cheese types have the nutty flavor. An important reaction in Emmentaler is the
highest salt content and those of the Swiss types have the conversion of pyruvic acid to propionic acid by propioni-
lowest. This is reflected in the basic salt taste of these bacterium. Propionic acid is found in Emmentaler in levels
cheeses. As we will see, the volatile chemicals formed from of up to 1%, and it is considered the basis of the sweet taste
the amino acid, peptides, lipids, and sugar are the back- of that cheese (31). Gouda has a defect called catty taint
bone of the characterizing flavors for the various cheese. that is due to the formation of 4-mercato-4-methylpen-
taone-2 (32).
Types of Cheeses. The family of cheeses generally rec- Cheddar cheese is by far the most consumed cheese in
ognized are the United States. It is produced by a unique process, ched-
daring, introduced in 1857 to repress the growth of spoil-
Fresh soft low-fat cheese age organisms during cheese-making. Cheddaring in-
Cream/Neufchatel volves the piling and repiling of blocks of warm cheese curd
in the cheese vat for ca 2 h. During this period the lactic
Gouda/Muenster
acid increases rapidly to a point where coliform bacteria
PortduSalut are destroyed.
Brie/Camembert The basic taste of cheddar is due to the peptide fraction
Blue cheeses and, in particular, to the umami and bitter components.
Goat cheeses The development of acetic acid during ripening contributes
to the sharpness of aged cheddar. The release of the acetic
Emmentaler
acid and amino acids continue during the ripening process.
Cheddar The medium chain fatty acids (C6 to CIS) that are released
Parmesan/Romano during the ripening process have also been shown to be
Whey/ricotta important in cheddar cheese flavor character (33).
Many other studies over a 10-year period indicated that
Processing. The basic processing involves the progres- it is necessary to produce the right level of acidity to pro-
sive dehydration and working of the coagulated and sepa- vide a reducing environment in the finished cheese so that
rated curds of milk to form a homogeneous compact mass. there may be a release of sulfur-containing compounds.
The lost of these compounds, in particular, methyl mercap-
tan, results in a cheese with little cheddar character (34-
Table 5. Salt Content of Certain Cheeses 36). Methanethiol has also been shown to be a significant
factor in aged cheddar (37-41). Methanethiol has a very
Cheese variety Salt (NaCl) (% w/w) fecal-like aroma with a threshold of detection reported at
Roquefort 4.1-5.0 0.02 ppb (42).
Feta 2.4-4.4 It has been suggested that acetylpyrazine and 2-meth-
Parmesan 2.1-3.5 oxy-3-ethylpyrazine are important in aged cheddar (43).
Edam 1.7-1.8 The possible microbial origins of pyrazines became evi-
Cheddar 1.6-1.7 dent when it was reported that dimethylpyrazine and 2-
Emmentaler 0.9-1.0
methoxy-isopropylpyrazine were isolated from milk con-
Table 6. Summary of the Flavor Chemistry of Dairy Products
Product Process Chemistry Major flavor contributors
Milk Homogenization and mild heat Natural components Balance of fats, salts, and lactose (milk sugar)
Defects Cooked >57C Maillard reactions Aldehydes and pyrazines
Prolonged cooking Caramelization Sulfur-containing components
Oxidation Oxidation Aldehydes
Sunlight exposure Sulfur reactions Methanethiol
Rancidity Lipolysis Butyric acid
Cream Fat separation Enzymolysis Methyl ketones (low level) diacetyl and lactones
Butter Further fat separation Enzymolysis Diacetyl and butyric acid
Cultured products Fermentation Lactic acid formation L( + ) Lactic acid
Yogurt Fermentation Acetaldehyde
Cheeses Salting NaCl
Aging Proteolysis Peptide formation
Swiss types Fermentation Propionibacteria Propionic acid
Cheddar types Cheddaring Lactic acid fermentation Lactic and acetic acid
Maillard reactions Acetyl pyrazine and other pyrazines
Blue types Fermentation Penicillium Methyl ketones (high amounts)
taminated by Pseudomonas taetrolens (44). Further sic start to an understanding of the complexities of dairy
alkylpyrazines have been isolated from mold ripened flavors.
cheese using Penicillium caseicolum cultures (45). The
overall flavor of good cheddar is a balance between the free
fatty acids and the other flavor components noted above. BIBLIOGRAPHY
The blue cheese family has been found to contain from
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port, National Agricultural Statistics Service, April 1998.
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generated from the use of the mold Penicillium roqueforti 2. S. F. Herb, P. Magidma, F. E. Lubby, and R. W. Riemenschei-
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the high levels of free fatty acids seen in the blue cheese American Oil Chemists' Society 39, 142-149 (1962).
made from cow's milk. Part of the flavor difference between
3. P. H. Haverkamp-Begemann and J. C. Koster, "4 Cis-
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(4:0) in Roquefort and the relative larger amount of C8:0 552-523 (1964).
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The major aroma character of the blue cheeses is due Journal of Dairy Science 48, 1557-1581 (1965).
to the high levels of methyl ketones found in the cheese. 5. S. Patton and G. W. Kurtz, "A Note on The Thiobarbituric Acid
These components have been isolated in milk and are as- Test for Milk Lipid Oxidation," Journal of Dairy Science 38,
sumed to be the product of the free fatty acid. The impor- 901 (1955).
tance of the methyl ketone in creating an imitation blue 6. J. E. Langler and E. A. Day, "Development and Flavor Prop-
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Secondary alcohol may be produced from the methyl ke- 47, 1291-1296 (1964).
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flavor profile to the methyl ketones, their intensity and Sulfide Precursor in Milk," Journal of Dairy Science 51, 122-
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Flavor of Milk," Journal of Dairy Science 39, 1469-1473
(1956).
CONCLUSION
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Stored Dry Whole Milk," Journal of Dairy Science 44, 1-9
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resent a great range of chemistry, biochemistry, and mi- 11. H. T. Badings and R. Neeter, "Recent Advances in the Study
crobiology. A summary of the major dairy products and of Aroma of Milk and Dairy Products," Netherlands Milk and
their associated significant flavor values is given in Table Dairy Journal 34, 9-30 (1980).
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terial. Science has yet to identify completely the compo- tection 43, 314-320 (1980).
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39. D. J. Manning, "Headspace Analysis of Hard Cheese," Journal
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23. E. H. Ramshaw, "Volatile Components of Butter and their
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24. A. H. Woo and R. C. Lindsay, "Statistical Correlation of Quan-
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IL, Changes in Flavor Quality and Ripening Products of Com- Teterboro, New Jersey
DAIRY INGREDIENTS: APPLICATIONS IN MEAT, Meat products can be classified in many different ways.
POULTRY, AND SEAFOODS Usually they are categorized as noncomminuted, coarsely
comminuted, and finely comminuted. The degree of com-
Meat and dairy products have several things in common. minution determines to a large extent the way of applying
Both are appreciated from organoleptic and nutritional dairy ingredients (see Table 2).
points of view. They have been traditionally regarded as
two of the main protein sources for humans. In a modern DAIRY INGREDIENTS IN MEAT PRODUCTS
diet, meat contributes about 35% of the protein intake, and
milk about 25% (1). The two most important ingredients from milk that find
Meat and dairy industries, furthermore, have a com- application in meat are predominantly milk protein and to
mon interest in maintaining a positive image for protein some extent the milk sugar or lactose.
of animal origin. However, in recent years there has been
criticism about the fat content of meat and dairy products, Lactose
and in some countries nutritional councils have recom-
mended substituting vegetable protein for animal protein Water binding in coarse and noncomminuted meats such
in the diet. In response to this criticism, meat and dairy as pumped ham is improved by extraction and swelling of
manufacturers have succeeded in introducing low-fat prod- meat proteins. For optimum extraction of protein from
ucts. A whole new range of meat and dairy foods is avail- meat, usually phosphate and salt are used. The concentra-
able, enabling the consumer to decide on the fat level de- tion of these ingredients is limited for organoleptic rea-
sired in the diet. In addition to providing protein and fat, sons. The effective salt and phosphate concentration on
meat and dairy products contribute to a great extent to the water and so the ionic strength can be increased by in-
intake of micronutrients. Meat is very important for the creasing the total solids of the brine mixture. For this pur-
intake of iron and certain vitamins such as thiamin and pose lactose is often used. Lactose has advantageous ef-
riboflavin, while dairy foods are critical for the intake of fects on
calcium and vitamins.
Liquid or solid dairy products are widely used in the Taste. Lactose has the capacity of masking the bitter
meat industry. They are mostly used with the objective to aftertaste of salts and phosphates.
improve taste or eye appeal, eg, cheese topping on burgers, Stability. Lactose improves water binding and slice-
cordon bleu entrees, and cheese franks. Fresh dairy cream ability and enhances the cured color.
is often used in pates or liver products and in many seafood Yield. Lactose is therefore used in liver products,
products. These applications are not within the scope of cooked hams, and cooked sausages. In sterilized prod-
this article on functionality. The two most important in- ucts the addition of lactose is less desirable because of
gredients from milk that find application in meat products the browning reaction.
are milk sugar (lactose) and predominantly milk protein.
Milk protein causes functional advantages, while lactose Lactose as an integrated part of whey powder or skim
is mostly used for taste improvement. milk powder (smp) is being used in many meat products.
This article reviews and updates the application of
these milk derivates in meat, poultry, and fish products.
Scientific backgrounds will be highlighted.
Table 2. Classification of Meat Product
Degree of
PROCESSED MEAT PRODUCTS comminution Examples
None Hams (cooked, smoked, dry), bacon, cooked
Processed meat products are all meat-based products that loins, shoulders, reformed hams
need more than just cutting from the carcass. It is esti- Coarse (Semi)dry sausages (salami, cervelat), fresh
mated that ca 25% of the worldwide meat production is sausages (bratwurst), hamburgers, meat
being processed (Table 1). In these processed meats dairy patties, meatballs, chicken nuggets
ingredients can be used as functional ingredients. Finely Frankfurters, hot dogs, polony, pariser, bologna,
mortadella, liver sausages/spreads, meat
loaves
Very hydrophobic residues Charged residues Very hydrophobic residues Charged residues
Hydrophobic residues Proline Hydrophobic residues Proline
Hydrophilic residues Crysteine Hydrophilic residues Crysteine
Figure 1. Amino acid sequence of /?-casein A. Figure 2. Amino acid sequence of a-lactalbumin B.
phates to a kind of cold meat slurry, then forming the ma-
trix in which the animal fatty tissue and possibly connec- Myofibrils
tive tissue material is dispersed.
In general, the final temperature during processing Mitochondria
does not exceed 15-180C. Often flavorings, binders, or
other additives are mixed in. Having this in mind, it will
be clear that hardly any of the abovementionedfinelycom- Myosin filaments
minuted products will show structures that are equal to
true and simple emulsions as defined in physical chemis- Actin filaments
try. Z-lines
The stability of finely comminuted meat products is
apart from production technology, formulation, the use of
binders, etcmainly determined by the quality of the meat
cuts used (6,7). Sarcoplasmic reticulum
With
Na-caseinate
Optimum stability
3% ssp/wsp proteins.
3% NaCl.
2% milk protein. To
recorder
The equipment for these tests is the gelograph (Fig. 9). Osci I Mating
The principle of this gelograph is as follows: A protein needle
Protein
solution that is placed in a waterbath is slowly heated (I0C/ solution
min). During this heat treatment the viscosity/gel strength Thermostatically
controlled water bath
of the solution is continuously measured by means of an
oscillating needle; this equipment operates in a nonde- Figure 9. The gelograph.
structive way; this means the gel structure that is formed
during the heating of the solution is not destroyed because
of minimal oscillating of the needle. In this way it is pos-
sible to imitate the gelling of meat proteins in pasteurized again. The reason for this phenomenon is not yet exactly
meat products (eg, a cooked ham). known (23,26,27).
An example is a product containing 60% lean meat, At a temperature of 570C there is again an increase in
which contains about 12% total meat protein. Roughly 50% gel strength. With further heating of the solution to 750C
of this protein is myofibrillar proteins. This is about 6%. the gel strength reaches a constant value of 150 m gels.
Suppose that 50% of total myofibrillar proteins are ex- Cooling down the solution results in a final gel strength of
tracted during massaging/tumbling. This means that 200 m gels. The same experiments are done in the pres-
the concentration of ssp will be around 3%. This is the ence of 2% milk proteins and 2% soy protein isolate. The
same concentration as used in the model experiments. Re- results are presented in Figure 12. A conclusion from this
sults of gelograph experiments are presented in Figures 10 figureaddition of 2% milk protein (which has no gellify-
and 11. ing capacity itself) results in a much higher gel strength of
Figure 10 shows the gel strength of a 3% wsp/ssp as a a heated meat protein solution.
function of temperature. The temperature starts at 2O0C This result supports the theory that there is a synergis-
(680F) and is increased at a rate of I0C/min; during this tic effect of milk proteins on the gellifying capacity of salt-
temperature increase the gel strength is measured as mili- soluble meat proteins, either milk proteins play a role in
gels. At 440C (UO0F) there is a sudden increase in gel the cross-linking of myosin molecules or they absorb a sig-
strength; this is caused by the aggregation of myosin mol- nificant amount of water, which results in a higher net con-
ecules (24). At higher temperatures the viscosity decreases centration of myosin molecules. Other nonmeat proteins
No addition
Temperature
No addition
Temperature
mGel
mGel
Temperature
Temperature
Time (min)
Time (min)
Figure 10. Results of an experiment on gelograph meat protein
Figure 12. Results of an experiment on gelograph meat protein
(no addition).
(no addition, caseinate, SPI).
Temperature
ufactured from materials such as trimmings, skin, fat, and
mechanically deboned poultry (mdp). The basic difference
between a poultry roll and a poultry bologna is that the
Time (min) bologna sausage contains curing salt and is finely emulsi-
fied (20). Poultry rolls normally have a certain ratio of fine
Figure 11. Results of an experiment on gelograph meat protein meat emulsion to meat chunks.
(no addition, caseinate). It is important to create an even color appearance
within the roll, ie, the color of the surrounding fine emul-
sion must match the color of the meat chunks. To obtain
only partially have this specific function (eg, soy protein this even and white color, it is recommended that milk pro-
isolate) or do not have it at all. teins be used in both basic components: part in the fine
emulsion and part mixed into the meat chunks.
POULTRY Some chicken or turkey bolognas are made from 100%
mechanically deboned poultry. From a technologic point of
Poultry Consumption view the poultry meat emulsion is not very different from
Whereas the consumption of red meat is stable or even the red meat emulsion. Sometimes poultry bolognas can
decreasing, poultry consumption has grown impressively have a dry mouthfeel. This can be corrected by the addition
over the last decade. The main reasons for the increase of of approximately 10% chicken skin/fat emulsion. Such a
consumption of poultry are a healthy image (lean, low in pre-emulsion is made of 1 part milk protein (sodium ca-
fat and cholesterol), increase in the amount of further- seinate), 5 parts chicken skin, 5 parts chicken fat, 6 parts
processed poultry meat (convenience), and relatively cheap water, and 2 parts ice.
source of animal protein. Without the assistance of such a prestabilized fat/skin
The consumption of poultry per capita in different areas emulsion, fatting out often occurs when the total fat con-
of the world is given in Table 5. tent reaches 20% or higher. The addition of milk protein
as a dry powder to such products (addition level generally
Poultry Rolls and Poultry Bolognas between 1.0 and 1.5%) improves the consistency of the final
Poultry rolls and poultry bolognas are in appearance very product as well; generally firmer and better sliceable prod-
similar to their red meat counterparts. They can be man- ucts are obtained.
Chicken Nuggets and Patties Table 6. Water-Packed Tuna
Since their introduction in the early 1980s, these poultry Component Percent of total
items have become very popular. Initially, a chicken nugget Steam-cooked tuna 75
was a solid piece of slightly marinated breast meat that Brine 25
was battered and breaded (20). Brine formula
Increased demand has forced the poultry processor to Water 86
use such parts as thigh meat, trimming, mechanically de- Salt 4
boned meat, and chicken skin. The target in combining all Milk protein hydrolysate 10
these ingredients in a nugget or a patty is to reach the
appearance, flavor, and bite of the original product as
closely as possible. Important in the stabilization of the
technologic point of view. Muscle fibers in seafood are al-
final product is the binding of the meat pieces, the water
most identical to fibers in red meat (31). A remarkable dif-
holding capacity, and the stability of the fat. ference is the very low content of collagen protein in fish-
Again, some basic rules in meat technology are very im- meat. This is the main reason for its softer texture and bite
portant: for optimal binding of the meat pieces, it is nec- compared to red meats.
essary to grind the meat before use; this creates relatively Because of the similarity between red meat and fish-
small meat pieces with a large surface area. During the
meat structure a lot of processing technologies from the
mixing stage, when salt and phosphates are added, it is red meat industry can be transferred to processed seafood.
important that sufficient meat proteins are extracted and This is especially true for fish sausages, fish nuggets, and
become hydrated in the continuous phase (28-30). On fry-
fish burgers.
ing, this continuous phase will gellify and cement the meat
pieces together. When milk protein is being used in these Canned Tuna
systems, they boost the meat protein gelation, resulting in Canned tuna, but eg, also canned salmon, mackerel, and
higher yields and better consistency of the final products. sardines, has been on the market for years as preserved
Products based on lean meat exclusively tend to be dry fish with a long shelf life. For a good heat transfer and
and tough after frying. By incorporation of prestabilized maintenance of the natural appearance and taste during
chicken fat/skin emulsion (usually 10%), flavor, consis- sterilization, it is absolutely necessary that the fish is
tency, and juiciness can be improved. canned with a liquid as heat transfer medium. Until re-
Whole Muscle Poultry Products cently the liquid used was usually oil, but as a result of
changes in the food consumption pattern and health con-
One of the most popular food items in this group of poultry sciousness of people, an aqueous solution has been applied
products is breast of turkey. Essentially the manufacturing more frequently in recent times. The switch from oil to an
process comes very close to the production process of re- aqueous solution is naturally associated with some
formed hams. Important differences are: lower injection changes in product characteristics, and it is apparent in
levels are applied (up to 25%); lower salt concentrations practice that milk protein hydrolysate is a perfect ingre-
are being used; no curing ingredients are being used, be- dient for stabilizing the canned product in respect to flavor,
cause a white color is desired; and the tumbling process is juiciness, and yield.
generally much shorter and less intense than that prac- In the preparation of canned tuna and other species of
ticed in ham manufacture. fish the starting point is usually precooked fish. After
For the production of breast of turkey both milk protein steam-cooking the fish is cooled and bones, skin, and the
(type sodium caseinate) and milk protein concentrates are dark fish flesh are removed carefully and the fish is suit-
used frequently. Usage levels vary from 0.8 to 1.5% (cal- able for canning. A formula for water-packed tuna is given
culated on the final product). Yield increases from 3.0 to in Table 6.
6.0% can be reached. At the same time the consistency,
binding, and sliceability of the product are improved. One Milk Protein Functionality
of the most important characteristics of milk proteins in A light color, mild flavor, juicy texture, and good water pen-
comparison to, eg, carbohydrate-based stabilizers is the etration during sterilization are extremely important char-
fact that milk proteins do not affect the original flavor and acteristics of premium quality canned tuna. Milk protein
palatability of the final product. hydrolysate promotes the juiciness of the fish structure,
gives a mild taste, and has an excellent effect on the water
SEAFOOD retention of the tuna during sterilization. Adding 10% milk
hydrolysate, as indicated in the brine formula, improves
Since the growing interest in food and health in general, the drain weight of the tuna by 6 to 8%. This means that
seafood items have become very popular over the last 10 milk proteins not only effect the quality of the final prod-
years. The major reasons for the impressive increase in uct, but have important economic advantages as well (30).
seafood consumption are sea foods are low in fat, high in
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See also DAIRY INGREDIENTS FOR FOODS; WHEY:
L. King, "Whey Protein Concentrates as Ingredients," Food Tech-
COMPOSITION, PROPERTIES, PROCESSING, AND USES.
nology Europe 3, 88-89 (1996).
A. Konno and M. Kimura, "Effects of Addition of Whey Protein
Concentrates on the Water-Retention Properties and Texture
of Ham," Journal of Japanese Society of Food Science and Tech-
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cessed Poultry Products," Fleischerei 42, HI-VI (1991).
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A. McCord, A. B. Smith and E. E. O'Neill, "Heat-Induced Gelation that have been introduced and refined since the time of
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C. Ramesh, Dairy-Based Ingredients, Eagan Press, Minn., 1997. use of pesticides and hormones. Well-managed herds can
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(1995).
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Microstructure of Partially Insolubilized Whey Protein Con- food. Consequently, the ability to transform milk and its
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Agric. Food Chem. 41, 1372-1378 (1993). extensive, as demonstrated by Figure 1.
S. Cunningham, "Marketing of Dairy Ingredients. Part 1," World L. Thorsen and T. Bergersen, "Quantitation of Milk Proteins in
of Ingredients Jan/Feb., 22-23, 25, 27 (1995). Heat-Treated Comminuted Meat Products," InformMAT2,62-
S. Cunningham, "Marketing of Dairy Ingredients. Part II," World 64 (1989).
of Ingredients March/April, 38-41 (1995). P. Walkenstrom and A. M. Hermansson, "Fine-Stranded Mixed
B. N. Dobson and D. P. Cornforth, "Nonfat Dry Milk Inhibits Pink Gels of Whey Proteins and Gelatin," Food Hydrocolloids 10,
Discoloration in Turkey Rolls," Poultry Science 71,1943-1946 51-62 (1996).
(1992). P. Walkenstrom and A. M. Hermansson, "High-Pressure Treated
B. N. Dobson et al., "Instrument for Measuring Bind Strength of Mixed Gels of Gelatin and Whey Proteins" Food Hydrocolloids
Restructured and Emulsion-Type Meat Products," J. Texture 11,195-208(1997).
Stud. 24, 303-310 (1993). P. Walkenstrom and A. M. Hermansson, "Mixed Gels of Gelatin
M. R. Ellekjaer, T. Naes, and P. Baardseth, "Milk Proteins Affect and Whey Proteins, Formed by Combining Temperature and
Yield and Sensory Quality of Cooked Sausages," J. Food ScL High Pressure," Food Hydrocolloids 11, 457-470 (1997).
61, 660-666 (1996). V. C. Weerasinghe et al., "Whey Protein Concentrate as a Protein-
S. B. El-Magoli, S. Larola, and P. M. T. Hansen, "Ultrastructure ase Inhibitor in Pacific Whiting Surimi," J. Food ScL 61, 367-
of Low-Fat Ground Beef Patties With Added Whey Protein 371 (1996).
Concentrate," Food Hydrocolloids 9, 291-306 (1995). J. N. de Wit, "Nutritional and Functional Characteristics of Whey
S. B. El-Magoli, S. Larola, and P. M. T. Hansen, "Flavor and Tex- Proteins in Food Products," Journal of Dairy Science 81, 597-
ture Characteristics of Low Fat Ground Beef Patties Formu- 608 (1998).
lated With Whey Protein Concentrate," Meat Science 42,179- O. Zorba et al., "The Possibility of Using Fluid Whey in Commi-
193 (1996). nuted Meat Products: Capacity and Viscosity of the Model
J. B. German and C. J. Dillard, "Fractionated Milk Fat: Compo- Emulsions Prepared Using Whey and Muscle Protein," Z.
sition, Structure, and Functional Properties," Food Technol. Lebensm.-Unters. Forsch. 200, 425-427 (1995).
52, 33-34, 36-38 (1998).
T P. Guinee and M. O. Corcoran, "Expanded Use of Cheese in
Processed Meat Products," Farm & Food 4, 25-28 (1994). MARTIEN VAN DEN HOVEN
A. Hendrickx, "New Protein Additive for Meat and Poultry Prod- Creamy Creations
ucts: Milk-Based Functional Protein Product," Fleischerei 43, Rijkevoort, The Netherlands
880, 883-884 (1992).
C. K. Hsu and E. Kolbe, "The Market Potential of Whey Concen-
trate as a Functional Ingredient in Surimi Seafoods," Journal
of Dairy Science 79, 2146-2151 (1996).
See also DAIRY INGREDIENTS FOR FOODS; WHEY:
L. King, "Whey Protein Concentrates as Ingredients," Food Tech-
COMPOSITION, PROPERTIES, PROCESSING, AND USES.
nology Europe 3, 88-89 (1996).
A. Konno and M. Kimura, "Effects of Addition of Whey Protein
Concentrates on the Water-Retention Properties and Texture
of Ham," Journal of Japanese Society of Food Science and Tech-
nology 40, 427-432 (1993). DAIRY INGREDIENTS FOR FOODS
H. A. M. Lemmers, "The Use of Dairy Ingredients in Further Pro-
cessed Poultry Products," Fleischerei 42, HI-VI (1991).
P. H. Lyons et al., "The Influence of Whey Protein/Carrageenan Milk and its products have been consumed by many gen-
Gels and Tapioca Starch on the Textural Properties of Low Fat erations of people of Western, Middle Eastern, Indian, and
Pork," Meat Science 51, 43-52 (1999). some African cultures. The nutritional value of dairy ma-
L. Mancini, "Dairy Ingredients, The natural Choice for Versatil- terials, properly handled, has been proven by widespread
ity," Food Engineering 64, 73-75 (1992). use, and their safety is assured by processing procedures
A. McCord, A. B. Smith and E. E. O'Neill, "Heat-Induced Gelation that have been introduced and refined since the time of
Properties of Salt-Soluble Muscle Proteins as Affected by Non- Pasteur. The great bulk of dairy products today recognize
meat Proteins," J. Food ScL 63, 580-583 (1998).
L. G. Phillips, M. J. Davis and J. E. Kinsella, "The Effects of Vari-
traditions of simple processes and physical separations,
ous Milk Proteins on the Foaming Properties of Egg White," avoiding chemicals and thereby preserving the natural
Food Hydrocolloids 3, 163-174 (1989). properties and the very desirable connotations of tradi-
E. Pitts, "The European Market for Dairy Ingredients," Journal tional products.
of the Society for Dairy Technology 48, 79-85 (1995). The more recently developed food-processing industries
K. Piyachomkwan and M. H. Penner, "Inhibition of Pacific Whit- have generated requirements for sophisticated perfor-
ing Surimi-Associated Protease by Whey Protein Concentrate," mance of dairy materials as ingredients for both familiar
J. Food Prot. 18, 341-353 (1995). and fabricated foods. Milk production does not require the
C. Ramesh, Dairy-Based Ingredients, Eagan Press, Minn., 1997. use of pesticides and hormones. Well-managed herds can
D. M. Smith and A. J. Rose, "Properties of Chicken Salt-Soluble produce milk with contaminant levels far below the re-
Protein and Whey Protein Concentrate Gels as Influenced by quirements of regulatory authorities. Active components
Sodium Tripolyphosphate," Poultry Science 74, 169-175
(1995).
that directly inhibit the processes of digestion, metabo-
S. Solberg, "Effective Product Development for Sausages," Liv- lism, and assimilation of nutrients are not present in milk.
smedelsteknik 38, 42-43 (1996). The nature of milk and its components is probably bet-
H. Y. Tan and D. M. Smith, "Dynamic Rheological Properties and ter characterized than the properties of any other basic
Microstructure of Partially Insolubilized Whey Protein Con- food. Consequently, the ability to transform milk and its
centrate and Chicken Breast Salt-Soluble Protein Gels," J. individual components into appropriate food ingredients is
Agric. Food Chem. 41, 1372-1378 (1993). extensive, as demonstrated by Figure 1.
Whole milk
tion of sweetened condensed milks are also required. Man- and electrodialysis are widely practiced (15,16). This has
ufacture by the appropriate use of heat and by control of allowed, in particular, the development of infant foods with
the mineral balance of the milks during processing are the low osmotic pressure and with managed mineral profiles
essential manufacturing processes. An improvement in the that appropriately meet nutritional needs for nutrient bal-
dispersibility of powdered products has been achieved by ance.
progressively improved drier design so that powder parti- Powders that contain milk fat are manufactured by
cles can be agglomerated without damage to the flavor or means that ensure that stale flavors, due to oxidation de-
nutritional properties of the product. More recently, effec- veloped during storage, do not arise in less than 12
tive coating of the particles with natural materials that months. Fat-containing powders that are intended for dis-
impart hydrophillic properties has been achieved. The re- persion in water require particular care in manufacture
duction of mineral levels by the processes of ion exchange (17).
High-fat powders, such as cream and butter powders filtration or centrifugation without coming into contact
which are particularly useful in the bakery industry, re- with any contaminating process aid. These processes yield
quire appropriate formulation to ensure that free-flow products that contain increased solid fat levels that are
properties are retained without loss of functional perfor- particularly useful for croissants and puff pastry (20).
mance (18). 3. Compounding of milkfat with vegetable oil to modify
spreadability properties of spreadable products results in
PRODUCTS IN WHICH MILKFAT IS THE DOMINANT a number of products that are successful at the retail level
COMPONENT and are attractive to the catering industry. Commonly,
these products employ 50% milkfat, 40% liquid vegetable
oil to increase the proportion of fat liquid at 5, and 10%
The use of cream, butter, and anhydrous milkfat (AMF),
hard stock to provide standup properties.
represent around 30% of the milkfat that is produced on
dairy farms worldwide. The 6.8 million tons used annually
means that milkfat is the third most widely used fat in The intensity of the yellow color of milkfat is, to some
worldwide commerce. The nature of fat on presentation to extent, controllable. The natural color of milk fat is caro-
the manufacturing process is pure and wholesome so that tene, a precurser of vitamin A, and is not implicated in any
the use of extensive clean-up processes and chemical pre- concern for health. Selection of the milkfat origin according
servative procedures are unnecessary. Milkfat has a desir- to breed of cow, feed source to the herd, and season of pro-
able and prestigious flavor, so the maintenance of that fla- duction will provide a range of color properties. More ex-
vor is of special importance. For this reason, refrigerated tensive color modification can be achieved by use of steam
storage of the products of milkfat is common. Because of a deodorization processes that are commonly employed in
significant level of naturally occurring materials that have the oils industry. It yields a white milkfat that is finding
antioxidant activity, and the widespread use of stainless extensive use in the manufacture of white cheeses and cof-
steel, which prevents contamination of milk with pro- fee whiteners and holds promise in other foods.
oxidants, extended shelf life can be achieved without re- Experimental investigation into the extensive modifi-
course to added antioxidents. cation of milkfat by complex processes such as interester-
The manufacturing processes that are used are inher- ification and hydrogenation has not, so far, yielded prod-
ently simple physical procedures such as churning and de- ucts having adequately improved benefits to justify the
hydration. The product range is shown in Figure 2. cost of the processes. Such approaches would simulta-
Rearrangement of the textural properties of milkfat is neously harm both the distinctive flavor and the natural-
achieved in a number of ways (19): ness of milkfat (Table 3).
Butter
manufacture Butter
Bulk salted
whey butter
In tins, sheets, pats, and bulk
Compound butter
Vegetable oils and (salted and unsalted)
mixes (fat mixes) Bulk unsalted
whey butter
Anhydrous blends
Cream Frozen cream Salted butter
Decolorized
anhydrous milkfat Unsalted butter
UHT cream Fractionated Salted lactic butter
anhydrous milkfat
Anhydrous Unsalted lactic butter
milk fat -Crystallized ghee
Ghee
Components
Casein-acid Broad functional performance, bland, Isoelectric precipitation, multiple 33,36
nutritionally strong washing procedure
Casein-rennet Nutritionally strong, including Enzymic precipitation and multiple 39
bioavailable calcium, stable bland washing
flavor, stretch properties for analogue
cheese
Whey protein
Lactalbumin Amino acid balance complementary to Heat precipitation and spray dried or ring 40
vegetable proteins dried
No interfering function
WPCa low protein level Milk powder alternative at economical Ultrafiltration to around 35% protein
price content
a
WPC , high protein level Soluble, bland, heat setting Ultrafilter and diafilter to around 75% 41
protein content
Isolates Pure proteins Ionic adsorption 42
Compounding
Specific functional performance Introduce vegetable proteins in blends or 43
by interreaction
Modification
Casemates
Sodium Solubility, natural emulsification, foam, Treat with sodium alkali and spray dry 36,44
fat binding, water holding
Bland flavor Carbon asorption
Calcium Colloidal protein, viscosity control Treat with calcium alkali and spray dry 45
Potassium Soluble and functional with low sodium Treat with potassium alkali
Various Special performance (e.g., high foam, low Various proprietary procedures 46
viscosity, gelation)
Whey proteins, WPCa Special performance (e.g., strong gels, Various proprietary procedures 47
heat stability)
Hydrolysates Nutritional performance, reduced Enzymic modification 4
allergenicity
0
WPC, whey protein concentrate.
Soft Cottage cheese
Dry salted
cheese
Semisoft Colby, Monterey, Egmont Young
Hard Granular, Cheddar, Cheshire Medium
Cheese Mature
Very hard Romano, Pepato, Parmesan
Brine salted
cheese
teristics as may be required for crust appearance, can be When used in the baking industry, it acts as a reducing
built-in during the manufacturing process. sugar to promote the Maillard reaction, which increases
Cheese flavors are often desired characteristics, and the browning of the crust. At higher temperatures it will
they range widely. They include fresh and carbohydrate- caramelize and so contribute to flavor.
derived flavor as in lactic cottage cheese and in creamy In formulated powdered products lactose crystals are
harvati; protein-derived flavor as in matured cheddar and slow to take up moisture and consequently minimize the
camembert; and fat-derived flavors as in parmesan and likelihood of caking and lumping. This same property is
blue cheeses. Further flavor extension by inclusion of nat- also a valuable aid to tableting.
ural materials such as spices and herbs can be used with Nutritionally, lactose has been shown to promote cal-
both natural and processed cheeses. Flavor contributions cium and phosphorous absorption, which is especially use-
are particularly significant to cheese sauces, dressings, ful in infant feeding preparations (56). It protects against
and parmesan toppings for European-style foods. destabilization of the caseinate complex during the drying
Particulate forms of cheese, prepared by grating, dicing, process. Its presence can also maintain biological activity
or drying, provide convenience for incorporation into food in the preparation of enzyme products. In brewing and
formulations. Varied flavor intensity (such as by enzyme baking applications, it is not fermented by conventional
treatment) can also be built into powdered cheeses. Pow- strains of yeast so its contribution to sweetness and color
dered yogurts are available, for coating and as formulation is not destroyed by the biological processes of those indus-
ingredients. These can be used, along with cream cheese, tries.
cottage cheese, and quarg for a range of cheese-cakes and The hydrolysis of lactose yields a sweet syrup that
similar products. contains glucose and galactose, which may have nutri-
New technologies, such as the use of ultrafiltration of tional advantages in some dietary applications. Lactose-
milk before cheesemaking, have already yielded commer- hydrolyzed syrups from permeates and wheys are com-
cially successful forms of feta cheese with increased shelf mercially available and are being used in confectionery
life and promise to further extend the range of product and ice cream (Table 6).
composition that will be created (Table 5).
Compositionally modified
Skim milk cheese Protein source Fat-reduced milk
Cream cheese Fat source flavor contribution and texture Cream addition, culturing
Modified cheese
Flavor enhanced Enzymic modification 53
Stretch control Acidity management
Processed cheese
Specific texture requirements, flavor Emulsification. Use of nondairy ingredients 53
modification
Specific shape e.g., Slices 54
Table 6. Lactose
Product class Performance requirement Process Reference
Component Low sweetness, reduction of water activity, enhanced browning. Concentration crystallization and 55,56,57,59
Promotion of calcium and phosphorus absorption (especially particle size control
in infant feeding), dispersing agent
Modified Sweet syrup Hydrolysis by lactase, 13,60
concentration
Transformed New materials Various 55,61
completely safe manner that would provide an alternative ticular food systems. Strong functional properties are pro-
to the use of antimicrobial agents. vided by dairy-based ingredients.
Natural antibodies are also present in very low concen- Casein protein has an open structure and has separate
tration in unprocessed milk, but traditional procedures areas of hydrophobic and hydrophyllic nature along the
have resulted in their inactivation. Procedures are now protein molecule. Consequently, it diffuses readily to in-
available that allow for preparation of protein products terfaces and has powerful emulsion-forming end stabiliz-
having biological activity, and there is evidence that dis- ing properties. Whey proteins unfold on heating and so,
ease control is achievable (62). Currently these products similarly, expose hydrophillic areas of the polypeptide
are targeted toward the problems of animal health. Sci- chains. They also gel and can provide natural thickening
entific enquiry is targeted toward the improvement of hu- and stabilizing function. The properties of caseinates and
man health. Wide-ranging implications for a new range of coprecipitates can be tailored by control of ionic content to
foods that have physiological functions exist and may pro- provide a range of viscosities, solubilities, foaming and
vide a new wave of the future (63,64). whipping (67), and surface activity (68). Measurements of
The recognition of the value of calcium naturally pres- the function of milk proteins have proved difficult to relate
ent in milk and cheese in meeting the nutritional needs of to the performance of these proteins in the complex envi-
aging people, particularly women, has resulted in a de- ronment of food systems (69), but considerable progress
mand for pure mineral ingredients of natural origin, fine has been made (70,71). Manufacturing techniques that
particle size, and clean flavor. The natural calcium content control the function of proteins are being practiced (72).
of milk is being recovered by precipitation processes for The functional properties of milkfat vary because of the
direct incorporation into foods (Table 7). effects on the secretory process in the mammary glands of
cows by the breed of the cow and by the type of feed that
PREPARED INGREDIENTS FOR FOODS she receives and that changes seasonally. Levels of tech-
nological control by temperature control during processing,
Sophisticated food ingredients have been specifically de- texturizing by physical means, and fractionation by con-
signed to provide physical functional performance for par- trolled crystallization minimize these variations (19).
Table 7. Nutritionally Valuable Components in Minor Concentrations
Product class Performance requirement of food formulations Process of manufacture Reference
Minerals Natural, origin, low flavor, bioavailable Precipitation
Biologically active
Lactoferrin Microbiological inhibition by iron binding. Sophisticated chromatography 65
Nutritionally available form of iron
Lactoperoxidase Natural antimicrobial system Sophisticated chromatography 65
Immunoglobulins Natural antibody active against a wide range of diseases Specialized ultrafiltration 66
Milkfats tailor-made for specific purposes are available possibilities for the future. While the opportunities for so-
(73). The primary role of milkfat, when incorporated into phisticated materials are exciting, the great bulk of dairy
a food, is the contribution that it makes to flavor, texture, ingredient purchases are based on the recognition of value
and consumer acceptability (74). for money and a clear understanding of the increasing
The benefits that dairy ingredients provide to food for- range of uses for products that can be produced by rela-
mulators differ according to the particular needs of each tively simple processes from a pure and natural raw ma-
industry. For confectionery products, milkfat is compatible terial.
with cocoa butter in that it becomes part of the continuous
fat phase and it contributes to smooth flavor and texture
ACKNOWLEDGMENTS
of milk chocolate. Caramel flavor is best developed from The authors gratefully acknowledge the valuable assistance of the
sweetened condensed milk by utilizing the browning prop- staff of the New Zealand Dairy Research Institute during the
erties of lactose and protein. Proteins, especially caseins, preparation of this paper.
enhance moisture retention by candy and control the quan-
tity of free and bound water (75). Hydrolyzed milk proteins
act as whipping agents for frappes and marshmallows (76). BIBLIOGRAPHY
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M. S. Haddadin, S. A. Ibrahim, and R. K. Robinson, "Preservation
73. D. Illingworth, J. C. Lloyd, and R. Norris, "Tailor-made Fats
from Milkfatthe New Zealand Experience," in Fats for the of Raw Milk by Activation of the Natural Lactoperoxidase Sys-
Future II, International Conference of New Zealand Institute tems," Food Control 7, 149-152 (1996).
of Chemistry, IUPAC, 1989. L. Hambraeus, "LactoferrinA Milk Protein in the News," Liv-
smedelsteknik 36, 42 (1994).
74. M. I. Gurr and R Walstra, "Fat Content of Dairy Foods in
W R. Harmer and C. Wijesundera, "Heat Stability of Milkfat in
Relation to Sensory Properties and Consumer Acceptability,"
Relation to Vegetable Oils," Australian Journal of Dairy Tech-
International Dairy Federation Bulletin, No. 244, 44-46
nology 51, 108-111 (1996).
(1990).
A. G. Khramtsov et al., "Application of Lactulose in Food for Chil-
75. L. B. Campbell and S. J. Pavlasek, "Dairy Products as Ingre- dren, Dietetic and Clinical Nutrition," Voprosy Pitaniya No. 2,
dients in Chocolates and Confections," Food Technology 41, 25-26 (1997).
78-85 (1987).
M. Kosempel, A. McAloon, and L. Roth, "Simulated Scale-Up and
76. L. Munksgaard and R. Ipsen, "Confectionery Products," in Cost Estimate of a Process for Alkaline Isomerization of Lac-
Dairy Ingredients for the Food Industry 3, International Dairy tose to Lactulose Using Boric Acid as Complexation Agent," J.
Federation, Brussels, Belgium, 1989. Chem. TechnoL Biotechnol. 68, 229-235 (1997).
77. W. B. Sanderson, "Cakes, Cookies, & Biscuits," in Dairy In- P. Lee and H. E. Swaisgood, "Modification of Milkfat Physical
gredients for the Food Industry, International Dairy Federa- Properties by Immobilized Fluorescens Lipase," J. Agric. Food
tion, Brussels, Belgium, 1985. Chem. 45, 3343-3349 (1998).
78. R. O. Cocup and W. B. Sanderson, "Functionality of Dairy In- V. V. Mistry and J. B. Pulgar, "Physical and Storage Properties of
gredients," Bakery Products Food Technology 41, 86-90 High Milk Protein Powder," International Dairy Journal 6,
(1987). 195-203 (1996).
79. J. M. G. Lankveld, "Meat and Meat Products," in Dairy In- D. L. Moreau and M. Rosenberg, "Storage Stability of Anhydrous
gredients for the Food Industry 2, International Dairy Fed- Milkfat Microencapsulated in Whey Proteins," Journal of
eration, Brussels, Belgium, 1987. Dairy Science 78 (Suppl. 1), 114 (1995).
80. van deu Hoven, "Functionality of Dairy Ingredients in Meat R. L. Motion, "Hydrolysates of Milk Protein," Proceedings of the
Products," Food Technology 41, 72-77 (1987). Nutrition Society of New Zealand 17, 56-63 (1992).
81. "Product UpdateIngredients from and for Dairy Products," M. S. Nam et al., "Lactoferrin: A Review," Korean Journal of Dairy
Food Technology 43, 108-122 (1989). Science 18, 289-298 (1996).
I. Nor-Aini et al., "Chemical and Physical Properties of Shorten-
ings Based on Palm Oil and Milkfat," ASEAN Food Journal 9,
GENERAL REFERENCES 141-146 (1994).
I. Nor-Aini et al., "Physical Characteristics of Shortenings Based
"Research Efforts Aim To Find New Uses for Milkfat Fractions in on Modified Palm Oil, Milkfat and Low Melting Milkfat Frac-
Food Ingredients," Canadian Dairy 75, 13 (1996). tion," Fett Wissenschaft Technologic 97, 253-260 (1995).
N. Dhanapati et al., "Effects of Mechanical Agitation, Heating and C. I. Onwulata, R. P. Konstance, and V. H. Holsinger, "Flow Prop-
pH on the Structure of Bovine Alpha Lactalbumin," Animal erties of Encapsulated Milkfat Powders as Affected by Flow
Science and Technology 68, 545-554 (1997). Agent," J. Food ScL 61, 1211-1215(1996).
C. I. Onwulata, P. W. Smith, and V. H. Holsinger, "Flow and Com- the rates of heat and mass transfer are described else-
paction of Spray-Dried Powders of Anhydrous Butteroil and where in the encyclopedia. Dehydration by heated air or
High Melting Milkfat Encapsulated in Disaccharides," J. Food
Sd. 60, 836-840 (1995).
heated surfaces is described in this article. Microwave, di-
C. I. Onwulata et al., "Particle Structures of Encapsulated Milkfat electric, radiant, and freeze-drying are described in other
Powders," Lebensm. Wiss. Technol. 29, 163-172 (1996). entries.
M. Papalois et al., "Australian Milkfat SurveyPhysical Proper-
ties," Australian Journal of Dairy Technology 51, 114117 Psychrometrics
(1996). The capacity of air to remove moisture from a food depends
D. Rousseau, A. R. Hill, and A. G. Marangoni, "Rheological Be-
haviour of Modified Milkfat," Journal of Dairy Science 78
on the temperature and the amount of water vapor already
(Suppl. 1), 103 (1995). carried by the air. The content of water vapor in air is ex-
V. K. S. Shukla, "Milkfat and Its Applications," World of Ingredi- pressed as either absolute humiditythe mass of water
ents, 30-31, 33 (Jan./Feb. 1995). vapor per unit mass of dry air (in kilograms per kilogram),
W. Strohmaier, "Lactulose, an Innovative Food IngredientPhys- termed moisture content in Fig. 1)or relative humidity
iological Aspects," Food Ingredients Europe Conference Pro- (RH) (in percent)the ratio of the partial pressure of water
ceedings, 69-72 (1997). vapor in the air to the pressure of saturated water vapor
C. Versteeg et al., "New Fractionated Milkfat Products," Austra- at the same temperature, multiplied by 100. Psychrometry
lian Journal of Dairy Technology 49, 57-61 (1994). is the study of the interrelationships of the temperature
X. Ye, "Studies on Minor Proteins in Bovine Milk," Journal of the and humidity of air. These properties are most conven-
Faculty of Applied Biological Science Hiroshima University 34,
194-195 (1995).
iently represented on a phychrometric chart (Fig. 1).
The temperature of the air, measured by a thermometer
bulb, is termed the dry-bulb temperature. If the thermom-
ROBIN M. FENWICK eter bulb is surrounded by a wet cloth, heat is removed by
K. J. KIRKPATRICK evaporation of the water from the cloth and the tempera-
New Zealand Dairy Board
ture falls. This lower temperature is called the wet-bulb
Wellington, New Zealand
temperature. The difference between the two tempera-
tures is used to find the relative humidity of air on the
See also DAIRY INGREDIENTS: APPLICATIONS IN MEAT, psychrometric chart. An increase in air temperature, or
POULTRY, AND SEAFOODS; WHEY: COMPOSITION,
reduction in RH, causes water to evaporate from a wet sur-
PROPERTIES, PROCESSING, AND USES.
face more rapidly and therefore produces a greater fall in
temperature. The dew point is the temperature at which
air becomes saturated with moisture (100% RH). Adiabatic
DEHYDRATION cooling lines are the parallel straight lines sloping across
the chart, which show how absolute humidity decreases as
Dehydration (or drying) is defined as the application of the air temperature increases.
heat under controlled conditions to remove the majority of
the water normally present in a food by evaporation (or in Sample Problems 1. Using the psychrometric chart
the case of freeze-drying by sublimation). This definition (Fig. 1), calculate the following.
excludes other unit operations that remove water from
foods (eg, mechanical separations, membrane concentra- 1. The absolute humidity of air that has 50% RH and
tion, evaporation, and baking) as these normally remove a dry-bulb temperature of 6O0C.
much less water than dehydration. The main purpose of 2. The wet-bulb temperature under these conditions.
dehydration is to extend the shelf life of foods by a reduc- 3. The RH of air having a wet-bulb temperature of 450C
tion in water activity. This inhibits microbial growth and and a dry-bulb temperature of 750C.
enzyme activity, but the product temperature is usually 4. The dew point of air cooled adiabatically from a dry-
insufficient to cause inactivation. The reduction in weight bulb temperature of 550C and 30% RH.
and bulk of food reduces transport and storage costs and, 5. The change in RH of air with a wet-bulb temperature
for some types of food, provides greater variety and con- of 390C, heated from a dry-bulb temperature of 5O0C
venience for the consumer. Drying causes deterioration of to a dry-bulb temperature of 860C.
both the eating quality and the nutritive value of the food. 6. The change in RH of air with a wet-bulb temperature
The design and operation of dehydration equipment aim of 350C, cooled adiabatically from a dry-bulb tem-
to minimize these changes by selection of appropriate dry- perature of70C to 4O0C.
ing conditions for individual foods. Examples of commer-
cially important dried foods are sugar, coffee, milk, potato, Solution to Sample Problems 1.
flour (including bakery mixes), beans, pulses, nuts, break-
fast cereals, tea, and spices. 1. 0.068 kg/kg of dry air. Find the intersection of the
6O0C and 50% RH lines and then follow the chart
THEORY horizontally right to read the absolute humidity.
2. 47.50C. From the intersection of the 6O0C and 50%
Dehydration involves the simultaneous application of heat RH lines, extrapolate left parallel to the wet-bulb
and removal of moisture from foods. Factors that control lines to read the wet-bulb temperature.
C. I. Onwulata, P. W. Smith, and V. H. Holsinger, "Flow and Com- the rates of heat and mass transfer are described else-
paction of Spray-Dried Powders of Anhydrous Butteroil and where in the encyclopedia. Dehydration by heated air or
High Melting Milkfat Encapsulated in Disaccharides," J. Food
Sd. 60, 836-840 (1995).
heated surfaces is described in this article. Microwave, di-
C. I. Onwulata et al., "Particle Structures of Encapsulated Milkfat electric, radiant, and freeze-drying are described in other
Powders," Lebensm. Wiss. Technol. 29, 163-172 (1996). entries.
M. Papalois et al., "Australian Milkfat SurveyPhysical Proper-
ties," Australian Journal of Dairy Technology 51, 114117 Psychrometrics
(1996). The capacity of air to remove moisture from a food depends
D. Rousseau, A. R. Hill, and A. G. Marangoni, "Rheological Be-
haviour of Modified Milkfat," Journal of Dairy Science 78
on the temperature and the amount of water vapor already
(Suppl. 1), 103 (1995). carried by the air. The content of water vapor in air is ex-
V. K. S. Shukla, "Milkfat and Its Applications," World of Ingredi- pressed as either absolute humiditythe mass of water
ents, 30-31, 33 (Jan./Feb. 1995). vapor per unit mass of dry air (in kilograms per kilogram),
W. Strohmaier, "Lactulose, an Innovative Food IngredientPhys- termed moisture content in Fig. 1)or relative humidity
iological Aspects," Food Ingredients Europe Conference Pro- (RH) (in percent)the ratio of the partial pressure of water
ceedings, 69-72 (1997). vapor in the air to the pressure of saturated water vapor
C. Versteeg et al., "New Fractionated Milkfat Products," Austra- at the same temperature, multiplied by 100. Psychrometry
lian Journal of Dairy Technology 49, 57-61 (1994). is the study of the interrelationships of the temperature
X. Ye, "Studies on Minor Proteins in Bovine Milk," Journal of the and humidity of air. These properties are most conven-
Faculty of Applied Biological Science Hiroshima University 34,
194-195 (1995).
iently represented on a phychrometric chart (Fig. 1).
The temperature of the air, measured by a thermometer
bulb, is termed the dry-bulb temperature. If the thermom-
ROBIN M. FENWICK eter bulb is surrounded by a wet cloth, heat is removed by
K. J. KIRKPATRICK evaporation of the water from the cloth and the tempera-
New Zealand Dairy Board
ture falls. This lower temperature is called the wet-bulb
Wellington, New Zealand
temperature. The difference between the two tempera-
tures is used to find the relative humidity of air on the
See also DAIRY INGREDIENTS: APPLICATIONS IN MEAT, psychrometric chart. An increase in air temperature, or
POULTRY, AND SEAFOODS; WHEY: COMPOSITION,
reduction in RH, causes water to evaporate from a wet sur-
PROPERTIES, PROCESSING, AND USES.
face more rapidly and therefore produces a greater fall in
temperature. The dew point is the temperature at which
air becomes saturated with moisture (100% RH). Adiabatic
DEHYDRATION cooling lines are the parallel straight lines sloping across
the chart, which show how absolute humidity decreases as
Dehydration (or drying) is defined as the application of the air temperature increases.
heat under controlled conditions to remove the majority of
the water normally present in a food by evaporation (or in Sample Problems 1. Using the psychrometric chart
the case of freeze-drying by sublimation). This definition (Fig. 1), calculate the following.
excludes other unit operations that remove water from
foods (eg, mechanical separations, membrane concentra- 1. The absolute humidity of air that has 50% RH and
tion, evaporation, and baking) as these normally remove a dry-bulb temperature of 6O0C.
much less water than dehydration. The main purpose of 2. The wet-bulb temperature under these conditions.
dehydration is to extend the shelf life of foods by a reduc- 3. The RH of air having a wet-bulb temperature of 450C
tion in water activity. This inhibits microbial growth and and a dry-bulb temperature of 750C.
enzyme activity, but the product temperature is usually 4. The dew point of air cooled adiabatically from a dry-
insufficient to cause inactivation. The reduction in weight bulb temperature of 550C and 30% RH.
and bulk of food reduces transport and storage costs and, 5. The change in RH of air with a wet-bulb temperature
for some types of food, provides greater variety and con- of 390C, heated from a dry-bulb temperature of 5O0C
venience for the consumer. Drying causes deterioration of to a dry-bulb temperature of 860C.
both the eating quality and the nutritive value of the food. 6. The change in RH of air with a wet-bulb temperature
The design and operation of dehydration equipment aim of 350C, cooled adiabatically from a dry-bulb tem-
to minimize these changes by selection of appropriate dry- perature of70C to 4O0C.
ing conditions for individual foods. Examples of commer-
cially important dried foods are sugar, coffee, milk, potato, Solution to Sample Problems 1.
flour (including bakery mixes), beans, pulses, nuts, break-
fast cereals, tea, and spices. 1. 0.068 kg/kg of dry air. Find the intersection of the
6O0C and 50% RH lines and then follow the chart
THEORY horizontally right to read the absolute humidity.
2. 47.50C. From the intersection of the 6O0C and 50%
Dehydration involves the simultaneous application of heat RH lines, extrapolate left parallel to the wet-bulb
and removal of moisture from foods. Factors that control lines to read the wet-bulb temperature.
Psychrometric
chart (10-120 0C Relative humidity (%)
Based on a barometric pressure of 101.325 kPa
Figure 1. Psychometric chart (10-12O0C based on barometric pressure of 101.325 kPa. Source:
Courtesy of Chartered Institution of Building Services Engineers.
3. 20%. Find the intersection of the 450C and 75%C the moisture content and Aw of foods are shown in Table 1.
lines and follow the sloping RH line upward to read The effect of reduced Aw on food stability is shown in Ta-
the % RH. ble 2.
4. 360C. Find the intersection of the 550C and 30% RH Water in food exerts a vapor pressure. The size of the
lines and follow the wet-bulb line left until the RH vapor pressure depends on
reaches 100%.
5. 50-100%. Find the intersection of the 390C wet-bulb 1. The amount of water present.
and the 5O0C dry-bulb temperatures and follow the 2. The temperature.
horizontal line to the intersection with the 860C dry- 3. The concentration of dissolved solutes (particularly
bulb line; read the sloping RH line at each intersec- salts and sugars) in the water.
tion (this represents the changes that take place
when air is heated before being blown over food. Water activity is defined as the ratio of the vapor pres-
6. 10-70%. Find the intersection of the 350C wet-bulb sure of water in a food to the saturated vapor pressure of
and 7O0C dry-bulb temperatures and follow the wet- water at the same temperature:
bulb line left until the intersection with the 4O0C dry-
bulb line; read sloping RH line at each intersection Aw = (4)
(this represents the changes taking place as the air M)
is used to dry food; the air is cooled and becomes
more humid as it picks up moisture from the food). where P (Pa) is vapor pressure of the food and P0 (Pa) the
vapor pressure of pure water at the same temperature. Aw
Water Activity
is related to the moisture content by the Brunauer-
Emmett-Teller (BET) equation
Deterioration of foods by microorganisms can take place
A
rapidly, whereas enzymatic and chemical reactions take W 1 C- I
+
place more slowly during storage. In either case, water is M(I - Aw) " M^ 1^C" Aw (5)
the curve, to point A, represents monolayer water, which The sorption isotherm indicates the Aw at which a food
is very stable, unfreezable, and not removed by drying. The is stable and allows predictions of the effect of changes in
second, relatively straight part of the curve (AB) repre- moisture content on Aw and hence on storage stability. It
sents water absorbed in multilayers within the food and is used to determine the rate and extent of drying, the op-
solutions of soluble components. The third portion (above timum frozen storage temperatures, and the moisture-
point B) is free water condensed within the capillary struc- barrier properties required in packaging materials.
ture or in the cells of a food. It is mechanically trapped The rate of change in Aw on a sorption isotherm differs
within the food and held only by weak forces. It is easily according to whether moisture is removed from a food (de-
removed by drying and easily frozen, as indicated by the sorption) or it is added to dry food (adsorption) (Fig. 2).
steepness of the curve. Free water is available for micro- This is termed a hysteresis loop. The difference is large in
bial growth and enzyme activity, and a food that has a some foods, eg, rice, and is important for example in de-
moisture content above point B on the curve is likely to be termining the protection required against moisture up-
susceptible to spoilage. take.
Nonhygroscopic foods have a constant water vapor pres-
Desorption
sure at different moisture contents. The difference is found
by using sorption isotherms.
Moisture content (%) When food is placed in a dryer, there is a short initial
settling down period as the surface heats up to the wet-
bulb temperature (AB in Fig. 4a). Drying then commences
and, provided that water moves from the interior of the
food at the same rate as it evaporates from the surface, the
Adsorption surface remains wet. This is known as the constant-rate
period and continues until a certain critical moisture con-
tent is reached (BC in Figs. 4a and b). In practice, however,
different areas of the surface of the food dry out at different
Relative humidity (%) rates and, overall, the rate of drying declines gradually
during the constant-rate period. Thus the critical point is
Figure 2. Water sorption isotherm. not fixed for a given food and depends on the amount of
food in the dryer and the rate of drying.
The three characteristics of air that are necessary for
Mechanism of Drying successful drying in the constant rate period are
When hot air is blown over a wet food, heat is transferred 1. A moderately high dry-bulb temperature.
to the surface, and latent heat of vaporization causes water 2. A low RH.
to evaporate. Water vapor diffuses through a boundary 3. A high air velocity.
film of air and is carried away by the moving air (Fig. 3).
This creates a region of lower water vapor pressure at the The boundary film of air surrounding the food acts as a
surface of the food, and a water vapor pressure gradient is barrier to the transfer of both heat and water vapor during
established from the moist interior of the food to the dry
air. This gradient provides the driving force for water re-
moval from the food.
Water moves to the surface by the following mecha-
nisms:
Moisture content
Drying air
Drying rate
Moisture content
(b)
Moisture
Food cells Figure 4. (a) and (b) Drying curves. The temperature and hu-
midity of the drying air are constant and all heat is supplied to
Figure 3. Movement of moisture during drying. the surface by convection.
drying. The thickness of the film is determined primarily and the surface temperature and rate of moisture loss).
by the air velocity. If this is too low, water vapor leaves the The size of food pieces has an important effect on the dry-
surface of the food and increases the humidity of the sur- ing rate in both the constant- and the falling-rate periods.
rounding air, to cause a reduction in the water vapor pres- In the constant-rate period, smaller pieces have a larger
sure gradient and the rate of drying (Similarly, if the tem- surface area available for evaporation, whereas, in the
perature of the drying air falls or the humidity rises, the falling-rate period, smaller pieces have a shorter distance
rate of evaporation falls and drying slows). for moisture to travel through the food. Other factors that
When the moisture content of the food falls below the influence the rate of drying include:
critical moisture content, the rate of drying slowly de-
creases until it approaches zero at the equilibrium mois- 1. The fat content of the food (higher fat contents gen-
ture content (ie, the food comes into equilibrium with the erally result in slower drying, as water is trapped
drying air). This is known as the falling-rate period. Non- within the food).
hygroscopic foods have a single falling-rate period (CD in 2. The method of preparation of the food (cut surfaces
Fig. 4a and b), whereas hygroscopic foods have two periods. lose moisture more quickly than losses through skin.
In the first period, the plane of evaporation moves inside
the food, and water diffuses through the dry solids to the 3. The amount of food placed into a dryer in relation to
drying air. It ends when the plane of evaporation reaches its size (in a given dryer, faster drying is achieved
the center of the food and the partial pressure of water falls with smaller quantities of food).
below the saturated water vapor pressure. The second pe-
riod occurs when the partial pressure of water is below the The rate of heat transfer is found using
saturated vapor pressure and drying is by desorption.
During the falling-rate period, the rate of water move- Q = hsA(Oa - O8) (6)
ment from the interior of the food to the surface falls below
the rate at which water evaporates to the surrounding air. The rate of mass transfer is found using
The surface therefore dries out. This is usually the longest
period of a drying operation and, in some foods, eg, grain -mc = KgA(Hs - HJ (7)
drying, where the initial moisture content is below the
critical moisture content, the falling-rate period is the only
part of the drying curve to be observed. During the falling- Because during the constant-rate period, an equilibrium
rate period, the factors that control the rate of drying exists between the rate of heat transfer to the food and the
change. Initially, the important factors are similar to those rate of mass transfer in the form of moisture loss from the
in the constant-rate period, but gradually the rate of mass food, these rates are related by
transfer becomes the controlling factor. This depends
mostly on the temperature of the air and the thickness of -mc = ^(0a ~ O8) (8)
the food. It is unaffected by both the RH of the air (except
in determining the equilibrium moisture content) and the
velocity of the air. The air temperature is therefore con- where Q (J/s) is the rate of heat transfer, hc W/m2/K the
trolled during the falling rate period, whereas the air ve- surface heat transfer coefficient for convective heating, A
locity and temperature are more important during the (m2) the surface area available for drying, Oa (0C) the av-
constant-rate period. In practice, foods may differ from erage dry-bulb temperature of drying air, O8 (0C) the aver-
these idealized drying curves owing to shrinkage, changes age wet-bulb temperature of drying air, mc (kg/s) the
in the temperature and rate of moisture diffusion in dif- change in mass with time (drying rate), Kg (kg/m2/s) the
ferent parts of the food, and changes in the temperature mass transfer coefficient, H8 (kilograms of moisture per
and humidity of the drying air. kilogram dry air) the humidity at the surface of the food
The surface temperature of the food remains close to the (saturation humidity), Ha (kilograms of moisture per kilo-
wet-bulb temperature of the drying air until the end of gram dry air) the humidity of air, and /I (J/kg) the latent
the constant-rate period, owing to the cooling effect of the heat of evaporation at the wet-bulb temperature.
evaporating water. During the falling-rate period the The surface heat transfer coefficient (hc) is related to
amount of water evaporating from the surface gradually the mass flow rate of air using the following equations: for
decreases but, as the same amount of heat is being sup- parallel airflow,
plied by the air, the surface temperature rises until it
reaches the dry-bulb temperature of the drying air. Most hc = 14.3G08 (9)
heat damage to food therefore occurs in the falling rate
period.
and for perpendicular airflow,
Calculation of Drying Rate
hc = 24.2G0-37 (10)
The rate of drying depends on the properties of the dryer
(the dry-bulb temperature, RH and velocity of the air, and Where G (kg/m2/s) is the mass flow rate of air.
the surface heat transfer coefficient) and the properties of For a tray of food in which water evaporates only from
the food (the moisture content, surface-to-volume ratio, the upper surface, the drying time is found using
Sample Problem 2. Peas with an average diameter of 6
-m c = ^- (00 - 0.) (11) mm and a density of 880 kg/m3 are dried in a fluidized-bed
/7 AX
dryer. The minimum voidage is 0.4 and the cross-sectional
where p (kg/m3) is the bulk density of food and x (m) the area of the bed is 0.25 m2. Calculate the minimum air ve-
thickness of the bed of food. locity needed to fluidize the bed if the air density is 0.96
The drying time in the constant-rate period is found kg/m3 and the air viscosity is 2.15 X 10" 5 N- s/m2.
using
Solution of Sample Problem 2. From equation 15
_ PMM1 - Mc)
(12) (880 - 0.96)9.81 (0.006)2(0.4)3 oc .l
* ~ hc(6a - B8) VF =
2.15 X 10- 180(1 - 0.4) = 8'5 m/S
where t (s) is the drying time, Af1 (kg/kg of dry solids) the
Derivations of these equations are described in Refs.
initial moisture content, and M0 (kg/kg of dry solids)
the critical moisture content. 6-8.
For water evaporating from a spherical droplet in a
Sample Problem 3. A conveyor dryer is required to dry
spray dryer, the drying time is found using
peas from an initial moisture content of 78% to 16% mois-
ture (wet-weight basis) in a bed 10 cm deep with a voidage
_ ^ M1 - Mf
of 0.4. Air at 850C with a relative humidity of 10% is blown
3hc(0a - 0S) 1 + M1 perpendicularly through the bed at 0.9 m/s. The dryer belt
measures 0.75 m wide and 4 m long. Assuming that drying
where PI (kg/m3) is the density of the liquid, r (m) the ra- takes place from the entire surface of the peas and there
dius of the droplet, Mf (kg/kg of dry solids) the final mois- is no shrinkage, calculate the drying time and energy con-
ture content. sumption in both the constant and the falling-rate periods.
In the falling-rate period, moisture gradients change (Additional data: The equilibrium moisture content of the
throughout the food and the temperature slowly increases peas is 9%, the critical moisture content 300% (dry-weight
from the wet-bulb temperature to the dry-bulb tempera- basis), the average diameter 6 mm, the bulk density 610
ture as the food dries. The following equation is used to kg/m3, the latent heat of evaporation 2300 kJ/kg, the sat-
calculate the drying time from the start of the falling-rate urated water vapor pressure at wet-bulb temperature 61.5
period to the equilibrium moisture content using a number mmHg, and the mass transfer coefficient 0.015 kg/m2/s).
of assumptions concerning, eg, the nature of moisture
movement and the absence of shrinkage of the food: Solution to Sample Problem 3. In the constant-rate pe-
riod, from equation 10:
= px(Mc - Me) llJM0 - Me\ (14)
* KJP. - PJ \M-^rJ hc = 24.2(0.9)037 = 23.3 W/m2/K
where M6 (kg/kg of dry solids) is the equilibrium moisture From Fig. 1 for 0a = 850C and RH - 10%,
content, M (kg/kg of dry solids) the moisture content at
time t from the start of the falling-rate period, P8 (mmHg) O8 = 420C
the saturated water vapor pressure at the wet-bulb tem-
To find the area of the peas,
perature, and Pa (mmHg) the partial water vapor pressure.
The velocity of the air needed to achieve fluidization of
spherical particles is calculated using Volume of a sphere = | nr3 = 4 X 3.142(0,00
G
= 339 X HT9 m3
0 _ (Ps - P)g dV (15)
Vf
It 180(1 - e) (15) Volume of the bed = 0.75 X 4 X 0.1 = 0.3 m3
Volume of peas in the bed = 0.3(1 - 0.4) = 0.18 m3
where iy (m/s) is the fluidization velocity, ps (kg/m3 the den-
sity of the solid particles, p (kg/m3) the density of the fluid, . _ volume of peas in bed
Number of peas =
g (m/s2) the acceleration due to gravity, ju (N s/m2) the volume each pea
viscosity of the fluid, d (m) the diameter of the particles, e _ 0.18 _ * Q 1 x 105
the voidage of the bed. ~ 339 X 10-9 '5'31 X 10
Formulas for foods of other shapes are described in Ref.
Area of a sphere = 4nnr2 = 4 X 3.142(0.003)2
5. The minimum air velocity needed to convey particles is
= 113 X KT6 m2
found using:
and
, \/[i%^>]
L oL p J d
6, Total area of peas = 5.31 X 105 X 113 X 10~6
= 60 m2
where ve (m/s) is the minimum air velocity and Cd (= 0.44
for Re = 500-200,000) the drag coefficient. From equation 8:
OQ o vx fin From Equation 14,
Drying rate = ' (85 - 42) = 0.026 kg/s
Z.o X IU6
_ (3 - 0.099)610 X 0.1 / 3 - 0.099 \
n S
From a mass balance * 0.015(61.5 - 6.15) V0.19 - 0.099/ " '
- 12.3 min
Volume of peas = 0.18 m3
Bulk density - 610 kg/in"3 From a mass balance, at the critical moisture content,
96.6 kg contains 25% solids = 24.16 kg. After drying in
the falling-rate period, 84% solids = 24.16 kg. Therefore,
Therefore,
Me = =
9l -" Drum area = ndl = 3.142 X 0.7 X 0.85 = 1.87 m2
Therefore, food when it is in the falling-rate period, when moisture
removal is most time consuming. The deep bed of food per-
Mass of food on the drum = (1.87 X 0.75)0.0006 mits variations in moisture content to be equalized and
X 1020 = 0.86 kg acts as a store to smooth out fluctuations in the product
flow between drying stages and packaging. However, the
From a mass balance (initially the food contains 80% mois- dryers may be several meters high, and it is therefore im-
ture and 20% solids), portant that foods are sufficiently strong to withstand com-
pression at the base and to retain an open structure to
Mass of solids = 0.86 X 0.2 = 0.172 kg permit the passage of hot air through the bed.
After drying, 80% solids = 0.172 kg. Therefore, Cabinet Dryers (Tray Dryers). These dryers consist of an
insulated cabinet fitted with shallow mesh or perforated
100 trays, each of which contains a thin (2-6 cm deep) layer of
Mass of dried food = - X 0.172 = 0.215 kg food. Hot air is circulated through the cabinet at 0.5-5
80
m/s per square meter tray area. A system of ducts and
Mass loss = 0.86 - 0.215 = 0.645 kg baffles is used to direct air over and/or through each tray,
to promote uniform air distribution. Additional heaters
From equation 17, may be placed above or alongside the trays to increase the
rate of drying. Tray dryers are used for small-scale pro-
Q = 1200 X 1.87 (150 - 100) = 1.12 X 105 J/s duction (1-20 tons/day) or for pilot-scale work. They have
1 12 X 105 low capital and maintenance costs, but compared to dryers
Drying rate = 2 257 x 106 kg/S =
'5 kg/S that have more sophisticated control they produce more
variable product quality.
In developing countries the high capital investment for
and sophisticated dryers often cannot be justified, but there is
a need for better-quality products than those produced by
Residence time required = ' = 13 s sun or solar drying. A small dryer consisting of a 60 kW
gas or kerosine heater/blower unit and a cabinet fitted
with 15 mesh trays has been developed to meet this need
As only three-quarters of the drum surface is used, 1 rev (14). In operation, air is passed across the food in each tray.
should take (100/75) X 13 = 17.3 s. Therefore, speed = 3.5 Trays are loaded at the top of the dryer and unloaded at
rev/min. the base using metal fingers to move the tray stack. The
dryer therefore operates semicontinuously and with
EQUIPMENT counter-current airflow. Typical tray loadings are 5 kg, and
the tray change cycle is 15-20 minutes.
Most commercial dryers are insulated to reduce heat
losses, and they recirculate hot air to save energy. Many Conveyor Dryers (Belt Dryers). Continuous conveyor
designs have energy-saving devices that recover heat from dryers are up to 20 m long and 3 m wide. Food is dried on
the exhaust air or automatically control the air humidity a mesh belt in beds 5-15 cm deep. The airflow is initially
(9,10). Computer control of dryers is increasingly sophis- directed upward through the bed of food and then down-
ticated (11) and also results in important savings in en- ward in later stages to prevent dried food from blowing out
ergy. The criteria for selection of drying equipment and of the bed. Two- or three-stage dryers (Fig. 5) mix and re-
potential applications are described in Table 3. The rela- pile the partly dried shrunken food into deeper beds (to
tive costs of different drying methods are reported as fol- 15-25 cm and 250-900 cm in three-stage dryers). This im-
lows (12): forced-air drying, 198; fluidized-bed drying, 315; proves uniformity of drying and saves floor space. Foods
drum drying, 327; continuous vacuum drying, 1840; freeze- are dried to 10-15% moisture content and then transferred
drying, 3528. Relative energy consumption (in kWh/kg of to bin dryers for finishing. This equipment has good control
water removed) are as follows: roller drying, 1.25; pneu- over drying conditions and high production rates. It is used
matic drying, 1.8; spray drying, 2.5; fluidized-bed drying, for large-scale drying of foods (eg, fruits and vegetables are
3.5 (13). dried in 2-3.5 h at up to 5.5 tons/h). It has independently
controlled drying zones and is automatically loaded and
Hot-Air Dryers
unloaded, which reduces labor costs. As a result, it has
largely replaced the tunnel dryer in many applications.
Bin Dryers (Deep-Bed Dryers). Bin dryers are cylindrical A second application of conveyor dryers is foam-mat
or rectangular containers fitted with a mesh base. Hot air drying in which liquid foods (eg, fruit juices) are formed
passes up through a bed of food at relatively low speeds into a stable foam by the addition of a stabilizer and aer-
(eg, 0.5 m3/s/m2 of bin area). These dryers have a high ation with nitrogen or air. The foam is spread on a perfo-
capacity and low capital and running costs. They are rated belt to a depth of 2-3 mm and dried rapidly in two
mainly used for finishing (to 3-6% moisture content) after stages by parallel and then counter-current airflows (Table
initial drying in other types of equipment. Bin dryers im- 4). Foam drying is approximately three times faster than
prove the operating capacity of initial dryers by taking the drying a similar thickness of liquid. The thin, porous mat
TableS. Characteristics of Dryers
Characteristics of the food
Final moisture
Initial moisture Drying rate content
content Size of pieces required required
Moderate Heat- Intermediate Mechanically Moderate
Type of dryer Solid Liquid to high Low sensitive Small to large strong to fast Slow Moderate Low
Bin * * * * * *
Cabinet * * * * * *
Conveyor * * * * * *
Drum * * #
Foam mat * * * *
Fluid bed * * * * * *
Kiln * * * * *
Pneumatic * * * * * *
Rotary * * * * * *
Spray * * * * *
Trough * * * * * * *
Tunnel * * * * * * *
Vacuum
band * * * * *
Vacuum
shelf * * * * * * * * *
Radiant * * * * *
Microwave or
dielectric * * * * * *
Solar (sun) * * * *
Feed
Table 4. Advantages and Limitations of Parallel Flow, Counter-Current Flow, Center-Exhaust, and Cross-Flow Drying
Type of air flow Advantages Limitations
Parallel or cocurrent type: Rapid initial drying. Little shrinkage of food. Low moisture content difficult to achieve as
Food-* Low bulk density. Less heat damage to food. cool, moist air passes over dry food
Airflow - No risk of spoilage
Counter-current type: More economical use of energy. Low final Food shrinkage and possible heat damage. Risk
Food - moisture content as hot air passes over dry of spoilage from warm moist air meeting wet
Airflow - food food
Center-exhaust type: Combined benefits of parallel and counter- More complex and expensive then single-
Food -^ current dryers but less than cross-flow dryers direction air flow
Airflow -* T <-
Cross-flow type: Flexible control of drying conditions by More complex and expensive to buy, operate,
Food-+ separately controlled heating zones, giving and maintain
Airflow T I uniform drying and high drying rates
of dried food is ground to a free-flowing powder that has Fluidized-Bed Dryers. Metal trays with mesh or perfo-
good rehydration properties. The rapid drying and low rated bases contain a bed of particulate foods up to 15 cm
product temperatures result in high-quality product. How- deep. Hot air is blown through the bed (Fig. 6), causing the
ever, a large surface area is required for high production food to become suspended and vigorously agitated (fluid-
rates, so capital costs are therefore high. ized). The air thus acts as both the drying and the fluidiz-
Feed
Enzyme Texture
activity Changes to the texture of solid foods are an important
cause of quality deterioration. The nature and extent of
pretreatments (eg, the addition of calcium chloride to
blancher water), the type and extent of size reduction, and
peeling each affect the texture of rehydrated fruits and
Mould growth vegetables. In foods that are adequately blanched, loss of
texture is caused by gelatinization of starch, crystalliza-
tion of cellulose, and localized variations in the moisture
content during dehydration, which set up internal
stresses. These rupture, compress, and permanently dis-
tort the relatively rigid cells, to give the food a shrunken,
shrivelled appearance. On rehydration the product ab-
Bacterial growth sorbs water more slowly and does not regain the firm tex-
Toxin production ture associated with the fresh material. There are sub-
stantial variations in the degree of shrinkage with
different foods.
Drying is not commonly applied to meats in many coun-
tries owing to the severe changes in texture compared with
Water activity other methods of preservation. These are caused by aggre-
gation and denaturation of proteins and a loss of water-
Figure 11. Effect of water activity on microbial, enzymic and holding capacity, which leads to toughening of muscle tis-
chemical changes to foods (7). Source: Courtesy of Marcel Dekker. sue.
The rate and temperature of drying have a substantial
effect on the texture of foods. In general, rapid drying and
are inhibited below Aw = 0.7; most yeasts are inhibited high temperatures cause greater changes than do moder-
below Aw = 0.8; and most bacteria below Aw = 0.9. The ate rates of drying and lower temperatures. As water is
interaction of Aw with temperature, pH, oxygen, and car- removed during dehydration, solutes move from the inte-
bon dioxide, or chemical preservative has an important ef- rior of the food to the surface. The mechanism and rate of
fect on the inhibition of microbial growth. When any one movement are specific for each solute and depend on the
of the other environmental conditions is suboptimal for a type of food and the drying conditions used. Evaporation
given microorganism, the effect of reduced Aw is enhanced of water causes concentration of solutes at the surface.
(Fig. 11). This permits the combination of several mild con- High air temperatures (particularly with fruits, fish, and
trol mechanisms that result in the preservation of food meats) cause complex chemical and physical changes to
without substantial loss of nutritional properties or sen- the surface and the formation of a hard, impermeable skin.
sory properties (Table 5). This is termed case hardening. It reduces the rate of drying
Enzymatic activity virtually ceases at Aw values below and produces a food with a dry surface and a moist interior.
the BET monolayer value. This is due to the low substrate It is minimized by controlling the drying conditions to pre-
mobility and its inability to diffuse to the reactive site on vent excessively high moisture gradients between the in-
the enzyme. Chemical changes are more complex. The two terior and the surface of the food.
most important things that occur in foods that have a low In powders, the textural characteristics are related to
Aw are Maillard browning and oxidation of lipids. The Aw bulk density and the ease with which they are rehydrated.
that causes the maximum rate of browning varies with dif- These properties are determined by the composition of the
ferent foods. However, in general, a low Aw restricts the food, the method of drying, and the particle size of the prod-
mobility of reactants and browning is reduced. At a higher uct. Low-fat foods (eg, fruit juices, potatoes, and coffee) are
Aw, browning reaches maximum. Water is a product of the more easily formed into free-flowing powders than are
condensation reaction in browning, and at higher moisture whole milk or meat extracts. Powders are instantized by
Table 5. Interaction of Aw, pH, and Temperature in Selected Foods
Food PH Aw Shelf life Notes
Fresh meat >4.5 >0.95 Days Preserve by chilling
Cooked meat >4.5 0.95 Weeks Ambient storage when packaged
Dry sausage >4.5 <0.90 Months Preserved by salt and low Aw
Fresh vegetables >4.5 >0.95 Weeks Stable while respiring
Pickles <4.5 0.90 Months Low pH maintained by packaging
Bread >4.5 >0.95 Days Preserved by heat and low Aw in crust
Fruitcake >4.5 <0.90 Weeks Preserved by heat and low Aw
Milk >4.5 >0.95 Days Preserved by chilling
Yogurt <4.5 <0.95 Weeks Preserved by low pH and chilling
Dried milk >4.5 <0.90 Months Preserved by low Aw
treating individual particles so that they form free-flowing Table 6. Bulk Density and Moisture Content of Selected
agglomerates of aggregates, in which there are relatively Powdered Foods
few points on contact (Fig. 12). The surface of each particle Bulk density Moisture content
is easily wetted when the powder is rehydrated, and par- Food (kg m3) (%)
ticles sink below the surface to disperse rapidly through
Cocoa 480 3-5
the liquid. These characteristics are respectively termed Coffee (ground) 330 7
wettability, sinkability, dispersibility, and solubility. For a Coffee (instant) 330 2.5
powder to be considered instant, it should complete these Coffee creamer 470 3
four stages within a few seconds. Cornstarch 560 12
The convenience of instantized powders outweighs the Egg, whole 340 2-4
additional expense of production, packaging, and transport Milk, powdered, skimmed 640 2-4
for retail products. However, many powdered foods are Milk, instant, skimmed 550 2-4
used as ingredients in other processes, and these are re- Salt, granulated 960 0.2
quired to possess a high bulk of density and a wider range Sugar, granulated 800 0.5
of particle sizes. Small particles fill the spaces between Wheat flour 450 12
larger ones and thus exclude air to promote a longer stor- Source: Refs. 24 and 25.
age life. The characteristics of some powdered foods are
described in Table 6.
rate of deterioration is determined by the storage tem-
Flavor and Aroma perature and the water activity of the food.
Heat not only vaporizes water during drying but also In dried milk the oxidation of lipids produces rancid fla-
causes loss of volatile components from the food. The ex- vors owing to the formation of secondary products, includ-
tent of volatile loss depends on the temperature and solids ing J-lactones. Most fruits and vegetables contain only
concentration of the food and on the vapor pressure of the small quantities of lipid, but oxidation of unsaturated fatty
volatiles and their solubility in water vapor. Volatiles that acids to produce hydroperoxides, which react further by
have a high relative volatility and diffusivity are lost at an polymerization, dehydration, or oxidation to produce al-
early stage in drying. Fewer volatile components are lost dehydes, ketones, and acids, causes rancid and objection-
at later stages. Control of drying conditions during each able odors. Some foods, (eg, carrots), may develop an odor
stage of drying minimizes losses. Foods that have a high of violets produced by the oxidation of carotenes to /?-
economic value due to their characteristic flavors (eg, herbs ionone. These changes are reduced by vacuum- or gas-
and spices) are dried at lower temperatures. packing, low storage temperatures, exclusion of ultraviolet
A second important cause of aroma loss is oxidation of or visible light, maintenance of low moisture contents, ad-
pigments, vitamins, and lipids during storage. The open, dition of synthetic antioxidants, or preservation of natural
porous structure of dried food allows access of oxygen. The antioxidants.
The technical enzyme glucose oxidase is also used to
protect dried foods from oxidation. A package that is per-
meable to oxygen but not to moisture and that contains
glucose and the enzyme is placed on the dried food inside
a container. Oxygen is removed from the headspace during
storage. Milk powders are stored under an atmosphere of
nitrogen with 10% carbon dioxide. The carbon dioxide is
absorbed into the milk and creates a small partial vacuum
Particles
in the headspace. Air diffuses out of the dried particles and
is removed by regassing after 24 h. Flavor changes, due to
oxidative or hydrolytic enzymes, are prevented in fruits by
Figure 12. Agglomerated powder. the use of sulfur dioxide, ascorbic acid, or citric acid, by
pasteurization of milk or fruit juices, and by blanching of Thiamin is also heat sensitive, but other water-soluble vi-
vegetables. tamins are more stable to heat and oxidation, and losses
Other methods used to retain flavors in dried foods in- during drying rarely exceed 510% (excluding blanching
clude losses).
Oil-soluble nutrients (eg, essential fatty acids and vi-
1. Recovery of volatiles and their return to the product tamins A, D, E, and K) are mostly contained within the dry
during drying. matter of the food, and they are not therefore concentrated
2. Mixing recovered volatiles with flavor-fixing com- during drying. However, water is a solvent for heavy-metal
pounds, which are then granulated and added back catalysts that promote oxidation of unsaturated nutrients.
to the dried product, eg, dried meat powders. As water is removed, the catalysts become more reactive,
and the rate of oxidation accelerates (Fig. 12). Fat-soluble
3. Addition of enzymes, or activation of naturally oc- vitamins are lost by interaction with the peroxides pro-
curring enzymes, to produce flavors from flavor pre- duced by fat oxidation. Losses during storage are reduced
cursors in the food (eg, onion and garlic are dried by low oxygen concentrations and storage temperatures
under conditions that protect the enzymes that re- and by exclusion of light.
lease characteristic flavors). Maltose or maltodextrin The biological value and digestibility of proteins in most
are used as a carrier material when drying flavor foods does not change substantially. However, milk pro-
compounds. teins are partially denatured during drum drying, and this
results in a reduction in solubility of the milk powder, ag-
Color gregation, and loss of clotting ability. A reduction in bio-
Drying changes the surface characteristics of food and logical value of 8-30% is reported, depending on the tem-
hence alters the reflectivity and color. Chemical changes to perature and residence time (30). Spray drying does not
carotenoid and chlorophyll pigments are caused by heat affect the biological value of milk proteins. At high storage
and oxidation during drying. In general, longer drying temperatures and at moisture contents above approxi-
times and higher drying temperatures produce greater pig- mately 5%, the biological value of milk protein is decreased
ment losses. Oxidation and residual enzyme activity cause by Maillard reactions between lysine and lactose. Lysine
browning during storage. This is prevented by improved is heat sensitive, and losses in whole milk range from 3-
blanching methods and treatment of fruits with ascorbic 10% in spray drying and 5-40% in drum drying (31).
acid or sulfur dioxide. For moderately sulfured fruits and The importance of nutrient losses during processing de-
vegetables the rate of darkening during storage is in- pends on the nutritional value of a particular food in the
versely proportional to the residual sulfur dioxide content. diet. Some foods, eg, bread and milk, are an important
However, sulfur dioxide bleaches anthocyanins, and resid- source of nutrients for large numbers of people. Vitamin
ual sulfur dioxide is an important cause of color deterio- losses are therefore more significant in these foods than in
ration in stored dried fruits and vegetables. those that either are eaten in small quantities or have low
The rate of Maillard browning in stored milk and fruit concentrations of nutrients.
products depends on the water activity of the food and the In industrialized countries, the majority of the popula-
temperature of storage. The rate of darkening increases tion achieve an adequate supply of nutrients from the mix-
markedly at high drying temperatures, when the moisture ture of foods that is eaten. Losses due to processing of one
content of the product exceeds 45%, and at storage tem- component of the diet are therefore insignificant to the
peratures above 380C (26). long-term health of an individual. In one example, com-
plete meals that initially contained 16.5 jug of vitamin A
Nutritive Value lost 50% on canning and 100% after storage for 18 months.
Although the losses appear to be significant, the original
Large differences in reported data on the nutritive value meal contained only 2% of the recommended daily allow-
of dried foods are due to wide variations in the preparation ance (RDA), and the extent of loss is therefore of minor
procedures, the drying temperature and time, and the stor- importance. The same meal contained 9 mg of thiamin and
age conditions. In fruits and vegetables, losses during lost 75% after 18 months' storage. The thiamin content is
preparation usually exceed those caused by the drying 10 times the RDA, so adequate quantities therefore re-
operation. For example, losses of vitamin C during prepa- mained. Possible exceptions are the special dietary needs
ration of apple flakes are reported to be 8% during slicing, of preterm infants, pregnant women, and the elderly. In
62% from blanching, 10% from pureeing, and 5% from these groups there may be either a special need for certain
drum drying (27). nutrients or a more restricted diet than normal. These spe-
Vitamins have different solubilities in water, and, as cial cases are discussed in detail in Refs. 32, 33 and 34.
drying proceeds, some (eg, riboflavin) become supersatu- Reported vitamin losses during processing give an in-
rated and precipitate from solution. Losses are therefore dication of the severity of each unit operation. However,
small (Table 7). Others, (eg, ascorbic acid) are soluble until such data should be treated with caution. Variation in nu-
the moisture content of the food falls to very low levels and trient losses between cultivars or varieties can exceed dif-
react with solutes at higher rates as drying proceeds. Vi- ferences caused by alternative methods of processing.
tamin C is also sensitive to heat and oxidation. Short dry- Growth conditions, or handling and preparation proce-
ing times, low temperatures, and low moisture and oxygen dures before processing, also ca'use substantial variation
levels during storage are necessary to avoid large losses. in nutrient loss. Data on nutritional changes cannot be di-
Table 7. Vitamin Losses in Selected Dried Foods
Loss (%)
Food Vitamin A Thiamin Vitamin B2 Niacin Vitamin C Folic acid Biotin
0
Fruits 6 55 O 10 56
Fig (sun-dried) 48 42 37
Whole milk (spray-dried) 15 10 10
Whole milk (drum-dried) 30 10 10
Pork 50-70
Vegetables6 5 <10 <10
Source: Refs. 28 and 29.
"Fruits: mean loss from fresh apple, apricot, peach, and prune.
^Vegetables: mean loss from peas, corn, cabbage, and beans (drying stage only).
Chloramine
H+
CHEMICAL DISINFECTING AGENTS NH2Cl + 2H2O ^ HOCl + NH4+ + OH ~
OH-
Lister used phenol (carbolic acid) as a germicide in 1867. At acid pH, solutions have greater germicidal activity
Although it is the parent compound of chemical disinfec- because greater amounts of HOCl are formed; however, for
tion, its use today is limited to substituted phenols, eg, the product stability a pH > 8 is used. Sodium hypochlorite
fcis-phenols used in germicidal soaps. Both chlorine (in the (NaOCl) in commercial liquid form contains 10-14% avail-
form of hypochlorite) and phenol were used to deodorize able chlorine. Calcium hypochlorite [Ca(OCl)2] is a powder
waste materials in the early 180Os, before Pasteur estab- with about 30% available chlorine. Chlorine-based sanitiz-
lished the germ theory of infection and putrefaction. The ers are normally used at concentrations that yield 100-200
use of disinfectant chemicals began in clinical surround- ppm available chlorine with contact times of 3-30 min. Or-
ings in the late nineteenth century. In 1908 the first large- ganic chlorines such as chloramine-T and isocyanuric acid
scale use of chlorine (chloride of lime) in water purification derivatives are more stable than hypochlorites in the pres-
started in Chicago, and its use for this purpose spread rap- ence of organic matter, they are less irritant and less toxic,
idly. Yet disinfectants were not readily accepted in food pro- and they release chlorine more slowly.
duction until the 1940s, when hypochlorite treatment was
permitted in the dairy industry as an alternative to steam
sterilization. The range of antimicrobial chemical agents
has been comprehensively reviewed (2).
Heavy metal ions such as Hg2+ , Cu 2+ and Ag+ are uni-
versal biocides, but they are generally too toxic to use on
food equipment. Alcohols such as ethanol and isopropanol
and others with chain length up to 8-10 carbon atoms are Chloramine-T
biocidal except for bacterial spores. Water is essential for Isocyanuric acid
the antimicrobial action of alcohols, and 60-70% (v/v) is derivatives
the most effective concentration. The alkylating agents for-
maldehyde and ethylene oxide are active gaseous disinfec- Chloramines have 25-30% available chlorine, but they
tants with a broad spectrum of biocidal activity, including are weaker bactericides than hypochlorites except that
bacterial spores. The sporicidal activity is probably due to they are more active at pH > 10. Isocyanuric acid products
their ability to penetrate into the spores and the fact that are active over the pH range 6-10. Both of these organic
they do not require water for their action. Formaldehyde chlorines can be formulated as detergent-sanitizers, but
is too toxic for use with food equipment because it is ab- they are relatively expensive (1).
sorbed onto surfaces as a reversible polymer (paraformal- Chlorine dioxide is another form of chlorine that has
dehyde) that slowly depolymerizes to give free formalde- antimicrobial properties. It is considered to have the same
hyde as a food contaminant. Ethylene oxide is the most antimicrobial activity as hypochlorite. Principal advan-
reliable substance for gaseous disinfection of dry surfaces, tages are that it is not as readily inactivated by organics
especially heat-sensitive materials such as plastics (3). as hypochlorite, and it retains activity at higher pH values
than does hypochlorite. Additionally, chlorine dioxide does
Halogens not react with ammonia, it can break down phenolics to
remove phenolic tastes and odors from water, and it does
The halogens include fluorine, chlorine, bromine, and io- not form trihalomethanes with nitrogenous organic com-
dine, all of which are extremely active oxidizing agents. ponents of water. Because chlorine dioxide is highly reac-
Fluorine is the most reactive, but it is too toxic, irritant tive, it cannot be produced and shipped in bulk. Therefore,
and corrosive to be used as a disinfectant (2). Bromine is it is generated at the site of use, usually by combining
also too toxic and irritant for widespread use, but it has separate solutions of chlorine and sodium chlorite at care-
some applications in mixed halogen compounds (4). Chlo- fully controlled reaction conditions. Chlorine dioxide deca-
rine is an effective disinfectant (Table 1) through the action hydrate can be prepared as a commercial product, but it
of hypochlorous acid (HOCl). Hypochlorous acid is unsta- must be refrigerated because it decomposes with rising
ble and it is normally stabilized by adding caustic soda to temperatures. Under certain conditions it can be explosive.
form sodium hypochlorite (NaOCl). HOCl can be formed Chlorine dioxide, although it is more expensive than hy-
by any of the following reactions: pochlorite, has been used for treatment of water supplies,
in plant chlorination of wastewater treatment, and chlo-
rination of recycled or recirculated waters where slime
Chlorine buildup may occur (5).
H+
Cl2 + H2O ^ HOCl + H + + Cl- Iodine is too insoluble in water to be used as a disin-
OH- fectant; however, if it is complexed with a nonionic surface
Table 1. Advantages and Disadvantages of Different Classes of Sanitizers
Hypochlorite Iodophor QAC Acid-Anionics
Antimicrobial spectrum
Gram-positive bacteria + + + +
Gram-negative bacteria + + +
Spores + - - -
Viruses + - +
Low toxicity + + +
Nonirritating to skin + +
Noncorrosive a +
Nonstaining + b + +
Stability during storage + + +
in hard water + + - +
with organic matter + +
Use at temperatures + + +
Mineral-protein films removed + - +
Leaves no residues +
Leaves no flavors or odors - + +
Detergent-sanitizer - + +
Self-indicating c + - -
Low cost + -
Note: Advantages attribute = . disadvantageous attribute = -.
"Only a problem if misused.
6
OnIy some plastic materials and painted walls; staining of skin is temporary.
0
By odor of available chlorine.
active agent, the resulting iodophor can be used as a where R1, R2, R3, and R4 are covalently bound organic
detergent-sanitizer (Table 1). Diatomic iodine (I2) is highly groups such as alkyl, methyl, benzyl, and cetylbenzyl. The
bactericidal; hypoiodous acid (HOI) and the hypoiodite ion H~ is a halogen, most often chlorine or occasionally bro-
(IO ~) are less bactericidal; the iodate ion (IO^~) is inactive. mide. These are synthesized compounds that are formed
by reacting tertiary amines with quarterizing agents such
OH" OH- as alkyl or cetyl halides. A wide array of groups may be
I2 + H2O ^+ HOI + H + + I- ^+ r + 1O3- substituted, and this may result in the formation of qua-
H H
ternaries with widely variable properties. The cation or
Iodophors are generally used at 12.5-25.0 ppm; at these positively charged proton of the molecule is microbiologi-
concentrations they are self-indicating, ie, the presence of cally active and lyophobic. The negatively charged halide
available iodine is indicated by the amber color of the so- is lyophilic. Because QACs are actively cationic, they are
lution. They must be used at < 5O0C to avoid the release not compatible with detergents or other compounds that
of toxic iodine vapor. Iodophors are formulated with an are anionic in solution. The chemical configuration for al-
acid, usually phosphoric acid, because they are more active kyldimethylbenzylammonium chloride, one of the fre-
at pH 3-5. They also solubilize and remove mineral and quently employed quarternaries, is
protein films from food-processing equipment (4).
flamed and infant skin with the possibility of serious sys- Heat, particularly moist heat, is the most reliable and most
temic toxicity (15). As a result, OTC products have gener- widely used method of destroying all forms of microbes (2).
ally been limited to 0.75% hexachlorophene. Higher The efficacy of heat treatment with steam or hot water
concentrations are sold with medical prescription. (8O0C or above) depends on the temperature achieved and
Restrictions on the use of hexachlorophene resulted in the time of exposure. Temperatures above 6O0C progres-
the development of a range of other disinfectants for use sively kill microbial cells. Vegetative cells may be killed or
in germicidal soaps. For example, Irgasan DP 300, also injured. Injured cells can recover in an appropriate envi-
known as triclosan, 2-4-4'trichlor-2'-hydroxy diphenyl ronment, for example, in foods. Heat injury has been de-
ether is active against Gram-positive and Gram-negative scribed in two ways: the extension of the lag phase of
organisms. growth (18) and the inability to grow on selective media,
for example, on salt-containing media for Staphylococcus
Other Antimicrobial Agents aureus (19) or violet red bile agar for coliform bacteria (20).
Chlorhexidine is one of a family of AT1 ^-substituted big- Because heat cannot be universally applied it is necessary
uanides (2). Its use was licensed in the UK and Canada, to rely on chemical agents for sanitation programs.
but not in the United States. Radiation is an alternative to gaseous disinfection.
Chlorhexidine is active against Gram-positive and Gamma (cobalt-60) and electron-accelerated /?-ray (<10
Gram-negative bacteria; it has limited antifungal activity, MeV) irradiation have good penetrating ability and, there-
but it is not active against acid-fast bacilli, bacterial fore, have the potential for use not only in disinfection, but
spores, or viruses. However, some resistant pseudomonads also in food processing. Ultraviolet radiation has a wave-
can contaminate aqueous solutions of this compound. It is length between 210 and 328 nm, with maximum antimi-
not compatible with anionic compounds. The digluconate crobial activity between 240 and 280 nm. Ultraviolet ra-
salt is freely soluble in water; however, the diacetate and diation is low energy, so it does not penetrate foods. It is
dihydrochloride salts are only poorly soluble. Alcoholic absorbed by glass and plastics, but it can be used for sur-
Chlorhexidine or a 4% Chlorhexidine detergent (Hibiscrub) face disinfection (2). Micrococcus radiodurans and bacte-
are highly effective skin germicides (16). rial and mold spores are highly resistant to ionizing and
The salicylanilides and carbanilides are families of anti- uv irradiation. The primary effect of radiation on living
microbial chemicals (17). One of the more popular disin- cells is by action on DNA. Radiation resistance is geneti-
fectants among these chemicals is 3,4,4'-trichlorocarbani- cally determined. Sublethally damaged cells can recover
lide. (TTC). It has been incorporated into soaps to give an by photoreactivation or by excision and recombination
antimicrobial product. events, which give rise to mutations (2).
Butanol Aqueous
column column
Decanter
Organic Aqueous
phase phase
Steam Steam
Straight
downcomer
Outlet
Clearance weir
under
downcomer
Flat Flow path
seal length and
bubbling area
Tray spacing
Free area
Inlet
Downcomer weir
area, top Figure 4. Cartridge tray assembly.
Free area
1. Throughputs and efficiencies can be as high as sieve Bubble-Cap Tray. Although many bubble-cap columns
or bubble-cap trays. still are in operation, bubble-cap trays rarely are specified
2. Very high flexibility can be achieved and turndown today because of high cost factors and the excellent perfor-
ratios of 4 to 1 are easily obtained without having to mance of the modern valve-type tray. The bubble cap, how-
resort to large pressure drops at the high end of the ever, does have a good turndown ratio and is good for low
operating range. liquid loads.
3. Special valve designs with venturi-shaped orifices Baffle Tray. Baffle trays are arranged in a tower in such
are available for duties involving low pressure drops. a manner that the liquid flows down the column by splash-
4. Although slightly more expensive than sieve trays, ing from one baffle to the next lower baffle. The ascending
the valve tray is very economical in view of its nu- gas or vapor, meanwhile, passes through this curtain of
merous advantages. liquid spray.
5. Because an operating valve is continuously in move- Although the baffle-type tray has a low efficiency, it can
ment, the valve tray can be used for light-to- be useful in applications where the liquid contains a high
moderate fouling duties. Valve trays can be success- fraction of solids.
Packings If properly used, high efficiency packings can provide
HETP values in the range 6-12 in. This can reduce column
For many types of duties, particularly those involving
heights, especially when a large number of trays is re-
small-diameter columns, packing is the most economical
quired. Such packings, however, are very expensive, and
tower internal. One advantage is that most packing can be
each application must be studied in great detail.
purchased from stock on a cubic-foot basis. In addition, the
With random and, in particular, high-efficiency packing,
mechanical design and fabrication of a packed column is
considerable attention must be given to correct liquid dis-
quite simple. Disadvantages of packing include its unsuit-
tribution. Certain types of high-efficiency packing are ex-
ability for fouling duties, breakage of ceramic packing, and,
tremely sensitive to liquid distribution and should not be
according to some reports, less predictive performance,
used in columns more than 2 ft in diameter. Positioning of
particularly at low liquid loads or high column diameters.
these devices and the design of liquid distribution and re-
The most widely used packing is the random packing,
distribution are important factors that should be deter-
usually Rashig rings, Pall rings, and ceramic saddles.
mined only by experts.
These are available in various plastics, a number of differ-
ent metals and, with the exception of Pall rings, in ceramic
materials. Although packings in plastic have the advan- Instrumentation
tage of corrosion resistance, the self-wetting ability of some One of the most important aspects of any distillation sys-
plastic packing, such as fluorocarbon polymers, sometimes tem is the ability to maintain the correct compositions from
is poor, particularly in aqueous systems. This considerably the columns by means of proper controls and instrumen-
increases the HETP when compared with equivalent ce- tation. Although manual controls can be supplied, this ap-
ramic rings. proach rarely is used today in the United States. Manual
High-efficiency metal mesh packing as shown in Figure control involves the extensive use of rotameters and ther-
6 has found increasing favor in industry during recent mometers, which, in turn, involves high labor costs, pos-
years. One type uses a woven wire mesh that becomes self- sible energy wastage, and, at times, poor quality control.
wetting because of capillary forces. This helps establish Far better control is obtained through the use of pneumatic
good liquid distribution as the liquid flows through the or electronic control systems.
packing in a zig-zag pattern.
Pneumatic Control Systems. The most common form of
distillation column instrumentation is the pneumatic-type
analogue control system. Pneumatic instruments have the
advantage of being less expensive than other types and,
because there are no electrical signals required, there is
no risk of an electrical spark. One disadvantage is the need
to ensure that the air supply has a very low dew point
(usually 4O0F) to prevent condensation in the loops.
tomer's request and were trucked 600 miles to the job site
without problems. Final size of the package was 65' X 12'
X 8'.
The packaged approach proved to be beneficial in a
number of ways. Factory fabrication and installation of
piping was far more economical than field finishing, while
erection time for the system was reduced considerably with
significant savings in local labor costs.
An alternative approach for larger systems is the fab-
rication of equipment modules. For one large batch-
distillation unit, the column itself can be supplied as one
module, the batch tank and reboiler as the second, and the
heat exchangers, decanter, pumps, and auxiliary items as
the third. This modular construction before shipment was
successful despite the fact that the batch tank was more
than 8 ft in diameter.
For systems involving columns in excess of 6-ft diame-
ter, prepackaging generally is not feasible. Components of
such systems normally have to be installed and piped at
the job site. Figure 9. Batch distillation/solvent recovery silhoutte mask.
BATCH DISTILLATION
N-I separate columns are required to separate N com-
With process plants becoming increasingly larger, there ponents.
has been a tendency for the chemical and petroleum in- A batch distillation process is very simple to control,
dustries to focus attention on the use of continuous distil- and there is no need to balance the feed and draw-off, as
lation because this approach becomes progressively more is the case with the continuous distillation approach.
economical as the scale of operation grows. As a result, Batch distillation is particularly useful when applied to
batch distillation has become a somewhat neglected unit feeds containing residues that have a tendency to foul sur-
operation. There are, however, many areas where batch faces as these residues remain in the still and cannot con-
distillation can be used more economically than continu- taminate the rectification column internals. For aqueous
ous. Batch sizes are available from about 300 to more than systems-handling materials that leave very heavy fouling,
5000 gal. A 300 gal unit is shown in Figure 9. it is possible to heat with direct steam injection into the
still and thus alleviate problems of buildup on the heat
Advantages transfer surfaces.
The main advantage of batch distillation is its flexibility.
A single unit can, by changing reflux ratios and boil-up COLUMN DESIGN
rates, be used for many different systems. It also is possi-
ble to separate more than two components in the same Before designing a batch column, it obviously is desirable
column, whereas with continuous distillation, at least to have as much detailed information on the system as is
possible. Data on vapor liquid equilibria (VLE), vapor and
liquid densities, liquid viscosity, and the boiling tempera-
tures of the components are essential if a column is to be
properly designed. Failure to have accurate VLE data
means that it is necessary to run a small-scale experiment
in order to characterize the system. In addition, the cus-
tomer must identify the product feed composition, the re-
quired composition of the residue and distillate, the batch
size, and the batch time. Having acquired this data, the
vendor finally can commence design work.
To illustrate the design principles, it is useful to study
the case of binary mixtures. A typical system is shown in
Figure 10. Once the VLE data have been established, it
becomes a straightforward task to calculate the number of
theoretical stages and reflux ratios.
There are two main techniques for operating a batch
column. One is to work with constant reflux ratio during
the complete run. The effect of this method is charted in
Figure 11. As the composition of the more volatile compo-
nent (MVC) in the still, xw, decreases, the fraction of MVC Constant reflux
in the top product decreases. For example, to obtain a set
composition of 90% in the total amount of top product col- Figure 11. A chart illustrates the effect of the method of working
lected, it will always be necessary to collect initially at a with constant reflux ratio during the complete run. One of two
higher composition of about 95% to compensate for a com-
position below specification at the end of the run. The ad-
vantage of constant reflux is that control and operation are
very simple.
The second method is to increase the reflux ratio during
the run in order to maintain a steady top-product compo-
sition. This is shown in Figure 12, where the increase in
the slope of the operating line is obtained by increasing the
reflux ratio. The gradient of the operating line (LAO is ob-
tained from the enrichment equation given below.
L D
Yn = -Xn +1 + xd
Equilibrium
curve
Operating
line Constant reflux
Mole fraction 1A1 in vapor
Figure 12. The second method is to increase the reflux ratio dur-
ing the run in order to maintain a steady top product composition.
McCabe and Thiele procedure the minimum reflux ratio, undergoes a sufficiently large change in value for change
minimum number of theoretical stages, and other such pa- in composition. Manual control of this type of reflux opera-
rameters. In batch distillation in particular, these proce- tion is not feasible.
dures are tedious and time-consuming because, of course, Numerous batch distillation systems have been sup-
the composition of the liquid in the still changes with time plied to customers who require the separation of many
and it is necessary to repeat the calculations many times. different components. To simplify the operation of these
Obviously, the procedures become even more time- systems, there are proprietary computers specifically de-
consuming with multicomponent systems. signed for process control. For example, use of certain mi-
For this type of design work, computer programs can be croprocessors enables the operator to switch from one type
used to enable the engineer to produce an efficient design of separation to another without having to make many
very quickly. One program is extremely flexible and oper- manual adjustments on the control panel. In addition, the
ates in a different series of modes, as is charted in Table computer can be programmed to automatically take care
1. Naturally, the VLE data have to be specified for all of all necessary tails cuts as well as to clean the system
modes. The program further assists in the determination during interims between the various separations.
of the number of theoretical stages. Other modes also are
available to provide different permutations of operation. Batch Systems/Continuous Distillation
To help determine the sizing of the column diameter, In a number of duties, it is essential that the base product
various programs can be used to incorporate different pro- contain only very small amounts of one component. For
prietary methods, including those of Fractionation Re- example, in the recovery of solvents from water, it is man-
search Inc. (FRI) of California. dated that the water may retain only trace quantities of
Column Internals solvents before being pumped to waste. Because one dis-
advantage of a batch system is that there is no stripping
The choice of internals for the column depends mainly on section, it is necessary to boil the batch pot for relatively
the product being processed and the size of the column to long periods of time in order to reduce the residual solvent
be used. To meet virtually every parameter, packed col- to trace quantities.
umns as well as sieve, bubble, and ballast trays are avail- To resolve this problem, a number of batch distillation
able. As a general rule, sieve trays are not used frequently systems with the capability of being operated in the con-
in batch columns because the turndown ratio of most trays tinuous mode have been supplied. By incorporating one,
of this type is only about 1.5 to 1. This reduces one of the two, or three feed points on the column, the feed can be
main advantages of batch columns, mainly flexibility. Usu- pumped directly to the column instead of to the batch tank.
ally, small batch columns are packed because the efficiency Furthermore, a separate small holdup/reboiler is fur-
of trays of less than 2-ft diameter often decreases rapidly. nished in certain cases so that the batch tank and its as-
Ballast trays, although expensive, are often used for larger sociated reboiler need not be used for the continuous opera-
columns because they are efficient and have turndown ra- tion.
tios of up to 9 to 1.
Control BIBLIOGRAPHY
The control of batch columns is very simple, and, therefore, This article was adapted from and is used with permission of A.
required instrumentation usually is quite inexpensive. Cooper, APV Distillation Handbook, 3rd ed., Lake Mills, Wise.,
Constant reflux operation can be handled by a ratio con- 1987. Copyrighted APV Crepaco, Inc.
troller or by using a timed deflection of condensate. For
operation with variable reflux, the control of the reflux ra- APV CREPACO, INC.
tio must be tied to some property of the top product that Lake Mills, Wisconsin
comes a matter of experience and skill in the selection of the elimination of grain with objectionable odors, which
botanicals and in the extraction and formulation of flavors. may have developed during storage or kiln drying at the
Although these elements are carefully guarded secrets, the elevators. Hybrid corn, usually of the readily available
producer must rely on three basic processes, namely mac- dent variety and plump rye, developed from Polish strains
eration, percolation, and distillation, or any combination (Rosen), are used for beverage alcohol production. Modern
thereof. Maceration involves the steeping of the raw ma- distilleries use Airveyor unloading systems, others the tra-
terials in the spirits, usually in a vat, to impart the desired ditional power shovel in conjunction with screw conveyors
aroma, flavor, and color. The liquid is then drawn off and and bucket elevators. Even though the grain has been sub-
provides the base for further processing. Percolation is ac- jected to a cleaning process at the elevator, it is passed over
complished by recirculating the spirits through a percola- receiving separators, a series of vibrating screens which
tor containing the raw materials. As the spirits seep down sift out the foreign materials. Air jets and dust collectors
through the raw material, the desired constituents are ex- remove any light material and magnetic separators re-
tracted, which will give the proper aroma, flavor intensity, move metallic substances.
and color. The distillation method is similar to that used Milling breaks the outer cellulose protective wall
in gin production. The ingredients are either immersed in around the kernel and exposes the starch to the cooking
the beverage spirits or placed in trays or pans in the head and conversion processes. Distillers require an even,
of the still. The rising vapors extract the essential flavors, coarse meal without flour. Milling is accomplished by three
which are then condensed and discharged as a colorless methods: (1) in roller mills, using pairs of corrugated rolls
liquid. This distillate contains the basic flavor that is used (breaks), run sharp to sharp (projections facing projec-
for further processing. tions); (2) in hammer mills, where a series of revolving
Cordials are characterized and marketed according to hammers within a close-fitting casing and rotating at
their generic names; eg, anisette (aniseed), creme de 1,800-3,600 rpm shear the grain to a meal, which is re-
menthe (peppermint), triple sec (citrus fruit peel), slow gin moved by suction through a screen, different for various
(sloe berries), and by their trade names (proprietary types of grain; and (3) in attrition mills (not widely used)
brands) of which Benedictine and Chartreuse are well- where the grain is ground by two counterrotating disks
known examples. (1,200-2,000 rpm). This mill is not entirely satisfactory be-
cause of excessive flour produced. A three-break roller mill
(three pairs of corrugated rolls, arranged vertically) with
THE MANUFACTURING PROCESS
rolls 23 cm in diameter X 76 cm long has a capacity of 3.5
m3 (100 bu) of corn per hour; a hammer mill 61 cm in width,
Any material rich in carbohydrates is a potential source of
10.6 m3 (300 bu) per hour; and an attrition mill with 41
ethyl alcohol, which for industrial purposes is obtained by
cm grinding plates, 3.5 m3 (100 bu) per hour, on the basis
the fermentation of materials containing sugar (molasses),
that 25% of the ground corn remains above the no. 12 mesh
or a substance convertible into sugar, such as the starches.
(1.68 mm) screens.
In the production of distilled spirits for beverage purposes,
however, cereal grains are the principal types of raw ma- Mashing
terial used. Any reference to alcohol in beverages is always
to ethyl alcohol (C2H5OH). Although other alcohols may be The mashing process, consists of cooking, ie, gelatinization
present, they are referred to as higher alcohols, fusel oils, of starch, and conversion (saccharification), ie, changing
or by their specific name. starch to grain sugar (maltose). Cooking can be carried out
The chemical composition of grain varies considerably at atmospheric or higher pressure in a batch or a contin-
and depends to a large extent on environmental factors uous system. For whisky production, batch cooking at at-
such as climatic conditions and the nature of the soil. An- mospheric pressure is widely used although some batch
other variable is the malt (sprouted or germinated grain) pressure cooking is practiced. For grain neutral spirits pro-
used. Malt is generally understood to be germinated bar- duction, both batch and continuous systems are used un-
ley, unless it is further qualified as rye malt, wheat malt, der pressure. After cooling conversion is accomplished in
etc. The purpose of malting is the development of the am- the cooking vessel by the addition of barley malt meal to
ylases, the active ingredients in malt. Amylases are en- the cooked grain. Some distillers pump the mash imme-
zymes of organic origin, which change grain starch into the diately to a converter for the necessary holding time and
sugar, maltose. Besides providing the means of converting thus make the cooking vessel available for the next cook.
the grain starch into sugar, the malt also contributes to The converted mash is cooled and pumped to the fermen-
the final flavor and aroma of the distillate. Malting tech- ters.
niques may produce a malt of such unusual character that Distillers vary mashing procedures, but generally con-
it may indeed furnish the outstanding characteristics of form to basic principles, especially in the maintenance of
the final product, as in Scotch whisky. Figure 2 shows the sanitary conditions. The cooking and conversion equip-
process flow sheet of a modern beverage spirits plant. ment is provided with direct or indirect steam, propeller
or rake-type agitation, and cooling coils or a barometric
Grain Handling and Milling condenser. Mashing procedures for rye, corn, and malt
grains are described below.
The beverage distilling industry utilizes premium cereal
grains. Each distiller supplements government grain stan- Rye. In the preparation of a bourbon mash, rye is gen-
dards with personal specifications, especially in regard to erally subjected to the corn-cooking process. However, rye
1. Cereal grains 11. Malt receiver 20. Converter 29. Heat exchanger
2. Malt 12. Cereal grain receiver 21. Mash coolers 30. Dephlegamtor
3. Malt bin 13. Automatic scale 22. Fermenter 31. Vent condenser
4. Cereal grain bin 14. Mill feeder 23. Final yeast propagator 32. Product cooler
5. Unloading elevator 15. Roller mills 24. Yeast culture and intermediate yeast propagator 33. Selective distillation column
6. Dust filter 16. Precooker 25. Fermented-mash holding vessel 34. Product concentrating column
7. Collector 17. Malt infusion 26. Stillage return system 35. Aldehyde concentrating column
8. Scalperator 18. Cooker 27. Stillage flow to recovery system 36. Fusel oil concentrating column
9. Millerator 19. Barometric condenser 28. Whisky separating column 37. Fusel oil decanter
10. Reclaiming exhauster
Figure 2. Material processflow,modern beverage spirits plant.
undergoes liquefication at a much lower temperature than Alcoholic fermentation is represented by the following
corn, which avoids thermal decomposition of critical grain reactions:
constituents adversely affecting the final flavor of the dis-
tillate. For that reason, many distillers mash rye sepa- maltase
rately. C12H22O11 -> C6H12O6 -> 2C2H5OH + 2CO2
Water is drawn at the rate of 35 L/m3 (28 gal/bu) and maltose dextrose ethyl carbon
rye and malt meal are added. The mash is slowly heated alcohol dioxide
to 540C and held for approximately 30 min. Proteolytic en-
zymes, active at 43-460C, aid in reducing the viscosity, and A fermentation efficiency of 95% is obtained based on the
the optimum temperature for /?-amylase is 540C. The mash sugar available. Of the starch converted to grain sugar and
is then heated to 63-670C and held for 30-45 min to ensure subsequently subjected to fermentation, 5-6% is consumed
maximum conversion. The mash (pH 6.0) is then cooled to in side reactions. The extent and type of these reactions
the fermenting temperature 20-220C. This process of con- depend on: (1) yeast strain characteristics, (2) the compo-
verting small grains is called infusion mashing. sition of the wort, and (3) fermentation conditions such as
the oxidationreduction potential, temperature, and de-
gree of interference by bacterial contaminants.
Corn. Although the starch in corn grains converts Secondary products formed by these side reactions
rather easily, higher cooking temperatures are necessary largely determine the characteristics and organoleptic
to make the starch available. Usually malt is not added at qualities of the final product. In the production of whisky,
the beginning, but to reduce viscosity, premalt of 0.5% may the secondary products (known as congeners) formed and
be added before cooking, preferably at around 660C. Thin retained during the subsequent operations include a num-
stillage (the residual dealcoholized fermented mash from ber of aldehydes, esters, higher alcohols (fusel oils), some
the whisky distillation process) is added by some producers fatty acids, phenolics or aromatics, and a great many un-
to adjust pH to 5.2-5.4. For cookers operating at atmo- identified trace substances (Table 3). In the production of
spheric pressure, a mashing ratio of 95-115 L (25-30 gal) grain neutral spirits, the congeners are removed from the
of slurry (grain, water, and stillage mixture) per 0.03 m3 distillate in a complex multicolumn distillation system.
(1 bu) and a holding time of 30 min at 10O0C are preferable. Some distillers, however, retain a small portion of the low-
The mash is cooled to 670C and malt is added. Primary boiling esters in the distillate when the grain neutral spir-
conversion, the saccharification taking place during con- its are to be matured. Fermentation of grain mashes is
version, is in the order of 70-80% of the available starches. initiated by the inoculation of the set mash with 2-3 vol %
The remainder of the conversion to fermentable sugar of ripe yeast prepared separately (see below) and followed
takes place during the fermentation process and is referred by three distinct phases.
to as secondary conversion. For batch cooking under pres-
sure only 65-83 L (17-22 gal) of water are drawn, and the 1. Prefermentation involves rapid multiplication of
maximum temperature is 120-1520C. In continuous pres- yeast from an initial 4-8 million/mL to a maximum
sure cooking, water is drawn at a ratio of 30 L/m3 (24 gal/ of 125-130 million/mL of the liquid and an increas-
bu) of meal and sufficient thin stillage is added to adjust ing rate of fermentation.
the pH to 5.2-5.4. The mash is pumped through the con-
tinuous pressure cooker, where it is exposed to tempera- 2. Primary fermentation is a rapid rate of fermenta-
tures of 170-1770C for 2-6 min, and then into a flash cham- tion, as indicated by the vigorous "boiling" of the fer-
ber where it is cooled immediately by vacuum to the menting mash, caused by escape of carbon dioxide.
malting (conversion) temperature of 630C. A malt slurry is During this phase secondary conversion takes place,
continuously introduced and the mixture proceeds through ie, the changing of dextrins to fermentable sub-
the water cooling system to the fermenters. stances.
3. Secondary fermentation is a slow and decreasing
Fermentation rate of fermentation. Conversion of the remaining
dextrins, which are difficult to hydrolyze, takes
In fermentation the grain sugars (largely maltose), pro- place.
duced by the action of malt enzymes (amylases) on gelat-
inized starch, are converted into nearly equal parts of ethyl The degree of conversion, agitation of the mash, and
alcohol and carbon dioxide. This is accomplished by the temperature directly affect the fermentation rate. Fermen-
enzymes in yeast. Yeast multiples by budding, and a new ter mash set at a concentration of 144 L (38 gal) of mash
cell is produced about every 70 min. Although yeasts of per bushel of grain 25.4 kg (56 Ib) will be fermented to
several genera are capable of some degree of fermentation, completion in two to five days, depending on the set and
Saccharomyces cerevisiae is almost exclusively used by the control temperatures. The set temperature (temperature
distilling industry. It has the ability to reproduce prolifi- of the mash at the time of inoculation) is largely deter-
cally under normal growth conditions found in distilleries, mined by the available facilities for cooling the fermenting
has a high fermentation rate and efficiency, and can tol- mash. If cooling facilities are adequate, temperatures of
erate relatively high alcohol concentrations (up to 15-16 27-3O0C may be employed; otherwise, the set temperature
vol %). A great variety of strains exist and the character- must be low enough to ensure that the temperature will
istics of each strain are evidenced by the type and amount not exceed 320C during fermentation. When no cooling fa-
of congeners the yeast is capable of producing. cilities are provided, the inoculation temperature must be
below 210C. Excessive temperatures during the prefermen- grain mash, sometimes referred to as fermented wort or
tation phase retard yeast growth and stimulate the devel- distillers beer. In addition to the alcohol and the desirable
opment of bacterial contaminants which are likely to pro- secondary products (congeners), the fermented mash con-
duce undesirable flavors. tains solid grain particles, yeast cells, water-soluble pro-
In the production of sour mash whisky U.S. federal reg- teins, mineral salts, lactic acid, fatty acids, and traces of
ulations require that a minimum of 25 vol % of the fer- glycerol and succinic acid. Although a great number of dif-
menting mash must be stillage (cooled, screened liquid re- ferent distillation processes are available, the most com-
covered from the base discharge of the whisky separating mon systems used in the United States are (1) the contin-
column, pH 3.8-4.1). In addition to producing a heavier- uous whisky separating column, with or without an
bodied whisky, this procedure provides the distiller with auxiliary doubler unit for the production of straight whis-
an economical means of adjusting the setting pH (4.8-5.2) kies; (2) the continuous multicolumn, system used for the
to inhibit bacterial development. It also provides buffering production of grain neutral spirits; and (3) the batch rec-
action during the fermentation cycle, which is important tifying column and kettle unit, used primarily in the pro-
because secondary conversion does not take place if the duction of grain neutral spirits that are subsequently
fermenting pH drops below 4.1 in the immediate stages. stored in barrels for maturation purposes. In the batch sys-
Thin stillage also provides a means of diluting the cooker tem, the heads and tails fractions are separated from the
mash to the proper fermenter mash concentration, 3,220- product resulting from the middle portion of the distilla-
3,870 L/m3 (30-36 gal/bu) of grain for the production of tion cycle.
spirits, and 4,080-4,850 L/m3 (38-45 gal/bu) for making Although most modern plants have various capacity
whisky. This concentration gives about a 12-16% soluble whisky stills available, a whisky separating column is usu-
solids in the fermenting liquid, within the range used in ally incorporated into the multicolumn system, thus ac-
beer fermentations but lower than that in wine fermen- quiring a greater range of distillation selectivity, ie, the
tation. removal or retention of certain congeners. For example,
Preparation of the yeast involves a stepwise propaga- absorptive distillation involving the addition of water to
tion, first on a laboratory scale and then on a plant scale the upper section of a column in the whisky distillation
to produce a sufficient quantity of yeast for stocking the system is a method of controlling the level of heavier com-
main mash in the fermenters. A strain of yeast is usually ponents in a product. In the beverage distillation industry,
carried in a test tube containing a solid medium (agar stills and auxiliary piping are generally fabricated of cop-
slant). A series of daily transfers, beginning with the re- per, although stainless steel is also used. All piping that
moval of some yeast from the solid medium, are made conveys finished products is tin-lined copper, stainless
into successively larger flasks containing liquid media steel, or glass.
diamalt (commercial malt extract) diluted to 15-20 Ball- The whisky column, a cylindrical shell that is divided
ing, malt extract, or strained sour yeast mashuntil the into sections and may contain from 14 to 21 perforated
required amount of inoculum is available for the starter plates, spaced 56-61 cm apart. The perforations are usu-
yeast mash, called a dona. After one day's fermentation, ally 1-1.25 cm in diameter and take up about 7-10% of the
the dona is added to a yeast mash normally composed of plate area. The vapors from the bottom of the still pass
barley malt and rye grains, and representing approxi- through the perforations with a velocity of 6-12 m/s. The
mately 2-3.5 wt % of the total grain mashed for each fer- fermented mash is introduced near the top of the still, and
menter. passes from plate to plate through down pipes until it
The yeast mash is generally prepared by the infusion reaches the base where the residual mash is discharged.
mashing method and then soured (acidified) to a pH of 3.9 The vapor leaving the top of the still is condensed and
4.1 by a 4-8-h fermentation at 41-540C with Lactobacillus forms the product. Some whisky stills are fitted with en-
delbrucki, which ferments carbohydrates to lactic acid. trainment removal chambers and also with bubble-cap
Satisfactory souring can be induced with an inoculum of plate sections (wine plates) at the top to permit operation
approximately 0.25% of culture per volume of mash. The at higher distillation proofs. Because whisky stills made of
water-to-meal ratio of 2,580-3,000 L/m3 (24-28 gal/bu) at- copper, especially the refinement section, supply a superior
tains a yeast mash balling of approximately 21. Before product, additional copper surface in the upper section of
inoculation with yeast, the soured mash is pasteurized to the column may be provided by a demister, a flat disk of
71-870C to curtail bacterial activity, then cooled to the set- copper mesh. The average whisky still uses approximately
ting temperature of 20-220C. The sour mash medium of- 1.44-1.80 kg/L (12-15 Ib of steam/proof gal) of beverage
fers an optimum condition for yeast growth and also has spirits distilled. Steam is introduced at the base of the col-
an inhibitory effect on bacterial contamination. In 16 h the umn through a sparger. Where economy is an important
yeast cell count reaches 150-250 million/mL. Some distill- factor, a calandria is employed as the source of indirect
ers use the sweet yeast method for yeast development. In heat. The diameter of the still, number of perforated and
this instance the lactic acid souring is not included and the bubble-cap plates, capacity of the doubler, and proof of dis-
inoculation temperature is usually above 26.60C to insure tillation are the critical factors that largely determine the
rapid yeast growth. characteristics of a whisky.
The basic continuous distillation system for the produc-
Distillation tion of grain neutral spirits usually consists of a whisky
Distillation separates, selects, and concentrates the alco- separating column, an aldehyde column (selective distil-
holic products of yeast fermentation from the fermented lation column), a product concentrating column (some-
times referred to as an alcohol or rectifying column, from to the fusel oil concentrating column. The product is with-
which the product is drawn), and a fusel oil concentrating drawn from the product concentrating column.
column. In addition, some distillers, to secure a greater Some accumulation of heads, at the top of the product
degree of refinement and flexibility, may include an alde- concentrating column, are removed at the condenser, and
hyde concentrating column (heads concentrating column) transferred to the aldehyde concentrating column, where
or a fusel oil stripping column. Bubble-cap plates are used the heads from the system are removed for disposal. The
throughout the system (except in the whisky column, fusel oil concentrating column removes the fusel oil from
which may have some bubble-cap plates). the system. Figures 3, 4, and 5 show the distribution and
This distillation system offers a wide range of flexibility concentration of alcohols and congeners through the selec-
for the refinement of distilled beverage spirits. Figure 3 tive distillation column, the product concentrating column,
shows a five-column, continuous distillation system for the and the heads concentrating column.
production of grain neutral spirits. A fermented mash
(generally 90% corn and 10% barley malt) with an alcohol By-Products. The discharge from the base of the whisky
concentration of approximately 7 vol % is pumped into the column is called stillage and contains in solution and in
whisky column somewhere between the 13th and 19th per- suspension substances derived from grain (except the
forated plate for stripping. The residual mash is dis- starch, which has been fermented), and from the mashing
charged at the base and pumped to the feed recovery plant; and fermentation processes. The suspended solids are re-
the overhead distillate [ranging in proof from 105 to 135 covered by screening and then subjected to a pressing and
(52.5 to 67.5%)] is fed to the selective distillation column a drying operation (dehydrating), usually in rotary, steam-
(also called the aldehyde column), which has over 75 tube dryers. The liquid portion, called thin stillage, is con-
bubble-cap plates. The main stream [10-20 proof (5-10%)] centrated by a multieffect evaporator to a syrup with a
from the selective distillation column is pumped to the solid content of 30-35%. This concentrate can be mixed
product concentrating column. A heads draw (aldehydes and dried with the previously screened-out solids, or it can
and esters) from the condenser is pumped to the heads be dried separately, on rotary-drum dryers. These by-
concentrating column (also called the aldehyde concen- products are known as distillers' dried grains and distill-
trating column), and a fusel oil and ester draw is pumped ers' solubles and are used by the feed industry to fortify
From
product
concentrating
column
To product
concentrating
column
190 proof
(95%) proof
From whisky
column
105-135
proof To fusel oil
column
proof
Steam
Proof
Esters, aldehyde, g/100 L
Fusel oil, g/100 L Figure 3. Selective distillation column.
proof
To product
storage
191.3 proof
dairy, poultry, and swine formula feeds. Distillers' feeds depth of the char (controlled by regulating the duration of
are rich in proteins (24-35%), fat (8%), choline, niacin, and the firing, 30-50 s), temperature and humidity, entry
other B-complex vitamins and contain vital fermentation proof, and, finally, the length of storage impart definite and
growth factors that produce good growth responses in live- intended changes in the aromatic and taste characteristics
stock and poultry. of a whisky. These changes are caused by three types of
reaction occurring simultaneously and continually in the
Maturation barrel: (7) extraction of complex wood constituents by the
liquid, (2) oxidation of components originally in the liquid
In the United States, the final phase of the whisky pro-
and of material extracted from the wood, and (3) reaction
duction process, called maturation, is the storage of bev-
erage spirits (which at this point are colorless and rather between the various organic substances present in the liq-
pungent in taste) in new, white oak barrels, whose staves uid, leading to the formation of new congeners.
and headings are charred. The duration (years) of storage Comprehensive studies of changes occurring during the
in the barrel depends on the time it takes a particular maturation of whisky have been published by a number of
whisky to attain the desirable ripeness or maturity. The investigators (4-11). Although these reports contain de-
staves of the barrel may vary in thickness from 2 to 2.85 tailed information on the concentration of various conge-
m. The outside dimensions of a 190-L (50-gal) barrel are ners throughout the course of the maturation period, little
approximately: height, 0.88 m (34.5 in.) and diameter at is revealed of the interrelationships between various con-
the head, 0.54 m. Whisky storage warehouses vary in con- geners except for the nonvolatile groups, such as solids,
struction from brick and mortar types, single and multiple nonvolatile acids, tannin, and color. Notable among the ob-
floors (as many as six) having capacities up to 100,000 bar- served changes are increases in the concentrations of acids,
rels of 190-L (50-gal) capacity, to wooden sheet-metal- esters, and solids. These studies reveal that throughout
covered buildings (called iron clads), generally not exceed- the maturation period a linear relationship exists between
ing a capacity of 30,000 barrels of 190-L (50-gal) capacity. the increase in acids and esters and the increase in dis-
It is customary to provide natural ventilation. The whisky solved solids; this suggests that acid and ester formation
in storage is subject to critical factors that determine the is dependent on some precursor that is extracted from the
character of the final product. The thickness of the stave, barrel at the same rate as the bulk of the solid fraction (9).
From
condenser
Aldehyde
and ester
draw
185 proof
(92.5%)
From
selective
distillation
column
193 proof
(96.5%)
Dilution
H2O
Selective
distillation
column
40 proof
(20%)
Steam
Proof (100%)
Aldehyde, g/100 L
Ester, g/100 L Figure 5. Aldehyde (heads) concentrating column.
In 1962 the U.S. Treasury Department increased the The maturing progress of a type of bourbon as measured
maximum allowable entry proof (storage in barrels) for by the principal ingredients is illustrated in Tables 4 and
straight whisky from 110 to 125 (55 to 62.5%). The indus- 5. It is evident that the congeners amount to only about
try engaged in a study in December 1985 to determine the 0.5-0.75% of the total weight. Yet it is this small fraction
flavor development, chemical composition, and evapora- that determines the quality of the final product. Thus ma-
tion loss rates of distillates at six different proofs from 109 tured whiskies vary widely in taste and aroma because of
to 155 (54.5 to 77.5%) over a planned 8-yr period, and the the wide variation in congener concentration. For example,
study was continued an additional 4 yr. Evaporation losses esters may vary from 8.0 to 18.0 g/100 L, and aldehydes
averaged approximately 3.0% a year over the 12-year pe- from 0.7 to 7.6 g/100 L. Nevertheless, there is no correla-
riod. tion between chemical analysis and quality, ie, taste and
In addition to chemical analysis, they applied regres- aroma. Only the consumer can detect the fine variations
sive analysis for most congeners listed in Table 4. Regres- and thus evaluate the quality of whiskies.
sion analysis illustrates the functional relationship be-
tween congeners. Except for fusel oil, there was an
appreciable continuing development of congeners through ANALYSIS
12 yr. Esters, the most important flavor constituent in
whisky, developed linearly over this time period. Later Analytical results are expressed in terms of one component
studies, using radioactive carbon for direct monitoring, de- for each chemical class; ie, acetic acid for acids, acetalde-
termined the congeners derived from ethanol during hyde for aldehydes, etc (Tables 4 and 5). Individual con-
whisky maturation. Esters (ethyl acetate) are formed in a stituents can, of course, be determined by more refined
system that is affected by changes in concentration of ace- techniques. Until the advent of gas chromatography,
tic acid, ethanol, and water, ie, a loss of water by evapo- tedious chemical procedures were generally required for
ration; an increase in acetic acid results in an increase of separation of the congeners. Distillation, countercurrent
ethyl acetate. distribution, and other physical methods affected concen-
Table 4. Chemical Analysis0 of Bourbon Whiskies Matured at Six Proofs from 109 to 155 (54.5 to 77.5%), g/100 L at 100
Proof (50%)
Age (yr) Proof Color" pH6 Solids Fixed acids Volatile acids Esters Fusel oil Aldehydes Furfural Tannins
Table 4. Chemical Analysis" of Bourbon Whiskies Matured at Six Proofs from 109 to 155 (54.5 to 77.5%), g/100 L at 100
Proof (50%) (continued}
Age (yr) Proof Color" pH6 Solids Fixed acids Volatile acids Esters Fusel oil Aldehydes Furfural Tannins
Note: Analyses performed annually on samples reduced to 100 proof (50%). Acids as acetic acid, esters are ethyl acetate, aldehydes as acetaldehyde, and
tannins as tannic acid (11).
"Absorbance at 430 nm at 100 proof (50%).
6
At 100 proof (50%).
c
Not determined.
tration of various congener groups. These concentrates re- techniques, a qualitative profile of alcoholic distillates can
acted to form chemical derivatives that were then sub- be obtained without prior treatment of the sample. Flame
jected to further separation. Paper and column ionization uses a hydrogen flame for the combustion of or-
chromatography have been used extensively for this work. ganic substances to produce electrons and negative ions,
After separation of the components, identification is pos- which are collected on an anode. The resulting electrical
sible by infrared and mass spectrometry. current is proportional to the amount of material burned.
With the high sensitivity (flame and /?-ray ionization de- /?-Ray ionization uses beta particles emitted from a source
tection) and efficiency offered by gas chromatographic such as strontium-90 to ionize the carrier gas and its com-
ponents. The measure of the electrical current resulting Table 6. U.S. Commercial Exports of Liquor by Class 1996
from the collection of electrons on the anode is used in the (in wine gal.)
determination or detection of the substance. This may aug- Class and type
ment sensory evaluations. A positive identification of the
separated congeners can be made by infrared and mass Domestic whiskey
spectrometers. Nmr may offer possibilities in the identifi- Bonded O
cation of congeners present in alcoholic beverages. Straight 8,293,519
Blended straights 34,814
Distilled over 160/p 2,355
Blended whiskey 158,576
PACKAGING Subtotal 8,489,264
Imported whiskey
Because distilled spirits are packaged under federal gov-
Scotland and N. Ireland 31,515
ernment supervision and the product is then distributed Bottled in U.K. O
to the various states in compliance with laws and regula- Bottled in U.S. 31,616
tions, many factors must be considered normally not in- Canadian 110,562
volved in glass packaging. First, the product represents a Bottled in Canada O
high value, because it includes the federal tax at the time Bottled in U.S. 110,562
of bottling. In the United States, a bottle of whisky retail- Ireland and others O
ing at $5.44 is taxed at $3.11. Obviously, care must be Subtotal 142,077
taken to avoid losses. Second, in addition to dealing with Total all whiskey 8,631,341
cases, bottles, cartons, closures, and labels, the distiller
Gin
must apply to each bottle a federal strip stamp indicating
that the excise tax has been paid and also apply bottle Domestic 553,942
stamps of the decal type to indicate identification or tax Imported O
payment in the seven states that require these in their Subtotal 553,942
system of control. With the heavy investment in product Vodka
taxes and the necessity of applying state stamps, the dis-
tiller's ability to build up a substantial case goods inven- Domestic 6,008,700
tory to provide immediate service to his customers in those Imported O
Subtotal 6,008,700
states having this requirement is limited. Third, because
this is a licensed industry, in addition to the normal record Rum
keeping necessary for efficient operations and control, fed-
eral and state records are required. Puerto Rico 1,034,908
Virgin Islands 89,834
Federal regulations prescribe and limit the standards Other domestic 244,789
of fill (size of containers). On October 1,1976, the adoption Subtotal dom. rum 1,369,531
of the metric system permitted distillers to incorporate the Subtotal imp. rum O
new sizes into their operations as circumstances allow. Subtotal all run 1,369,531
Once the metric size is adopted for a brand, the distiller
may not revert to the former standard. Brandy
Now, only the metric size will be permitted, such as 1.75 Domestic 260,337
L (59.2 fl oz); 1.00 L (33.8 fl oz); 750 mL (25.4 fl oz); 500 Imported O
mL (16.9 fl oz); 200 mL (6.8 fl oz); and 50 mL (1.7 fl oz). Subtotal 260,337
Individual states likewise limit the number of sizes that
can be distributed within their borders and need not adopt Cordials and Specs.
all the sizes made available by the federal government. Domestic 578,408
The most common packaging operation utilized in the Imported O
industry is the straight-line system with a line speed from Subtotal 578,408
120 to 200 bottles/min. Along with the general progress in
packaging, the distilling industry is moving in the direc- Cocktails and mixed drinks
tion of automatic-line operation with variable frequency Domestic 110,167
control systems keyed to the fill and labeling operations. Imported O
This is only possible, however, when volume on certain Subtotal 110,167
sizes is substantial. Most distillers are faced with mechan-
ical equipment changes, requiring approximately four Tequila
hours per line, to handle various sizes of bottles. In addi- Subtotal 308,068
tion to material specifications for quality control on all sup-
plies, built-in quality-control inspection systems are in- Non-whiskey
cluded on the bottling lines. Likewise, the quality-control Domestic 8,881,075
department, independent of bottling operations, takes ran- Imported 308,058
dom samples for evaluation purposes. Total 9,183,133
D I S T I L L E D BEVERAGE SPIRITS 539
Table 6. U.S.Commercial Exports of Liquor by Class 1996 Malt whisky. An alcoholic distillate made from a fer-
(in wine gal.) (continued) mented wort derived from malted barley only, and distilled
Class and type in pot stills. It is the second fraction (heart of the run) of
the distillation process.
N.E.S.
Proof. In Canada, the UK, and the United States, the
Domestic 14,630,239 alcoholic concentration of beverage spirits is expressed in
Imported 0 terms of proof. The United States statutes define this stan-
Subtotal 14,630,239
dard as follows: proof spirit is held to be that alcoholic li-
Total Dom. Distilled Spirits 32,000,574
Total Imp. Distilled Spirits 450,135
quor that contains one-half its volume of alcohol of a spe-
Grand Total 32,450,713 cific gravity of 0.7939 at 15.6"C; ie, the figure for proof is
always twice the alcoholic content by volume. For example,
100" proof means 50% alcohol by volume. In the UK as well
as Canada, proof spirit is such that at 10.6"C weighs ex-
EXPORTS OF DISTILLED SPIRITS actly twelve-thirteenths of the weight of a n equal bulk of
distilled water. A proof of 87.7" would indicate a n alcohol
The United States is well known throughout the world for concentration of 50%.A conversion factor of 1.142 can be
its world-class whiskies and these are exported to many used to change British proof to U.S. proof.
lands. Tastes differ widely in other countries. In some, like Proof gallon. A U.S. gallon of proof spirits or the al-
Germany and Japan the major export by far is bourbon coholic equivalent thereoc ie, a U.S.gallon of 231 ins3
whisky. In others, like Belgium, it is vodka. In all, bourbon, (3,785 cm3) containing 50% of ethyl alcohol by volume.
the prototypical U.S. whisky, is the largest distilled spirit Thus a gallon of liquor at 120" proof is 1.2 proof gal; a
export. Table 6 shows exports of distilled spirits in 1996. gallon at 86" proof is 0.86 proof gal. A British and Canadian
proof gallon is a n imperial gallon of 277.4 (4,546 cm3)
GLOSSARY at 100" proof (57.1% of ethyl alcohol by volume). An im-
perial gallon is equivalent to 1.2 U.S. gal. To convert Brit-
Balling. A measure of the sugar concentration in a ish proof gallons to U.S. proof gallons, multiply by the fac-
grain mash, expressed in degrees and approximating per- tor 1.37. Since excise taxes are paid on the basis of proof
cent by weight of the sugar in solution. gallons, this term is synonymous with tax gallons.
Bushel. A distillers bushel of any cereal gain is 25.4 kg Single whisky. The whisky, either grain or malt, pro-
(56 lb). duced by one particular distillery. Blended Scotch whisky
Congeners. The flavor constituents in beverage spirits is not a single whisky.
that are responsible for its flavor and aroma and that re- Spirits. Distilled spirits including all whiskies, gin,
sult from the fermentation, distillation, and maturation brandy, rum, cordials, and others made by a distillation
processes. process for nonindustrial use.
Feints. The third fraction of the distillation cycle de- Tails. A residual alcoholic distillate.
rived from the distillation of low wines in a pot still. This Wash. The liquid obtained by fermenting wort with
term is also used to describe the undesirable constituents yeast. It contains the beverage spirits and congeners de-
of the wash which are removed during the distillation of veloped during fermentation.
grain whisky in a continuous patent still (Coffey). These
are mostly aldehydes and fuse1 oils. Wine gallon. Measure of actual volume; U.S. gallon
(3.7845118 L) contains 231 in.3 (3,785 cm3); British (Im-
Foreshots. The first fraction of the distillation cycle perial) gallon contains 277.4 in.3 (4,546 cm3).
derived from the distillation of low wines in a pot still.
Wort. The liquid drained off the mash tun and contain-
Fusel oil. An inclusive term for heavier, pungent- ing the soluble sugars and amino acids derived from the
tasting alcohols produced during fermentation. Fusel oil is grains.
composed of approximately 80% amyl alcohols, 15% butyl
alcohols, and 5% other alcohols.
Grain whisky. An alcoholic distillate from a fermented BIBLIOGRAPHY
woFt derived from malted and unmalted barley and maize
(corn), in varying proportions, and distilled in a continuous 1. Proceedings Before and By Direction of the President Concern-
patent still (Coffey). ing the Meaning of the Tkrm Whisky, U.S.Government Print-
Heads. A distillate containing a high percentage of low- ing Office, Washington, D.C., 1909.
boiling components such as aldehydes. 2. Business Week (Feb. 17,1962).
High wines. An all-inclusive term for beverage spirit 3. Business Week (Mar. 21,1977).
distillates that have undergone complete distillation. 4. S. Baldwin et al., Journal ofAgricultura1 and Food Chemistry
Low wines. The term for the initial product obtained 16, 381 (1967).
by separating (in a pot still) the beverage spirits and con- 5. C. A. Crampton and L. M. Tolman, Journal of the American
geners from the wash. Low wines are subjected to at least Chemical Society 30,97 (1908).
one more pot still distillation to attain a greater degree of 6. A.J. Liebmann and M. Rosenblatt, Industrial and Engineer-
refinement in the malt whisky. ing Chemistry 36,994(1943).
7. A. J. Liebmann and B. Scherl, Industrial and Engineering H. F. Willkie, Beverage Spirits in AmericaA Brief History, The
Chemistry 41, 534 (1949). Newcomen Society in North America, Downington, Pa., 1949.
8. P. Valaer and W. H. Frazier, Industrial and Engineering H. F. Willkie and J. A. Proschaska, Fundamentals of Distillery
Chemistry 28, 92 (1936). Practice, Joseph E. Seagram & Sons, Inc., New York, 1943.
9. M. C. Brockmann, Journal of the Association of Official Ag- F. B. Wright, Distillation of Alcohol, London, 1918.
ricultural Chemists 33, 127 (1950). H. Wustenfeld, Trinkbranntweine und Liquore, Berlin, Germany,
10. G. H. Reazin et al., Journal of the Association of Official Ag- 1931.
ricultural Chemists 59, 770 (1976). C. L. Yaws, J. R. Hopper, "Methanol, Ethanol, Propanol and Bu-
tanol, Physical and Thermodynamic Properties," Chemical En-
11. S. Baldwin and A. A. Andreasen, Journal of the Association gineering 119 (June 7, 1976).
of Official Agricultural Chemists 53, 940 (1974).
12. Bureau of the Census, U.S. Department of Commerce, Dis-
tilled Spirits Council of the U.S., Aug. 1989. JOSEPH L. OWADES
Consultant
Sonoma, California
GENERAL REFERENCES
Annual Statistical Revue (1976), Distilled Spirits Council of the DRY MILK
US, Inc., Washington, D.C., 1977.
A. Barnard, The Whiskey Distilleries of the United Kingdom, Lon-
don, 1887.
HISTORY
H. Barron, Distillation of Alcohol, Joseph E. Seagram & Sons, Inc.,
New York, 1944. The development of the dry milk industry apparently
C. S. Boruff and L. A. Rittschol, Agric. Food Chem. 7, 630 (1959). stems from the days of Marco Polo in the thirteenth cen-
Canada, Its History, Products, and Natural Resources, Depart- tury. Reports are that Marco Polo encountered "sun dried
ment of Agriculture of Canada, Ottawa, 1906. milk" on his journeys through Mongolia and that from this
A. Cooper, The Complete Distiller, London, 1760. beginning dry milk products evolved.
H. G. Crowgey, Kentucky Bourbon, The Early Years of Whiskey Through early pioneering scientists, such as Nicholas
Making, The University Press of Kentucky, Lexington, 1971. Appert and Gail Borden, basic processing methods were
Distillers Feed Research, Distillers Feed Research Council, Cin- developed for drying milk products. Martin Ekenberg and
cinnati, Ohio, 1971.
G. A. DeBecze, "Alcoholic Beverages, Distilled/' Encyclopedia of Lewis Merrill have been acknowledged as developers of the
Industrial Chemical Analysis, Vol. 4, Interscience Division of first commercial roller- and spray-process drying systems,
John Wiley & Sons, Inc., New York, 1967, pp. 462-494. respectively, in the United States.
The Excise Act, 1934, Department of National Revenue, Ottawa, Since the initial development of commercial drying sys-
Canada, 1947, Chap. 52, pp. 24-25. tems, significant technological advances have been made
G. Foth, Handbuch der Spiritusfabrikation, Verlag Paul Parey, resulting in such widely recognized and used dry milk
Hamburg, Germany, 1929. products as nonfat dry milk, dry whole milk, and dry but-
G. Foth, Die Praxis des Brennereibetriebs, Verlag Paul Parey, termilk, which may be manufactured by roller- or spray-
Hamburg, Germany, 1935. dryers (now mostly by the latter) or by more unique pro-
A. Herman, E. M. Stallings, and H. F. Willkie, "Chemical Engi-
cesses such as foam or freeze drying. These same dry milk
neering Developments in Grain Distillery," Trans. Am. Inst.
Chem. Eng. 31, 1942. products also may be processed in such a manner as to
A. J. Liebmann, "Alcoholic Beverages," in R. E. Kirk and D. F. make them readily soluble and thus "instantized."
Othmer, eds., Encyclopedia of Chemical Technology, Vol. 1, In-
terscience Publishers, New York, 1947, pp. 228-303.
A. McDonald, Whisky, Glasgow, UK, 1934.
PROCESSING
Methods of Analysis, 12th ed., Association of Official Agricultural
Chemists, New York, 1975. The steps in a typical dry milk processing operation are as
G. W. Packowski, "Alcoholic Beverages, Distilled" in A. Standen, follows:
ed., Kirk-Othmer Encyclopedia of Chemical Technology, Vol. 1,
2nd ed., Interscience Division of John Wiley & Sons, Inc., New Receipt of fresh, high-quality milk from modern dairy
York, 1963, pp. 501-531. farms, delivered in refrigerated, stainless steel bulk
G. W. Packowski, "Distilled Beverage Spirits," in M. Grayson, ed., tankers.
Kirk-Othmer Encyclopedia of Chemical Technology, Vol. 3, 3rd
ed., Wiley Interscience, New York, 1978, pp. 830-869. Separation of the milk (if nonfat dry milk is to be
D. R. Peryam,/mi Qual Control 11, 17 (1950). manufactured) to remove milkfat, which commonly
Regulations, Distilleries and Their Products, Circular ED 203, De- is churned into butter. If dry whole milk is to be man-
partment of National Revenue, Ottawa, Canada, Mar. 30, ufactured, the separation step is omitted but may be
1961. replaced by clarification.
Regulations under the Federal Alcohol Administration Act, Alco- Pasteurization by a continuous high-temperature
hol, Tobacco Products and Firearms (27 CFR) ATF P 5100.8 short-time (HTST) process whereby every particle of
(12177), U.S. Government Printing Office, Washington, D.C.
milk is subjected to a heat treatment of at least
J. Samuelson, The History of Drink, London, 1880.
E. D. Unger, H. F. Willkie, and H. C. Blankmyer, "The Develop- 71.70C for 15 sec.
ment and Design of a Continuous Cooking and Mashing Sys- Holding the pasteurized milk at an elevated tem-
tem for Cereal Grains," Trans. Am. Inst. Chem. Eng. 40,1944. perature for an extended period of time (76.70C for
7. A. J. Liebmann and B. Scherl, Industrial and Engineering H. F. Willkie, Beverage Spirits in AmericaA Brief History, The
Chemistry 41, 534 (1949). Newcomen Society in North America, Downington, Pa., 1949.
8. P. Valaer and W. H. Frazier, Industrial and Engineering H. F. Willkie and J. A. Proschaska, Fundamentals of Distillery
Chemistry 28, 92 (1936). Practice, Joseph E. Seagram & Sons, Inc., New York, 1943.
9. M. C. Brockmann, Journal of the Association of Official Ag- F. B. Wright, Distillation of Alcohol, London, 1918.
ricultural Chemists 33, 127 (1950). H. Wustenfeld, Trinkbranntweine und Liquore, Berlin, Germany,
10. G. H. Reazin et al., Journal of the Association of Official Ag- 1931.
ricultural Chemists 59, 770 (1976). C. L. Yaws, J. R. Hopper, "Methanol, Ethanol, Propanol and Bu-
tanol, Physical and Thermodynamic Properties," Chemical En-
11. S. Baldwin and A. A. Andreasen, Journal of the Association gineering 119 (June 7, 1976).
of Official Agricultural Chemists 53, 940 (1974).
12. Bureau of the Census, U.S. Department of Commerce, Dis-
tilled Spirits Council of the U.S., Aug. 1989. JOSEPH L. OWADES
Consultant
Sonoma, California
GENERAL REFERENCES
Annual Statistical Revue (1976), Distilled Spirits Council of the DRY MILK
US, Inc., Washington, D.C., 1977.
A. Barnard, The Whiskey Distilleries of the United Kingdom, Lon-
don, 1887.
HISTORY
H. Barron, Distillation of Alcohol, Joseph E. Seagram & Sons, Inc.,
New York, 1944. The development of the dry milk industry apparently
C. S. Boruff and L. A. Rittschol, Agric. Food Chem. 7, 630 (1959). stems from the days of Marco Polo in the thirteenth cen-
Canada, Its History, Products, and Natural Resources, Depart- tury. Reports are that Marco Polo encountered "sun dried
ment of Agriculture of Canada, Ottawa, 1906. milk" on his journeys through Mongolia and that from this
A. Cooper, The Complete Distiller, London, 1760. beginning dry milk products evolved.
H. G. Crowgey, Kentucky Bourbon, The Early Years of Whiskey Through early pioneering scientists, such as Nicholas
Making, The University Press of Kentucky, Lexington, 1971. Appert and Gail Borden, basic processing methods were
Distillers Feed Research, Distillers Feed Research Council, Cin- developed for drying milk products. Martin Ekenberg and
cinnati, Ohio, 1971.
G. A. DeBecze, "Alcoholic Beverages, Distilled/' Encyclopedia of Lewis Merrill have been acknowledged as developers of the
Industrial Chemical Analysis, Vol. 4, Interscience Division of first commercial roller- and spray-process drying systems,
John Wiley & Sons, Inc., New York, 1967, pp. 462-494. respectively, in the United States.
The Excise Act, 1934, Department of National Revenue, Ottawa, Since the initial development of commercial drying sys-
Canada, 1947, Chap. 52, pp. 24-25. tems, significant technological advances have been made
G. Foth, Handbuch der Spiritusfabrikation, Verlag Paul Parey, resulting in such widely recognized and used dry milk
Hamburg, Germany, 1929. products as nonfat dry milk, dry whole milk, and dry but-
G. Foth, Die Praxis des Brennereibetriebs, Verlag Paul Parey, termilk, which may be manufactured by roller- or spray-
Hamburg, Germany, 1935. dryers (now mostly by the latter) or by more unique pro-
A. Herman, E. M. Stallings, and H. F. Willkie, "Chemical Engi-
cesses such as foam or freeze drying. These same dry milk
neering Developments in Grain Distillery," Trans. Am. Inst.
Chem. Eng. 31, 1942. products also may be processed in such a manner as to
A. J. Liebmann, "Alcoholic Beverages," in R. E. Kirk and D. F. make them readily soluble and thus "instantized."
Othmer, eds., Encyclopedia of Chemical Technology, Vol. 1, In-
terscience Publishers, New York, 1947, pp. 228-303.
A. McDonald, Whisky, Glasgow, UK, 1934.
PROCESSING
Methods of Analysis, 12th ed., Association of Official Agricultural
Chemists, New York, 1975. The steps in a typical dry milk processing operation are as
G. W. Packowski, "Alcoholic Beverages, Distilled" in A. Standen, follows:
ed., Kirk-Othmer Encyclopedia of Chemical Technology, Vol. 1,
2nd ed., Interscience Division of John Wiley & Sons, Inc., New Receipt of fresh, high-quality milk from modern dairy
York, 1963, pp. 501-531. farms, delivered in refrigerated, stainless steel bulk
G. W. Packowski, "Distilled Beverage Spirits," in M. Grayson, ed., tankers.
Kirk-Othmer Encyclopedia of Chemical Technology, Vol. 3, 3rd
ed., Wiley Interscience, New York, 1978, pp. 830-869. Separation of the milk (if nonfat dry milk is to be
D. R. Peryam,/mi Qual Control 11, 17 (1950). manufactured) to remove milkfat, which commonly
Regulations, Distilleries and Their Products, Circular ED 203, De- is churned into butter. If dry whole milk is to be man-
partment of National Revenue, Ottawa, Canada, Mar. 30, ufactured, the separation step is omitted but may be
1961. replaced by clarification.
Regulations under the Federal Alcohol Administration Act, Alco- Pasteurization by a continuous high-temperature
hol, Tobacco Products and Firearms (27 CFR) ATF P 5100.8 short-time (HTST) process whereby every particle of
(12177), U.S. Government Printing Office, Washington, D.C.
milk is subjected to a heat treatment of at least
J. Samuelson, The History of Drink, London, 1880.
E. D. Unger, H. F. Willkie, and H. C. Blankmyer, "The Develop- 71.70C for 15 sec.
ment and Design of a Continuous Cooking and Mashing Sys- Holding the pasteurized milk at an elevated tem-
tem for Cereal Grains," Trans. Am. Inst. Chem. Eng. 40,1944. perature for an extended period of time (76.70C for
25-30 min.)a step used only in the manufacture of sheet. The dry milk next is conveyed by an auger to a ham-
high-heat nonfat dry milk, which commonly is used mermill where it undergoes a physical treatment to con-
as an ingredient in yeast-raised bakery products and vert it into uniformly fine particles which then are pack-
meat products. aged, usually in 25-kg polyethylene-lined multiwall bags.
Condensing the milk by removing water in an evap- Two basic configurations of spray dryers presently are
orator or vacuum pan until a milk solids content of in use, these being horizontal (box) and vertical (tower)
40% is reached. dryers. In both, pasteurized fluid milk, which has been con-
Delivery of the condensed product to the dryer. densed to a total solids of 40% or greater, is fed under pres-
sure to a spray nozzle, or an atomizer, where the dispersed
Commercial U.S. drying processes are of two types liquid then comes into contact with a current of filtered,
roller (drum) and spray. The former currently is used only heated air. The droplets of condensed milk are dried almost
to a limited extent. In this process, two large rollers, usu- immediately and fall to the bottom of the fully enclosed,
ally steam-heated internally and located adjacent and par- stainless steel drying chamber. The dry milk product con-
allel to each other, revolve in opposite directions contacting tinuously is removed from the drying chamber, trans-
a reservoir of either pasteurized fluid or condensed milk. ported through a cooling and collecting system, and finally
During rotation, the fluid milk product dries on the hot conveyed into a hopper for packagingusually into 25-kg
roller surface. After approximately three-quarters of a rev- bags, or in tote bins.
olution, a carefully positioned, sharp stationary knife de-
taches the milk product, now in the form of a thin dry THE PRODUCT
BATCH DRYERS
WARREN S. CLARK, JR.
American Dairy Products Institute It will be apparent that batch operated equipment usually
Chicago, Illinois is related to small production runs or to operations requir-
Dry buttermilk is the product resulting from the re- DRYERS: TECHNOLOGY AND ENGINEERING
moval of water from liquid buttermilk derived from the
manufacture of butter. It contains not less than 4.5% milk- Throughout the food processing industries, there are many
fat and not more than 5% moisture. and varied requirements for thermal drying. Some involve
All of these products may be processed in such a way the removal of moisture or volatiles from various food in-
that their dispersing and reliquefaction properties are sub- gredients or products that differ in both chemical and
physical characteristics. Others involve the drying of so-
stantially improved. When this is accomplished, the prod-
lutions or liquid suspensions and different approaches to
ucts are called instantized. "Single-pass" and "agglomer-
the problem. To assist manufacturers in arriving at a rea-
ating" processes are used to make instant dry milk
sonably accurate first assessment of the type, size, and cost
products, with the primarily method being the latter. of element for a particular duty, this article describes the
Table 1 reflects the annual domestic production of non- most widely used types of both batch and continuous dry-
fat dry milk, dry whole milk, and dry buttermilk during ers in the food industries and gives an indication of ap-
the period 1960 to 1998. Standards for dry milk products proximate sizes and capital costs for typical installations.
initially were developed by the dairy industry in 1929. Three basic methods of heat transfer are used in indus-
Since that time, additional product standards have been trial dryers in varying degrees of prominence and combi-
developedand revisedboth by industry and govern- nations, specifically, convection, conduction, and radiation.
ment agencies. These standards are based on various gen- In the chemical processing industry, the majority of dry-
eral and specific product characteristics, which serve as a ers employ forced convection and continuous operation.
basis for determining overall quality of the dry milk prod- With the exception of the indirectly heated rotary dryer
ucts. Table 2 shows the approximate composition and food and the film drum dryer, units in which heat is transferred
value of the three most commonly manufactured dry milk by conduction are suitable only for batch use. This limi-
products. tation effectively restricts them to applications involving
somewhat modest production runs.
Radiant, or "infrared," heating is rarely used in drying
UTILIZATION materials such as fine chemicals or pigments. Its main ap-
plication is in such operations as the drying of surface coat-
An industry-wide survey of end uses for dry milk products ings on large plane surfaces since for efficient utilization,
is conducted annually by the American Dairy Products In- it generally is true that the material being irradiated must
stitute. Data compiled in the survey are published under have a sight of the heat source or emitter. There is, how-
the title Dry Milk ProductsUtilization and Production ever, in all the dryers considered here a radiant component
Trends. Included in the census data are end-use markets in the heat-transfer mechanism.
for nonfat dry milk, dry whole milk, and dry buttermilk. Direct heating is used extensively in industrial drying
For the past several years the largest markets for nonfat equipment where much higher thermal efficiencies are ex-
dry milk have been dairy, prepared dry mixes, confection- hibited than with indirectly heated dryers. This is because
ery, and bakery. These market areas accounted for 781 mil- there are no heat exchanger losses and the maximum heat
lion pounds in 1998approximately 89% of the domestic release from the fuel is available for the process. However,
sales. The primary market for dry whole milk is confec- this method is not always acceptable, especially where
tionery. In 1998, this market area accounted for 88 million product contamination cannot be tolerated. In such cases,
pounds of dry whole milkover 66% of the domestic sales indirect heating must be used.
for this product. Dry buttermilk is used in three primary With forced-convection equipment, indirect heating em-
marketsdairy, bakery, and prepared dry mixes. In 1998, ploys a condensing vapor such as steam in an extended
these markets used 39.6 million pounds of dry butter- surface tubular heat exchanger or in a steam jacket where
milkrepresenting 89% of domestic sales. conduction is the method of heat transfer. Alternative sys-
tems that employ proprietary heat-transfer fluids also can
be used. These enjoy the advantage of obtaining elevated
temperatures without the need for high-pressure opera-
GENERAL REFERENCES
tion as may be required with conventional steam heating.
This may be reflected in the design and manufacturing cost
American Dairy Products Institute, Standards for Grades of Dry of the dryer. Furthermore, in addition to the methods listed
Milks Including Methods of Analysis, Bulletin 916 (Rev.),
above, oil- or gas-fired indirect heat exchangers also can
American Dairy Products Institute, Chicago, 111., 1990.
American Dairy Products Institute, Dry Milk Products be used.
Utilization and Production Trends, 1997, Bulletin 1000, Amer- In general, dryers are either suitable for batch or con-
ican Dairy Products Institute, Chicago, 111., 1999. tinuous operation. A number of the more common types
C. E. Beardslee, Dry MilksThe Story of an Industry, American are listed in Table 1, where an application rating based on
Dry Milk Institute, Chicago, 111., 1948. practical considerations is given. In the following review,
C. W. Hall and T. I. Hedrick, Drying of Milk and Milk Products, some of the factors likely to influence selection of the vari-
2nd ed., AVI Publishing, Westport, Conn., 1971. ous types are discussed for particular applications.
BATCH DRYERS
WARREN S. CLARK, JR.
American Dairy Products Institute It will be apparent that batch operated equipment usually
Chicago, Illinois is related to small production runs or to operations requir-
Table 1. Product Classification and Dryer Types as an Aid to Selection
Evaporation rate, Fluids, Pastes, Granules,
lb/ft2 - h liquid dewatered pellets,
mean rate = Eav suspension cake Powders extrudates Operation
Forced convection (cross-airflow) 0.15-0.25
Eav = 0.2 Poor Fair Fair Good Batch
Forced convection (throughflow) 1.0-2.0
Eav = 1.5 Good Batch
Agitated pan (sub-atmospheric) 1.0-5.0
Eav = 3.0 Fair Fair Fair Poor Batch
Agitated pan (atmospheric) 1.0-5.0
Eav = 3.0 Fair Fair Fair Poor Batch
Double-cone tumbler (sub atmospheric) 1.0-3.0
Eav = 2.0 Poor Fair Poor Batch
Fluidized bed (throughflow) 2-50
Eav = 26 Good Good Continuous
Conveyor band (throughflow) 2.0-10.0
Eav = 6.0 Fair Good Continuous
Rotary (indirect) 1.0-3.0a
Eav = 2.0 Poor Good Fair Continuous
Rotary (direct) 2.0-6.0a
Eav = 4.0 Fair Fair Good Continuous
Film drum (atmospheric) 3.0-6.0
Eav = 4.5 Good Fair Continuous
Pulumatic or flash 50-250
Eav = 150 Fair Good Fair Continuous
Spray 7.0-33.0
Eav = 20.0 Good Continuous
3
"Evaporation rates for rotary dryers are expressed in lb/ft h.
tems incorporating large-volume, low-pressure fans that, Thruflo Type 1C1 2-truck Type No. 2
with the use of properly insulated enclosures, usually pro- units filter cake 2-truck
filter cake
vide thermal efficiencies in the region of 50-60%. However,
in special applications of this type of dryer that call for 2 Thruflo units
total air rejection, this figure is somewhat lower and is
largely related to the volume and temperature of the ex- 1 Thruflo unit
haust air. Capital investment is relatively low, as are in-
stallation costs. Furthermore, by using the fan systems,
both power requirements and operating costs also are min-
imal. Against these advantages, labor costs can be high. Number of two-truck units
In such a plant, the drying cycles are extended, with
2445 hours being quite common in certain cases. This is Figure 1. Comparative performance curves for Thruflo and con-
a direct result of the low evaporative rate, which normally ventional units.
is in the region of 0.15-0.25 lb/ft2 h.
Following the recent trend and interest shown in pre-
forming feedstock and in particular with regard to the de-
sign of extruding and tray-filling equipment for dewatered would be between seven and eight for the same duty. The
cakes, it is now possible to obtain the maximum benefit of advantage is more apparent when it is seen that respective
enhanced evaporative rates by using through-air circula- floor areas occupied are 55 ft2 for the Thruflo dryer pic-
tion dryers when handling preformed materials. Figure 1 tured in Figure 2 and 245 ft2 in the case of conventional
shows how a high-performance dryer can product 1950 units using transverse airflow.
pounds of dried material in a 24-h period at a terminal Reference to the drying curves for the processing of ma-
figure of 0.5% moisture when handling a preformed filter terials in solid or filter cake form or, in fact, in the case of
cake having an initial moisture content of 58%. The very wet powders, clearly indicates that the ultimate rate-
great improvement in performance can readily be seen governing factor is the rate of diffusion of moisture from
from the curve, in which it is clear that the corresponding the wet mass. This becomes increasingly so during the fall-
number of conventional two-truck recirculatory units ing rate period of drying. This situation, however, can be
are in use and all fall into the category of conduction-type
dryers. The most usual type of heating is by steam, al-
though hot water or one of the proprietary heat-transfer
fluids can be used.
Two particular types are the double-cone dryer (Fig. 3)
with capacities of <400 ft3 and the agitated-pan dryer not
normally larger than 8 ft diameter, where average evapo-
rative rates per unit wetted area usually are in the region
of 4 lb/ft2 h. These units are comparatively simple to op-
erate and, when adequately insulated, are thermally quite
efficient, although drying times can be extended. They are
especially suitable for applications involving solvent recov-
ery and will handle powders and granules moderately well.
They do, however, suffer from the disadvantage with some
materials that the tumbling action in double-cone dryers
and the action of the agitator in agitated-pan machines can
produce a degree of attrition in the dried product that may
Figure 2. Thruflo dryer. prove unacceptable.
Similarly, quite large rotary vacuum dryers are used for
pigment pastes and other such materials, especially where
organic solvents present in the feedstock have to be recov-
improved by preforming the product in order to increase ered. These units normally are jacketed and equipped with
the effective surface area presented to heat and mass an internal agitator that constantly lifts and turns the ma-
transfer. The logical extension of this technique is to total terial. Heat transfer here is entirely by conduction from
dispersion drying (flash or pneumatic dryers, fluid beds, the wall of the dryer and from the agitator. Owing to the
etc) where discrete particles can be brought into contact nature of their construction, initial cost is high relative to
with the hot gas. This produces rapid heat transfer with capacity. Installation costs also are considerable. In gen-
correspondingly short drying times. eral, these dryers find only limited application.
Batch-type fluidized-bed dryers have, therefore, super-
seded forced-convection units in many cases, notably in the
drying of Pharmaceuticals. These machines generally are CONTINUOUS DRYERS
available in a range of standard sizes with batch capacities
of 50-200 Ib, although much larger units are made for spe- For the drying of liquids of liquid suspensions, two types
cial applications. of dryers can be used: film drum dryers for duties in the
When considering this type of dryer, it is important to region of 600 Ib/h for a larger dryer of about 4 ft diameter
ensure that the feed material can be fluidized in both ini- X 10 ft face length or large spray dryers (as in Fig. 4) with
tial and final conditions. It also should be remembered that drying rates of approximately 22,000 Ib/h. Where tonnage
standard fan arrangements are not equally suitable for a production is required, the drum dryer is at a disadvan-
variety of materials of different densities. Therefore, it is
necessary to determine accurately the minimum fluidizing
velocity for each product.
If the feedback is at an acceptable level of moisture con-
tent for fluidization, this type of dryer provides many ad-
vantages over a batch-type unit. Simplified loading and
unloading results in lower labor costs, high thermal effi-
ciencies are common, and the drying time is reduced to
minutes as opposed to hours in conventional units. Cur-
rent developments of this type of equipment now include
techniques for the simultaneous evaporation of water and
the granulation of solids. This makes the units ideal for
use in the pharmaceutical field.
The various batch dryers referred to operate by means
of forced convection, the transfer of thermal energy being
designed to increase the vapor pressure of the absorbed
moisture while the circulated air scavenges the overlying
vapor. Good conditions thus are maintained for continued
effective drying. Alternatively and where the material is
thermosensitiveimplying low temperatures with conse-
quently low evaporative ratessome improvement can be
effected by the use of subatmospheric dryers, ie, by reduc-
ing the vapor pressure. Several different configurations Figure 3. Double-cone vacuum dryer.
in support of theoretical calculations for the determination
of the best dryer size but also to establish where a satis-
factory film can be formed.
It must be emphasized that the method of feeding the
product to the dryer is of paramount importance to selec-
tion or design. There are, of course, certain materials that
are temperature-sensitive to such a degree that their han-
dling would preclude the use of an atmospheric drum
dryer. In such cases, special subatmospheric equipment
may provide the answer, although the capital cost in re-
lation to output generally would restrict its use to premium
grade products.
As an alternative, the spray dryer offers an excellent
solution to many drying problems. Many materials that
would suffer from thermal degradation if dried by other
methods often can be handled by spray drying owing to the
rapid flash evaporation and its accompanying cooling ef-
fect. The continuous method of operation also lends itself
to large outputs and with the correct application of control
equipment, to low labor cost as well.
SPRAY DRYERS
Feed Spreading
rollers roller
Feed
Discharge trough
Discharge
Dryer with top
feed rollers
Discharge
Side trough feed
Discharge
Feed
Discharge Discharge
Discharge
Double drum dryer with
Figure 5. Feeding arrangements for Double drum dryer center feed and bottom
with center feed discharge
drum dryers.
of atomization used. An example of this is the tower con- consideration is given to labor costs for either type of plant
figuration designed to accommodate the inverted jet of the since these are likely to be approximately the same. Prob-
two-fluid nozzle whereas the cylinder and cone of the more ably the most obvious figure emerging from this compari-
usual configuration are designed for the spray pattern pro- son is the 20% price differential in favor of the continuous-
duced by a disk-type atomizer (Fig. 6). band dryer. Furthermore, while energy costs favor spray
The product collection systems incorporated in spray- drying, they are not significantly lower.
drying installations are many and varied and can consti- It is, of course, impossible to generalize since the eco-
tute a substantial proportion of the total capital invest- nomic viability of a drying process ultimately depends on
ment. In some cases, this can be as high as 20-25% of the the cost per pound of the dried product and, as mentioned
installed plant cost. It also must be remembered that to be previously, the spray dryer usually has a greater amount
suitable for spray drying, the feed must be in a pumpable of water to remove by thermal methods than other types.
condition. Therefore, consideration must be given to the In the particular case illustrated, the spray dryer would
upstream process, ie, whether there is any need to reslurry have an approximate diameter of 21 ft for the evaporation
in order to make the feed suitable for spray drying. of 6000 Ib/h. If, however, the feed solids were reduced to
It generally is accepted that mechanical dewatering is 30% by dilution, the hourly evaporation rate would in-
less costly than thermal methods and while the spray
crease to 14,000 Ib and the chamber diameter would be
dryer exhibits quite high thermal efficiencies, it often is at
a disadvantage relative to other drying systems because of about 30 ft with corresponding increases in thermal input
the greater absolute weight of water to be evaporated and air volume. The system would, as a result, also require
owing to the nature of the feed. It is, however, interesting larger fans and product collection systems. The overall
to consider this point further. A classic case for comparison thermal efficiency would remain substantially constant at
is provided by a thixotropic material that may be handled 76% with reducing feed solids. Installed plant costs, how-
either in a spray dryer using a mechanical disperser doing ever, increase proportionally with increasing dryer size
work on a filtered cake to make it amenable to spray necessary for the higher evaporation involved in producing
drying or alternatively, drying the same feedstock on a a dried output equivalent to that shown in Table 2.
continuous-band dryer. In the latter instance, the cake is Spray drying does have many advantages, particularly
fed to an extruder and suitably preformed prior to being with regard to the final product form. This is especially so
deposited on the conveyor band. where pressing grade materials are required, ie, in the pro-
The operating costs presented in Table 2 are based on duction of ceramics and dust-free products such as dye-
requirements for thermal and electrical energy only. No stuffs. It is certain that with the introduction of new ge-
Feed
Centrifugal
Air inlet atomizer
Air inlet
Nozzle atomizer
Air outlet
Feed
Air outlet
Product Product
Figure 6. Alternative configurations of spray dryers showing (a) tall form type and (b) conical.
Table 2. Comparison between Direct-Fired Band Dryer and Spray-Dryer Costs in the Processing of Titanium Dioxide
Spray dryer Band dryer
Initial moisture content, WAV 50% 50%
Final moisture content, WAV 0.5% 0.5%
Feed, Ib/h 12,000 12,000
Evaporation Ib/h 5970 5970
Output, Ib/h 6030 6030
Inlet air temperature, 0F 1150 393
Exhaust air temperature, 0F 250 300
Direct gas firing Gas CV = 1000 Btu/ft2 Gas CV = 1000 Btu/ft2
Hourly operating cost gas and electricity $39.00 $42.26
Thermal efficiency 76.0% 69.5%
Installed horsepower 149 154
Floor area occupied, ft2 650 2100
Installed cost $465,000 $330,000
Energy cost per pound of dried product $0.065 $0.070
ometries and techniques there will be further development In addition, many thermosensitive materials can be
into areas such as foods and in the production of powders dried successfully by this method. Such an arrangement
that may be easily reconstituted. lends itself to the handling of pasty materials since the
rapid flashing off of moisture and consequent surface
drying limits the possibility of wall buildup or agglomer-
ROTARY DRYERS ation within the dryer. On the other hand, countercurrent
operation normally is used where a low terminal mois-
Another type of dryer that is very much in evidence in the ture content is required. In this arrangement, the high-
chemical and process industries is the continuous rotary temperature gases are brought into contact with the prod-
dryer. This machine generally is associated with tonnage uct immediately prior to discharge where the final traces
production and as a result of its ability to handle products of moisture in the product must be driven off.
having a considerable size variation, can be used to dry a In both these types, however, gas velocities can be suf-
wide range of materials. The principal sources of thermal ficiently high to produce product entrainment. They there-
energy are oil, gas, and coal. While typical inlet tempera- fore would be unsuitable for low-density or fine-particle
tures for direct-fired dryers using these fuels is in the order materials such as carbon black. In such cases, the indirect-
of 120O0F, in certain instances they may be as high as fired function-type dryer is more suitable since the dryer
1500-160O0F depending largely on the nature of the prod- shell usually is enclosed in a brick housing or outer steel
uct handled. Where feed materials are thermosensitive, jacket into which the hot gases are introduced. As heat
steam heating from an indirect heat exchanger also is used transfer is entirely by conduction, conventional flighting
extensively. These dryers are available in a variety of de- and cascading of the material is not used. Rather, the in-
signs but in general, can be divided into two main types: side of the shell is fitted with small lifters designed to
those arranged for direct heating and those designed for gently turn the product while at the same time maintain-
indirect heating. As seen from Figure 7, certain variants ing maximum contact with the heated shell.
do exist. For example, the directindirect dryer uses both Another type of indirectly heated dryer that is particu-
systems simultaneously. larly useful for fine particles or heat-sensitive materials is
Where direct heating is used, the product of combustion the steam-tube unit. This dryer can be of the fixed-tube
are in intimate contact with the material to be dried while variety equipped with conventional lifting flights designed
in the case of the indirect system, the hot gases are ar- to cascade the product through a nest of square section
ranged to circulate around the dryer shell. Heat transfer tubes, or alternatively, a central rotating tube nest can be
then is by conduction and radiation through the shell. used. Figure 8 shows a fixed-tube rotary dryer, which nor-
With the indirectdirect system, hot gases first pass mally has an electrical vibrator fitted to the tube nest in
down a central tube coaxial with the dryer shell and return order to eliminate the possibility of bridging of the product
through the annular space between the tube and the shell. with consequent loss of heat-transfer surface. Since the
The material being cascaded in this annulus picks up heat heat exchanger is positioned within the insulated shell in
from the gases and also by conduction from direct contact this type of dryer, the air rejection rate is extremely low
with the central tube. This design is thermally very effi- and thermal efficiencies are high. In general, this design
cient. Again, while there are a number of proprietary de- is suitable only for free-flowing materials.
signs employing different systems of airflow, in the main A considerable amount of work has been done on the
these dryers are of two types: parallel and countercurrent development of various types of lifting flights, all designed
flow. With parallel flow, only high-moisture-content mate- to produce a continuous curtain of material over the cross
rial comes into contact with the hot gases, and, as a result, section of the dryer shell. Other special configurations in-
higher evaporative rates can be achieved than when using volve cruciform arrangements to produce a labyrinth path.
countercurrent flow. The object is to give longer residence times where this is
Direct firing
Parallel flow
Counter-current flow
Indirect/direct firing
Exaust
fan Filter
Cyclone
Feed
Cyclone
Product
recycle
Feed
Cleanout ,
duct Heater
Main
fan
Figure 9. Multipass (a) and air recycle (b) arrangements in flash dryers.
porting band or alternatively upward. Sometimes a com- of modular construction are illustrated in Figures 10, 11,
bination of the two may be dictated by the nature of the and 12.
wet feed. It occasionally happens that extruded materials With this type and size of dryer, the average product
have a tendency to coalesce when deposited on the band, throughput is about 5600 Ib/h and involves an evaporation
in which case one or more sections at the wet end of the of 1600 Ib/h moisture. It is not unusual, however, to find
dryer may be arranged for upward airflow to reduce the equipment with evaporative capacities of 3000 Ib/h. Such
effect. Wherever possible, through-air circulation is used outputs involve quite a large band area with correspond-
as opposed to transverse airflow. This results in greatly ingly large floor area requirements. Various types of feed-
increased evaporative rates as may be seen from Table 1. ing arrangements are available to spread or distribute the
An illustration of the relatively high performance of a wet product over the width of the band. Here again, the
band dryer operating on this system as compared with a nature of the feed is an important prerequisite for efficient
unit having transverse airflow can be cited in a case in- drying. Steam-heated, finned drums have been used as a
volving the processing of a 70% moisture content filter means of producing a partially dried, preformed feed.
cake. When this material is dried in a conventional unit, While the amount of predrying achieved is reflected in in-
the cycle time is in the region of 28 h. This is reduced to creased output for a given dryer size or, alternatively, en-
55 min in the through-circulation band dryer largely as a ables a smaller dryer to be used, these items are usually
result of using an extruder-performer designed to produce much more costly than many of the mechanical extruders
a dimensionally stable bed of sufficient porosity to permit that are available.
air circulation through the feed. Generally, these extruders operate with rubber covered
In view of this, transverse airflow usually is used only rollers moving over a perforated die plate with feed in the
where the type of conveyor necessary to support the prod- form of pressed cakes or more usually, as the discharge
uct does not allow through-flow or where the product form from a rotary vacuum filter. Others of the pressure type
is not suitable for this method of airflow. The most usual employ a gear pump arrangement, with extrusion taking
method of heating is by steam through heat exchangers place through a series of individual nozzles, while some use
mounted in the side plenums or above the band, although screw feeds that usually are set up to oscillate in order to
direct oil and gas firing sometimes is used. In such cases, obtain effective coverage of the band. Alternative designs
the products of combustion normally are introduced to a include rotating cam blades or conventional bar-type gran-
hot well or duct at an elevated temperature from where ulators, although the latter often produce a high propor-
they are drawn off and mixed with circulating air in each tion of fines because of the pronounced shearing effect.
zone or section of the dryer. This makes the product rather unsuitable because of the
Another alternative with direct firing is to use a series entrainment problems that can occur.
of small individual burners positioned so that each serves Each of the types available is designed to produce
one or more zones of the dryer. Typical single-pass dryers continuousdiscontinuous extrudates or granules, with
Figure 10. Continuous conveyor band dryer ar-
rangement for direct gas firing.
the grid perforations spaced to meet product characteris- the feed and delivery ends of the machine housing the drive
tics. In selecting the proper type of extruder, it is essential and terminals remain the same and form an increased pro-
to carry out tests on semiscale equipment as no other valid portion of the cost of the smaller dryer. While the cost of
assessment of suitability can be made. the extruder also must be taken into account in the com-
As a further illustration of the desirability of using a parison, cost reduction still would be about 15%. Of course,
preforming technique, tests on a designated material ex- other advantages result from the installation of the
hibited a mean evaporative rate of 1.9 Ib ft2 h when pro- smaller dryer. These include reduced radiation and con-
cessed in filter-cake form without preforming. When ex- vection losses and a savings of approximately 40% in the
truded, however, the same material being dried under floor area occupied.
identical conditions gave a mean evaporative rate of 3.8 Ib This type of plant does not involve high installation
ft2 h. This indicates, of course, that the effective band area costs, and both maintenance and operating labor require-
required when working on extruded material would be ments are minimal. Since they generally are built on a
only 50% of that required in the initial test. Unfortunately, zonal principle, with each zone having an integral heater
the capital cost is not halved as might be expected since and fan, a good measure of process control can be achieved.
Figure 12. Band dryer and extru-
der with dye stuffs.
Furthermore, they provide a high degree of flexibility be- 2. Does the quantity to be handled per unit time sug-
cause of the provision of variable speed control on the con- gest batch or continuous operation?
veyor.
3. From a knowledge of the product, select the type(s)
of dryer that it appears would handle both the wet
SELECTION feedstock and the dried product satisfactorily and re-
late this to the equipment having the highest appli-
The application ratings given in Table 1 in which are listed cation rating in Table 1.
the approximate mean evaporative rates for products un- 4. From a knowledge of the required evaporative duty,
der a generic classification are based on APV experience ie, the total mass of water to be evaporated per unit
over a number of years in the design and selection of drying time and by the application of the approximate Eav
equipment. It should be appreciated, however, that drying figure given in Table 1, estimate the size of the dryer.
rates vary considerably in view of the variety of materials 5. Having established the size of the dryer on an area
and their widely differing chemical and physical charac- or volumetric basis, refer to the appropriate curve in
teristics. Furthermore, drying conditions such as tempera- Figures 13 and 14 and establish an order of cost for
ture and the moisture range over which the material is to the particular type of unit.
be dried have a very definite effect on the actual evapora-
tive rate. It is important, therefore, when using the figures Although a great deal of fundamental work has been
quoted that an attempt is made to assess carefully the na- carried out into the mechanics of drying, which provides a
ture of the product to be handled and the conditions to basis for recommendations, it is most desirable for pilot
which it may be subjected in order to achieve greater ac- plant testing to be done. This is necessary not only to sup-
curacy. With these factors in mind, it is hoped that the port theoretical calculations but also to establish whether
foregoing observations on drying techniques along with the a particular dryer will handle the product satisfactorily. In
appropriate tables and curves will provide a basis for mak- the final analysis, it is essential to discuss the drying ap-
ing an assessment of the type, size, and cost of drying plication with the equipment manufacturer who has the
equipment. necessary test facilities to examine the alternatives objec-
In making a preliminary assessment for dryer selection, tively and has the correlated data and experience from
there are a number of further points to consider: field trials to make the best recommendation.
1. What is the nature of the upstream process? Is it EFFICIENT ENERGY UTILIZATION IN DRYING
feasible to modify the physical properties of the feed,
eg, mechanical dewatering to reduce the evaporative It generally is necessary to employ thermal methods of dry-
load? ing in order to reach what is termed a "commercially dry"
Order of cost (thousands of dollars)
Figure 14. Approximate capital costs of (5) pneumatic dryers (direct-fired, stainless steel, includ-
ing primary cyclone), (6) double-cone dryers (stainless steel, excluding vacuum equipment),
(7) drum dryers (cast-iron drums, dip feed), (8) tray dryers (steam/electric-heated).
condition. As a result, drying forms an important part of tions to emphasize that in the final analysis, the primary
most food and chemical processes and accounts for a sig- concern is the "cost per unit weight" of the dried product.
nificant proportion of total fuel consumption. This single fact must largely govern any approach to dryer
The rapid escalation of fuel costs over the past 10 yr, selection and operation. Additionally, there is an increas-
together with the prevailing uncertainty of future avail- ing necessity to consider the unit operation of drying in
ability, cost, and possible supply limitations, highlights the concert with other upstream processes such as mechanical
continued need to actively engage in the practice of energy dewatering and preforming techniques in a "total energy"
conservation. Some of the factors affecting dryer efficiency evaluation.
and certain techniques designed to reduce the cost of the In considering which factors have a bearing on dryer
drying operation are discussed in the next few sections. efficiency and what can be done to maximize that effi-
In making an appraisal of factors affecting dryer effi- ciency, the following aims should be kept in mind:
ciency, it is useful to draw up a checklist of those items 1. Maximum temperature drop across the dryer system
that have a significant bearing on both operation and econ- indicating high energy utilization. This implies max-
omy. It also is appropriate prior to examining various op- imum inlet and minimum outlet temperature.
2. Employ maximum permissible air recirculation, ie, in horsepower more than offset the power required for the
reduce to an absolute minimum the quantity of dryer extruder. This differential is approximately 15 kW and the
exhaust, having due regard for humidity levels and overall saving in total energy is approximately 10% ie, 466
possible condensation problems. kW compared with 518 kW. Furthermore, the fact that the
3. Examine the possibility of countercurrent drying, ie, dryer has appreciably smaller overall dimensions provides
two-stage operation with exhaust gases from a final an added bonus in better utilization of factory floor space.
dryer being passed to a predryer, or alternatively,
preheating of incoming air through the use of a heat Drying Techniques
exchanger located in the exhaust gases.
If, as stated, the prime concern is the cost per pound of
4. Utilize "direct" heating wherever possible in order to dried product, then major savings can be achieved by re-
obtain maximum heat release from the fuel and ducing the amount of water in the feedstock to a minimum
eliminate heat-exchanger loss. prior to applying thermal methods of drying. Again, since
5. Reduce radiation and convection losses by means of it generally is accepted that the mechanical removal of wa-
efficient thermal insulation. ter is less costly than thermal drying, it follows that con-
siderable economies can be made when there is a substan-
While the above clearly are basic requirements, there tial amount of water that can be readily removed by
are a number of other areas where heat losses occur in filtration or centrifuging. This approach, however, may in-
practice, including sensible heat of solids. Furthermore, volve changing the drying technique. For example,
other opportunities exist for improving the overall effi- whereas a liquid suspension or mobile slurry would require
ciency of the process. These are related to dryer types, a spray dryer for satisfactory handling of the feed, the dry-
methods of operation, or possibly the use of a combination ing of a filter cake calls for a different type of dryer and
of drying approaches to obtain optimum conditions. certainly presents a totally different materials handling
situation.
Types of Dryers In approaching a problem by two alternative methods,
Considering the requirements for high inlet temperature, the overall savings in energy usage may be considerable
the "flash" or pneumatic dryer offers great potential for as illustrated in Figure 15, which is a plot of feed moisture
economic drying. This stems from the simultaneous flash content versus dryer heat load. As may be seen, the differ-
cooling effect that results from the rapid absorption of the ence in thermal energy used in (A) drying from a moisture
latent heat of vaporization and allows the use of high inlet content of 35% down to 0.1%, or alternatively (B) drying
temperatures without thermal degradation of the product. the same material from 14% down to 0.1% is 24.3 X 106
This type of dryer also exhibits extremely high evaporative
rate characteristics, but the short gas-solids contact time
can in certain cases make it impossible to achieve a very
low terminal moisture. However, a pneumatic dryer work-
ing in conjunction with a rotary or a continuous fluidized-
bed dryer provides sufficient residence time for diffusion of
moisture to take place. Such an arrangement combines the
most desirable features of two dryer types and provides a
Dryer feed moisture content (% W.W.B.)
Table 3. Comparison of Operating Conditions and Energy Utilization of Pneumatic-and-Spray Dryers Processing
Concentrates
Parameter Pneumatic dryer Spray dryer
Feed rate 88,200 Ib/h 88,200 Ib/h
Filtrate rate 21,500 Ib/h
Evaporative rate 9200 Ib/h 30,700 Ib/h
Production rate 57,500 Ib/h 57,500 Ib/h
Initial moisture content 14% 35%
Final moisture content 0.1% 0.1%
Air inlet temperature, 0F 752 752
Air outlet temperature, 0F 230 230
Total thermal input 21.43 X 106 Btu/h 66.2 X 106 Btu/h
Basic air volume (BAV) at NTP 28,10ONCFM 86,700 NCFM
Fuel consumption 1080 Ib/h 3290 Ib/h
Total dryer horsepower 187 kW 53OkW
Total filter horsepower 295 kW
Total system horsepower 482 kW 53OkW
Total thermal input expressed as kilowatts 6280 kW 19,400 kW
Total energy input to system 6762 kW 19,930 kW
Note: An assumed volumetric flow of 3 ft3/min ft2 of fitter area with approximately 1 hplO ft3 min has been used as being typical of the flow rates and energy
requirements for the filtration or mechanical dewatering equipment.
Cyclone
collector
Drying
column
Circulating
fan
Wet Fresh
feed Product air
Recycle
gases
Back-mixer
Screw
feeder
Table 4. Comparison of Self-Inertizing Thermoventuri comparing the two dryers on the basis of their cross-
Dryer Versus Total Rejection Thermoventuri Dryer sectional areas, the total rejection dryer would have rather
Parameter Closed circuit Total rejection more than double the area of the closed-circuit system.
There are obvious limitations to the use of such a tech-
Evaporation, Ib/h 1,250 1,250 nique, but the advantages illustrated are very apparent,
IMC, % wwb 85 85
FMC, % wwb 10 10
especially the savings in thermal energy alone, viz,
Feed, Ib/h 1,500 1,500 695,000 Btu/h representing about 29.2% of the total re-
Air inlet temperature, 0F 932 662 quirements of the conventional drying system.
Air outlet temperature, 0F 302 248
Exhaust dry airflow, Ib/h 1,368 16,400 Effect of Changing Feed Rates
Exhaust losses, Btu/h 79,700 744,000
Heat losses, Btu/h 120,000 150,000 Since it has a significant bearing on efficiency, another fac-
Total heat input, Btu/h 1,680,400 2,375,700 tor of major importance to consider when designing dryers
Efficiency, % 87.9 62.4 of this type is the possible effect of reducing feed rate. What
variation in quantity of feed is likely to occur as a result of
operational changes in the plant upstream of the dryer and
as a result, what turndown ratio is required of the dryer?
operation is tending toward superheated vapor drying, and With spray dryers and rotary dryers, the mass airflow can
in practice 40-50% of the gases in circulation are water be varied facilitating modulation of the dryer when oper-
vapor. This suggests that the specific heat of the gas will ating at reduced throughputs.
be approximately 0.34 Btu/lb 0F compared with about 0.24 This, however, is not the case with pneumatic and true
Btu/lb 0F in a conventional total rejection dryer. Since the fluidized-bed dryers since the gases perform a dual func-
mass of gas for a given thermal capacity is appreciably less tion of providing the thermal input for drying and acting
than in a conventional dryer and, as previously mentioned, as a vehicle for transporting the material. Since the mass
oxygen levels are low, much higher operating tempera- flow has to remain constant, the only means open for mod-
tures may be used. This permits a reduction in the size of ulating these dryers is to reduce the inlet temperature.
the closed-circuit dryer. For the case given in Table 4 and This clearly has an adverse effect on thermal efficiency. It
therefore is of paramount importance to establish realistic While demands for energy efficient drying may have be-
production requirements. This will avoid the inclusion of come somewhat relaxed recently with the stabilizing of en-
excessive scale-up factors or oversizing of drying equip- ergy costs, the fact remains that spray dryers and evapo-
ment and thereby maximize operating efficiency. rators are among the most energy-intensive processing
Figure 17 illustrates the effects on thermal efficiency of systems and the future of energy costs is still uncertain.
either increasing the evaporative capacity by increased in- The extra functionality that may be required of the pow-
let temperatures or alternatively, reducing the inlet tem- ders is to a large extent determined by the drying condi-
perature with the exhaust temperature remaining con- tions, including pre- and posttreatment of the concentrate
stant at the level necessary to produce an acceptable dry and final powder. Desirable characteristics are dust-free
product. While the figure refers to the total rejection case and good reconstitution properties that involve carefully
of the previous illustration where design throughput cor- controlled drying conditions, often with added agglomera-
responds to an efficiency of 62.4%, the curve shows that if tion and lecithination steps.
the unit is used at only 60% of design, dryer efficiency falls The interest in the production of high-value specialty
to 50%. The converse, of course, also is true. dried products instead of straight commodity products has
In this brief presentation, an attempt has been made to been accentuated by the government's reduced support to
highlight some of the factors affecting efficiency in drying dairy producers, whereby there will be less milk solids
operations and promote an awareness of where savings available. Processors naturally are looking into ways to
can be made by applying new techniques. While conditions better use these available supplies by producing products
differ from one drying process to another, it is clear that with improved functional, nutritional, and handling prop-
economies can and should be made. erties and, coincidentally, products with higher profit mar-
gins.
This is particularly noticeable in the utilization of whey
SPRAY DRYING: NEW DEVELOPMENTS, NEW
ECONOMICS and whey product derivatives. A larger percentage of the
total whey produced today is handled and processed so
In the field of spray drying, the past 10 years have wit- that it will be suitable as food ingredients for human con-
nessed many new developments initiated mainly to meet sumption. It also is finding new applications by being re-
three demands from food and dairy processorsbetter en- fined into whey protein concentrate and lactose through
ergy efficiency, improved functional properties of the fin- crystallization, hydrolyzation, and separation by ultrafil-
ished powder, and production of new, specialized dried tration.
products. This has been accompanied by progress made in To handle the increase in plant size and complexity and
the automation of drying systems and in stricter require- to meet demands for closer adherence to exact product
ments for the reduction of environmental impacts result- specifications, dryer instrumentation has been improved
ing from the operation of spray dryers. and operation gradually has evolved from manual to fully
automated. Today, it is normal for milk drying plants to be
controlled by such microprocessor-based systems as the
APV ACCOS, with automation covering the increasingly
complex startup, shutdown, and CIP procedures as well as
sophisticated automatic adjustment of the dryer operating
parameters to variations in ambient-air conditions.
Finally, more stringent demands governing environ-
mental aspects of plant operations have resulted in that
virtually all spray dryers today have to be equipped with
exhaust air pollution control devices such as wet scrubbers
or bag filters.
Efficiency (%)
Product out
Figure 18. Flat-bottomed drying chamber incorporates rotating
powder discharger and can be equipped with an air broom.
Figure 20. Spray-dried autolyzed yeast (2000 X magnification).
Particle is hollow and filled with crevices.
Figure 19. Steam is added around and into the atomizing disk Figure 21. Spray-dried autolyzed yeast with steam injection
to minimize air in the atomized liquid droplet. (2000 X magnification). Particle is solid and essentially void-free.
Air heater Feed
Atomizer
Air out
Air out
ticularly narrow particle size distribution and/or coarse tide. During this operation, the temperature of the parti-
characteristics. Since the particle size is dependent on the cles will not increase much owing to the cooling effect re-
feed rate, dryers with pressure nozzles are somewhat lim- sulting from water evaporation.
ited relative to changing product characteristics and op- The rate of drying will be very high at first but then
erating rates. declines as the moisture content of the particles decreases.
When the powder reaches the bottom of the drying cham-
Pneumatic (Two-Fluid) Nozzles. This type of nozzle uses ber, it has attained its final moisture and normally is
compressed air to accomplish the atomization of the feed picked up in a pneumatic cooling system to be cooled down
product. The advantage with this type of atomizer is that to a suitable bagging or storage temperature. Powder that
it allows a greater flexibility in feed capacity than what is carried with the air is separated in cyclone collectors. As
can be obtained with pressure nozzles. However, particle the powder is cooled in the pneumatic system, it also is
size distribution is not as good as what can be obtained subjected to attrition. This results in a powder that is fine,
with the centrifugal or high-pressure nozzle-type atomiz- dusting, and has relatively poor redissolving properties.
ers, and because of the large quantities of compressed air Single-stage dryers are made in different configura-
required, operating costs tend to be quite high. tions. The basic ones are described below.
Single-Stage Drying Box Dryers. A very common type of dryer in the past,
Defined as a process in which the product is dried to its the drying air enters from the side of a boxlike drying
final moisture content within the spray-drying chamber chamber. Atomization is from a large number of high-
alone, the single-stage dryer design is well known through- pressure nozzles also mounted in the side of the chamber.
out the industry, although some difference in airflow pat- Dried powder will collect on the flat floor of the unit, from
terns and chamber design exist. which it is removed by moving scrapers. The exhaust air
As illustrated, the drying air is drawn through filters, is filtered through filter bags that also are mounted in the
heated to the drying temperature, typically by means of a chamber. In some instances, cyclones will be substituted
direct-combustion natural-gas heater, and enters the spray for the filter bags.
drying chamber through an air distributor located at the
top of the chamber. The feed liquid enters the chamber Tall-Form Dryers. These are very tall towers in which
through the atomizer, which disperses the liquid into a the airflow is parallel to the chamber walls. The atomiza-
well-defined mist of very fine droplets. The drying air and tion is by high-pressure nozzles. This type of dryer is used
droplets are very intimately mixed, causing a rapid evap- mainly for the production of straightforward, commodity-
oration of water. As this happens, the temperature of the type dried powders.
air drops, as the heat is transferred to the droplets and
used to supply the necessary heat of evaporation of the Wide-Body Dryers. While the height requirement is less
liquid. Each droplet thus is transformed into a powder par- than for the tall-form type, the drying chamber is consid-
erably wider. The atomizing device can be either centrifu- moisture within the particles that can move by capillary
gal or nozzle type. The product is sprayed as an umbrella- action are extracted and (2) the falling-rate period when
shaped cloud, and the airflow follows a spiral path inside diffusion of water to the particle surface becomes the de-
the chamber. As shown in Figs. 18 and 22, this type of termining factor. Since the rate of diffusion decreases with
dryer is designed either with a flat or conical bottom. the moisture content, the time required to remove the last
Flat-Bottom Dryer. The flat-bottom dryer is not a new few percent of moisture in the case of single-stage drying
development, but the design has gained renewed interest takes up the major part of the residence time within the
in recent years. dryer. The residence time of the powder thus is essentially
The chamber has a nearly flat bottom from which the the same as that of the air and is limited to between 15
powder is removed continuously by means of a rotating and 30 s. As the rate of water removal is decreasing toward
pneumatic powder discharger. The dryer has the obvious the end of the drying process, the outlet air temperature
advantage of considerably reduced installed height re- has to be kept fairly high in order to provide enough driv-
quirements compared to cone-bottom dryers, and it is also ing force to finish the drying process within the available
easy for operators to enter the chamber for cleaning and air residence time in the chamber.
inspection. Another advantage is that the rotating powder In multiple-stage drying, the residence time is in-
discharger provides a positive powder removal from the creased by separating the powder from the main drying air
chamber and a well-defined powder residence time. This and subjecting it to further drying under conditions where
has been shown to be important in the processing of heat- the powder residence time can be varied independently of
sensitive products such as enzymes and flavor compounds. the airflow. Technically, this is done either by suspension
Depending on the product involved, a pneumatic powder in a fluidized bed or by retention on a moving belt. Since a
cooling system also may be installed. longer residence time can be allowed during the falling-
Typically, this type of dryer is used for egg products, rate period of the drying, it is possible and desirable to
blood albumin, tanning agents, ice cream powder and top- reduce the drying air outlet temperature. Enough time to
pings. The flat- and bottom chamber, incidentally, may be complete the drying process can be made available under
provided with an air broom, which is indicated by the col- more lenient operating conditions.
ored section in Figure 18. By blowing tempered air onto The introduction of this concept has led to higher ther-
the chamber walls while rotating, this device blows away mal efficiencies. Fifteen years ago, the typical inlet and
loose powder deposits and cools the chamber walls to keep outlet temperatures of a milk spray dryer were 360-2050F.
the temperature below the sticking point of certain prod- Today, the inlet temperature is often above 43O0F, with out-
ucts. Some items with which the air bottom technique has let temperatures down to about 1850F.
been successful are for fruit and vegetable pulp and juices,
meat extracts, and blood. Two-Stage Drying. In a typical two stage drying process
Cone-Bottom Dryer. Figure 22, meanwhile, shows a as shown in Figure 23, powder at approximately 7% mois-
conical-bottom chamber arrangement with a side air out- ture is discharged from the primary drying chamber to an
let, high-pressure nozzle atomization, and pneumatic APV fluid bed for final drying and cooling. The fact that
product transport beneath the chamber. This single-stage the powder leaves the spray dryer zone at a relatively high
dryer is very well suited to making relatively large parti- moisture content means that either the outlet air tern-
cles of dairy products or proteins for cattle feed. If the prod-
uct will not withstand pneumatic transport, it may be
taken out unharmed directly from the chamber bottom.
Feed
Air heater
Multiple-Stage Dryers Atomizer
Air out
The best way to reduce energy usage in spray drying is, of
course, to try and reduce the specific energy consumption
of the process. With advances in atomizer and air distrib-
utor designs it has been possible with many products to
operate with higher dryer inlet temperature and lower out-
let temperature. While this procedure substantially cuts
Integrated
energy needs and does not harm most heat-sensitive prod- fluid bed
ucts, care must be taken and proper balance struck. The
nature of the product usually defines the upper limit, ie, Product
the denaturation of milk protein or discoloring of other out
products. A higher inlet temperature requires close control External
of the airflow in the spray-drying chamber, and particu- fluid bed
larly around the atomizer. Furthermore, it must be noted Product
that a lower outlet temperature will increase the humidity out
of the powder.
Generally speaking, the drying process can be divided
into two phases: (1) the constant-rate drying period when
drying proceeds quickly and when surface moisture and Figure 23. Two-stage drying with external fluid bed.
perature can be lowered or the inlet air temperature in-
creased. Compared to single-stage drying, this will result
in better thermal efficiency and higher capacity from the
same size drying chamber. As the product is protected by
its surrounding moisture in the spray-drying phase, there
normally are no adverse effects on product quality result- Total
ing from the higher inlet air temperature. energy cost
The outlet air from the chamber leaves through a side
air outlet duct, and the powder is discharged at the bottom
of the chamber into the fluid bed. This prolongs the drying
Spray-Bed Dryer
While the concept of a three-stage drying system with an
integrated fluid evolved from traditional dryer technology,
it served to spur the development of a modified technique
Integrated referred to by APV as the "Spray Bed Dryer." This machine
fluid bed is characterized by use of an integrated fluid bed at the
bottom of the drying zone but with drying air both entering
Product
out and exiting at the top of the chamber. Atomization can be
with either nozzles or a centrifugal atomizer.
External The chamber fluid bed is vigorously agitated by a high
fluid bed fluidization velocity. Particles from the spray-drying zone
Product enter the fluid bed with a moisture content as high as 10-
out 15% depending on the type of product and are dried in the
bed to about 5%. Final drying and cooling take place in an
external fluid bed.
The structure of the powder produced in the Spray Bed
differs considerably from the conventional. It is coarse,
consists of large agglomerates, and consequently has low
bulk density but exhibits excellent flowability. The dryer
is very suited to the processing of complicated products
having high contents of fat, sugar, and protein. Two of the
many possible variations of this type drying are shown in
Figures 26 and 27.
Spray-drying systems divided into two or more stages
undoubtedly will be a characteristic of almost all future
dryer installations. The advantages resulting from this
technology will provide dairy and food processors with the
necessary flexibility and energy efficiency required to meet
today's uncertain market and whatever changes will be
called for in the future.
Pollution-Control Devices
Virtually, all plants have a system to ensure clean exhaust
air while collecting powder at an efficiency of about 99.5%,
Figure 25. (a,b) Three-stage dryer combines conical drying and may be supplied with secondary pollution-control col-
chamber, integrated stationary fluid bed with directional air flow lection equipment if necessary. In most new spray dryers
and external vibrating fluid bed. Provides optimum conditions for this is accomplished using bag filter collectors after the
producing nondusty, hygroscopic, and high-fat-content products. primary collection device. In the case of such products as
acid whey where the use of bag collectors is not practical,
high-efficiency scrubbers are used. Some multipurpose
Atomization can be either by pressure nozzles or by a plants have both plus an elaborate system of ducts and
centrifugal-type atomizer. dampers to switch between the devices as different prod-
The three-stage system is exceptionally suitable for the ucts are dried.
production on nondusty, hygroscopic, and high-fat-content An added benefit from the use of sanitary bag collectors
products. The dryer can produce either high-bulk-density is an improvement in the yield of sale product. Although
powder by returning the fines to the external fluid bed, or this increase typically is not more than 0.5%, it still can be
powder with improved wettability by straight-through ag- of substantial value over a year of operation.
glomeration with the fines reintroduced into an atomizing
zone. The concept also allows the addition of liquid into the Heat-Recovery Equipment
internal fluid bed, thus opening the path to the production Although it is possible to reduce the direct heating energy
of very sophisticated agglomerated and instantized prod- consumption by the use of multiple-stage drying, optimum
ucts, ie, excellent straight-through lecithinated powders. thermal conditions generally require that heat recupera-
Whey powder from such a system shows improved quality tors be used as well. A few approaches are shown in
because of the higher moisture level present when the pow- Figure 28.
der enters the integrated fluid bed, providing good condi- Despite the many recuperators available for recovering
tions for lactose after crystallization within the powder. heat from drying air, only a few are suited for the spray-
Figure 26. One variation of APV Crepaco Spray Bed
Dryer arrangements (see Fig. 27 for other variation).
Basic dryer with centrifugal atomizer and integrated
fluid bed, which is agitated by high fluidation velocity.
Preheater Air
heater
Bag filter
Air
heater
Air (
inlet
Dry
section
drying process. This is due to the dust-laden air that is Air-to-Air Heat Recuperators. For optimum flexibility,
involved in the process and that tends to contaminate heat this heat exchanger is of modular design, each module con-
exchange surfaces. To be effective, therefore, recuperators sisting of 804 tubes welded to an end plate. Available in
for spray-dryer use should have the following properties: various standard lengths, the modules can be used for
counterflow, cross-flow, or two-stage counterflow as
Modular system sketched in Figure 29. While the first two designs are
High thermal efficiency based on well-known principles, the two-stage counterflow
Low pressure drop (patent pending) system is an APV development. This re-
Automatic cleaning cuperator consists of two sections, a long dry element and
a shorter wet section. During operation, hot waste air is
Large temperature range
passed downward through the dry module tubes and
Stainless steel cooled to just above the dew point. It then goes to the wet
Large capacity section where latent heat is recovered. The inner surfaces
Low price of these shorter tubes are kept wet be recirculating water.
The system, therefore, not only recovers free and latent
Two such recuperators are the air-to-air tubular and the heat from the waste air but also scrubs the air and reduces
air-to-liquid plate designs. the powder emission by more than 80%. Effectiveness and
Waste air
inlet
Waste air
outlet
Fresh air
outlet
Fresh air
intlet
Waste air
inlet
Fresh air
outlet
Waste air
inlet
Fresh air
outlet
Fresh air
inlet
economy are such that the system replaces a conventional outlet and inlet air to be preheated, a liquid heat-recovery
recuperator-scrubber combination. system is available. This plate recuperator as shown in
Figure 30 uses various standard plates as the base with
Air-to-Liquid Recuperator. In cases where an air-to-air waste air being cooled in counterflow by circulating a
recuperator is impractical or uneconomical because of water/glycol mixture. At high temperature, circulating
space limitations or the length of the distance between the thermal oils are used. Heat recovered by this means gen-
WATER OUTLET
WATER INLiT
erally is recycled to preheat the drying air but can be used strong mechanical stirring in order to become homogene-
for other purposes such as heating water, clean-in-place ously dispersed or dissolved in the liquid. What is happen-
(CIP) liquids, or buildings. ing is that as water aided by capillary forces penetrates
into the narrow spaces between the particles, the powder
Other Heat-Recovery Methods. While many spray- will start to dissolve. As it does, it will form a thick, gel-
drying plants are equipped with bag filters to minimize like mass that resists further penetration of water. Thus,
emissions to the environment and recover valuable pow- lumps will be formed that contain dry powder in the middle
der, the filtration system can be coupled with a finned-tube and, if enough air is locked into them, will float on the
recuperator for heat-recovery purposes. This type of recu- surface of the liquid and resist further dispersion.
perator is particularly effective when the air is not dust- In order to produce a more readily dispersible product,
loaded. It is compact, very flexible and normally, very in- the specific surface of the powder has to be reduced and
expensive. the liquid needs to penetrate more evenly around the par-
Some degree of heat recovery can also be accomplished ticles. In an agglomerated powder with its open structure,
by using available low-temperature waste streams to pre- the large passages between the individual powder parti-
heat the drying air through a finned-tube heat exchanger. cles will assist in quickly displacing the air and allow liquid
Examples of such sources of waste heat include evaporator to penetrate before an impenetrable gel layer is formed.
condensate and scrubber liquids. The powder thus can disperse into the bulk of the liquid,
after which the final dissolution can take place.
SPRAY DRYERS: FLUID-BED AGGLOMERATION Although there always is some degree of overlap be-
tween them, the reconstitution of an agglomerated product
Most powderlike products produced by spray drying or can be considered as consisting of the following steps:
grinding are dusting, exhibit poor flow characteristics, and
are difficult to rehydrate. 1. Granular particles are wetted as they touch the wa-
It is well known, however, that agglomeration in most ter surface.
instances will improve the redispersion characteristics of 2. Water penetrates into the pores of the granule struc-
a powder. Added benefits of the agglomerated powder is ture.
that it exhibits improved flowability and is nondusting. All 3. The wetted particles sink into the water.
of these are characteristics for which the demand has in- 4. The granules disintegrate into their original small-
creased in recent years. est particles, which disperse in the water.
Depending on the application or the area of industry 5. The small dispersed particles dissolve in the water.
where the process is being used, the process sometimes is
also referred to as granulation or instantizing. It is important to realize that it is the total time re-
quired for all these steps that should be the criterion in
Instant Powders evaluating a product's instant properties. It is not unusual
Powders with particle size less than about 100 /zm typically to see products characterized only on their wettability
tend to form lumps when mixed with water and require This neglects the importance of the dispersion and disso-
Exhaust
Feed air
Bag
collector
Fines return
system
To powder
storage
Figure 31. Straight-through agglomeration.
lution steps, the time for which may vary considerably The steam condensation method usually cannot provide
with different agglomeration methods. enough wetting without adversely heating the material
For powders that are produced by spray drying, there and is used less frequently on newer systems.
are a number of ways in which the agglomeration can be After having been brought into a sticky state, the par-
accomplished in the spray dryer itself. This often is re- ticles are contacted under such conditions that a suitable,
ferred to as the "straight-through" process and is illus- stable agglomerate structure can be formed. The success
trated in Figure 31. Note that fines powder from the cy- of this formation will depend on such physical properties
clone is conveyed up to the atomizer, where it is introduced as product solubility and surface tension as well as on the
into the wet zone surrounding the spray cloud. Cluster for- conditions that can be generated in the process equipment.
mation will occur between the semimoist freshly produced For most products, possible combinations of moisture
particles and the recycled fines. The agglomerated product and temperature can be established as shown in Figure
then is removed from the bottom of the drying chamber, 32. Usually, the window for operation is further narrowed
cooled, and packaged. This method produces a degree of down by the specifications for product characteristics.
agglomeration that is sufficient for many applications. Once the agglomerate structure is created, the added mois-
An alternative approach to agglomeration is referred to
as the "rewet method." This is characterized by processing
an already existing fine dry powder into an agglomerate
using fluidized-bed technology.
Exhaust
Liquid air
Powder in
Steam
Agglomerated
product
Powder in Bag
collector
Compressed air
Binder
liquid
Sifter
Fines and
Finished oversize
product return
Figure 34. Fluid bed rewet ag-
glomeration system.
Table 5. Frequently Used Binders The final zone is for cooling where either ambient or
For food products For chemical products cooled air is used to cool the agglomerates to a suitable
packaging temperature.
Malto dextrines Lignosulfonates During processing, air velocities are adjusted so that
Gum arable Poly(vinyl alcohol) (PVA) fine, unagglomerated powder is blown off the fluidized
Starch Any of the food product binders
Gelatin
layer. The exhaust air is passed through a cyclone sepa-
Molasses rator for removal and return of entrained powder to the
Sugar inlet of the agglomerator. When there are high demands
for a narrow particle size distribution, the agglomerated
powder is passed through a sifter, where the desired frac-
tion is removed while over- and undersize material is re-
reproducibility of a volumetric feeder is satisfactory and cycled into the process.
there is no need for a complicated feed system such as a As with all rewet agglomeration equipment, the opera-
loss-in-weight or similar type. tion must be performed within certain operating parame-
The fluid bed unit is constructed with several processing ters. Overwetting will lead to poor product quality, while
zones, each with a separate air supply system. The first underwetted powder will produce fragile agglomerates and
section is the rewet and agglomeration section where ag- an excessive amount of fines. However, fluid-bed agglom-
glomerates are formed. Here, the powder is fluidized with eration does offer a great degree of flexibility in controlling
heated air in order to utilize its thermoplastic character- the final result of the process. The characteristics of the
istics. formed agglomerate can be influenced by operating con-
The binder liquid almost always is water or a water- ditions such as binder liquid rate, fluidizing velocity, and
based solution, whereas steam, as already explained, temperature. Typically, the fluid-bed rewet method will
rarely is used. The binder liquid is sprayed over the flu- produce agglomerated products with superior redispersion
idized layer using two fluid nozzles driven by compressed characteristics.
air. For large systems, numerous nozzles are used. Powder As indicated by this partial list, this method has been
deposits are minimized by accurate selection of spray noz- used successfully with a number of products.
zle angles and nozzle position patterns. Powder movement
is enhanced by the vibration of the fluid-bed unit itself and Dairy products
by the use of a special perforated air distribution plate with
Infant formula
directional air slots. A proper detailed design is vital in
order to have a trouble-free operation. Calf milk replacer
From the agglomeration zone, the powder automati- Flavor compounds
cally will flow into the drying area where the added mois- Corn syrup solids
ture is removed by fluidization with heated air. In some Sweeteners
instances, more than one drying section is required, and
in such cases, these sections are operated at successively Detergents
lower drying temperatures in order to reduce thermal ex- Enzymes
posure of the more heat-sensitive dry powder. Fruit extracts
Malto dextrines cloud, thus forming agglomerates at this point as well. Ma-
Herbicides terial from the integrated fluid bed is taken to an external
Egg albumin fluid bed for final drying and cooling.
The spray-bed dryer is a highly specialized unit that can
In most cases, the agglomeration can be accomplished produce only agglomerated powder. It is best suited for
using only water as a rewet medium. This applies to most small to medium-sized plants since the efficiency of the
dairy products and to malto dextrine-based flavor formu- agglomeration process unfortunately decreases as the
lations. For some products, increased agglomerate size and plant increases in size. This is because the spray zone be-
strength has been obtained by using a solution of the ma- comes too far removed from the fluid-bed zone as the size
terial itself as the binder liquid. In the case of relatively of the dryer increases.
water-insoluble materials, a separate binder material has Agglomerates from the spray-bed dryer exhibit excel-
been used, but it must be one that does not compromise lent characteristics. They are very compact and show high
the integrity of the final product. The addition of the binder agglomerate strength and good flowability.
material may have a beneficial effect on the end product
at times. This is seen, for example, in flavor compounds Considerations and Conclusions
when a pure solution of malto dextrine or gum arabic may While the agglomeration process improves the redisper-
further encapsulate the volatile flavor essences and create sion, flowability, and nondustiness of most fine powders, it
better shelf life. In other instances, the added binder can invariably decreases the bulk density. The comparison in
become part of the final formulation as is the case with Table 6 clearly shows that agglomeration improves the
some detergents. powder wettability and dispersibility. Individual powder
For some materials, the addition of a binder compounds particles with a mean diameter of less than 100 //m are
is an unavoidable inconvenience. At such times, the se- converted into agglomerates ranging in size from 250 to
lected binder must be as neutral as possible and must be 400 /zm, with the rewet method being able to produce the
added in small quantities so that the main product is not coarser agglomerate. The powder bulk density will de-
unnecessarily diluted. An example of this is herbicide for- crease from about 43 lb/ft3 to approximately 28 Ib/ft3. Use
mulations, which often have a very well defined level of of the rewet method will expose the product to one addi-
active ingredients. tional processing step that, in this case, will somewhat af-
For products containing fat, the normal process often is fect the proteins and result in a slightly poorer solubility.
combined with a step by which the agglomerates are Since fluid bed agglomeration can be operated as an in-
coated with a thin layer of surface-active material, usually dependent process, it can be used with already existing
lecithin. This is done by mounting an extra set of spray power-producing equipment. It offers great flexibility and
nozzles near the end of the drying section where the sur- ease of operation, and provides a convenient way to add
factant is applied. functionality, nondustiness, and value to a number of prod-
Variations of the fluid-bed rewet technology have been ucts.
developed whereby the system serves as a mixer for sev-
eral dry and wet products. An example of this may be seen
in the APV fluid mix process for the continuous production SPIN FLASH DRYERS
of detergent formulations from metered inputs of the dry
and wet ingredients. This provides an agglomerated end Background Information
product that is produced with minimum energy input
when compared to traditional approaches. While mechanical dewatering of a feed slurry is signifi-
cantly less expensive than thermal drying, this process re-
Spray-Bed Dryer Agglomeration sults in a paste or filter cake that cannot be spray dried
and can be difficult to handle in other types of dryers. The
While the fluid-bed rewet agglomeration method produces spin flash dryer is one option available for continuous pow-
an excellent product that is, in most respects, superior to der production from pastes and filter cakes without the
that made directly by the straight-through process, a new need for grinding.
generation of spray dryers has evolved that combines fluid- Powders generally are produced by some form of drying
bed agglomeration with spray drying. These are referred operation. There are several generic types of dryers, but
to as "spray-bed" dryers. The concept was developed from all must involve the evaporation of water, which can take
spray dryers having a fluid bed integrated into the spray anywhere from 1000 to 2500 Btu/lb depending on dryer
chamber itself and is depicted in Figure 35. What distin- type. The most common of these dryers probably is the
guishes the spray-bed dryer is that it has the drying air spray dryer because of its ability to produce a uniform pow-
both entering and leaving at the top of the chamber. At- der at relatively low temperatures. However, by its defi-
omization can be with nozzles or by a centrifugal atomizer. nition, a spray dryer requires a fluid feed material to allow
During operation, the chamber fluid bed is vigorously its atomization device to be employed. Generally, there
agitated by a high fluidization velocity, and as the particles is a maximum viscosity limitation in the range of 1000-
from the spray-drying zone, they enter the fluid bed with 1500 SSU (Saybolt Seconds Universal viscosity unit) (see
a very high moisture content and agglomerate with the Fig. 36).
powder in the bed. Fines carried upward in the dryer by Figure 37 illustrates the amount of water that must be
the high fluidizing velocity have to pass through the spray evaporated to produce 1 Ib of bone dry powder from a range
Exhaust
air
Feed H.R
pump
Compressed
air
Agglomeration
nozzles
Bag
collector
Table 6. Reconstitutability and Physical Structure of Different Types of Skim Milk Powder
Ordinary spray dried Integrated fluid-bed Rewet agglomerated
powder agglomeration powder
Wettability, s >1000 <20 <10
Dispersibility: % 60-80 92-98 92-98
Insolubility index <0.10 <0.10 <0.20
Average particle size, jam <100 >250 >400
Density, lb/ft3 40-43 28-34 28-31
of different feed solids. It can clearly be seen that even a The spin flash dryer can be described as an agitated
5% increase in total solids will reduce the water evapora- fluid bed. As shown in Figure 38, the unit consists primar-
tion and, hence, the dryer operating costs by about 20%. If ily of a drying chamber (9), which is a vertical cylinder with
this water removal can be done mechanically by, for ex- an inverted conical bottom, an annular air inlet (7), and an
ample, filtration or centrifuging, the cost will be infinitely axially mounted rotor (8). The drying air enters the air
lower than that required to heat and evaporate the same heater (4), is typically heated by a direct-fired gas burner
water. The direct energy cost can be calculated as equiva- (5), and enters the hot-air inlet plenum (6) tangentially.
lent to 3-8 Btu/lb, compared to an average 1500 Btu/lb for This tangential inlet, together with the action of the rotor,
evaporation. This increase in solids, however, inevitably causes a turbulent whirling gas flow in the drying cham-
will result in an increase in viscosity that may exceed the ber.
limitations of a spray dryer. The wet feed material, typically filter cake, is dropped
Options available for drying these higher-viscosity feed into the feed vat (1) where the low-speed agitator
materials are listed in Table 7. The spin flash dryer is (2) breaks up the cake to a uniform consistency and gently
among the newest of the dryer options and has the capa- presses it down into the feed screw (3). Both agitator and
bility of drying most materials ranging from a dilatent feed screw are provided with variable speed drives.
fluid to a cohesive paste. In the case of a dilatent fluid feed, the agitated vat and
screw would be replaced with a progressive cavity pump
Description and several liquid injection ports at the same elevation as
the feed screw.
The spin flash dryer was developed and introduced in 1970 As the feed material is extruded off the end of the screw
in response to a demand by the chemical industry to pro- into the drying chamber, it becomes coated in dried powder.
duce a uniform powder on a continuous basis from high- The powder-coated lumps then fall into the fluid bed and
viscosity fluids, cohesive pastes, and sludges. are kept in motion by the rotor. As they dry, the friable
Table 7. Dryer Options for High-Viscosity Materials
Direct suspension dryers
Pneumatic or flash dryers
Spin flash dryers
Fluid-bed dryers
Indirect dryers
Screw conveyor dryers
Vacuum pan dryers
Steam tube rotary dryers
Figure 36. Typical APV Anhydro spin flash dryer with general
dryer characteristics. Dryer characteristics: drying method tor. These larger lumps tend to fall back into the fluid bed
direct gas contact; flowcocurrent; food materialdilatent fluids,
cohesive paste, filter cake, moist granules; drying mediumair,
to continue drying.
inert gas, low-humidity waste gas; inlet temperatureup to Air exiting from the bag collector (10) passes through
180O0F; capacityup to 10 tons per hour of final product; product the exhaust fan (12) and is clean enough for use in a heat-
residence time5-500 s. recovery system. Dried powder is discharged continuously
from the bottom of the bag collector through the discharge
valve (11).
Two important features make the spin flash dryer suit-
able for products that tend to be heat-sensitive: (1) the dry
surface material is abraded by a combination of attrition
powder is carried away as soon as it becomes light enough
in the bed and the mechanical action of the rotor. Thus, a and therefore is not reintroduced into the hot-air zone, and
balanced fluidized bed is formed that contains all inter- (2) the fluid bed consists mainly of moist powder, which
mediate phases between raw material and finished prod- constantly sweeps the bottom and lower walls of the drying
uct. chamber and keeps them at a temperature lower than the
The dryer and lighter particles become airborne in the dryer air outlet temperature. In addition to this self-
drying airstream and rise up the walls of the drying cham- cooling capacity, the lower edge of the drying chamber di-
ber, passing the end of the feed screw and providing, in rectly above the hot-air inlet can be provided with an aux-
effect, a continuous backmixing action within the heart of iliary cooling ring.
the dryer. At the top of the chamber, they must pass Figure 39 illustrates the very rapid reduction in air
through the classification orifice, which can be sized to pre- temperature that occurs as a result of the high heat-
vent the larger particles from passing on to the bag collec- transfer rate obtained in the fluid bed.
Pounds water per pound dry product
Operating Parameters
Inlet temperature of the drying air introduced into the
chamber is dependent on the particular characteristics of
the product being dried but generally would be similar to
that used on a spray dryer for the same product.
Outlet temperature is selected by test work to provide
Figure 38. Fluid bed provides rapid air temperature reduction. the desired powder moisture and is controlled by the speed
of the feed screw. Since the spin flash dryer produces a finer
particle size than does a spray dryer, it has been found that
a slightly lower outlet temperature may be used to obtain
0.5
0.6
3
65
257
60
1292
0.1
1.6
sulfate
5
275
78
60
1112
diatomaceous
catalyst on
0.32
Nickel
earth
311
3
33
15
662
70
Ferrite (azo dye) 15985) stearate Polyvanadate
0.76
2.7
35
55
914
320
20
Tartrazine index Calcium
0.32
0.14
43
212
126
16
70
yellow
0.3
(color
Food
Figure 41. Spin flash dryer being prepared for shipment.
9
203
28
10
437
70
5.0
0.7
203
410
10
50
50
the same powder moisture. This provides an increase in
thermal efficiency.
Air velocity through the cross section of the drying
0.9
1.0
15
55
257
932
62
chamber is an important design factor and is determined
in part by the final particle size that is required. A lower
carbonate carbonate
Calcium
velocity will tend to reduce the final dried particle size car-
(pure)
0.8
5
968
338
O
67
32
ried out of the chamber. The major factor, however, is the
stability of the very complex bed that must neither settle
back into the air distributor nor blow out of the top of the
with binder
Calcium
0.45
chamber. Once the maximum velocity has been determined
0.3
55
58
536
194
50
by test work for a given product, the diameter of a drying
chamber can be selected to provide the desired water evap-
oration rate.
Aluminum
silicate
5.5
0.2
Capacity can be adjusted to suit the output from the
20
20
842
212
60
preceding process equipment, which may be difficult to
control and slow in response time. This is achieved by a
cascade control from a feed vat level sensor to the inlet
Dolomite oxide Alumina
0.4
12.5
194
65
70
482
29
0.3
Table 8. Products Dried on Spin Flash Equipment
0.6
iron
5
55
35
617
212
tinuously.
0.45
Closed-Cycle Drying
0.4
293
15
590
60
34
4.5
40
482
60
70
Capacity
Powder, Ib/h 880 880
Performance data
Feed solids, % 30 45
Feed rate, Ib/h 2,995 1,951
Water evaporation, Ib/h 2,115 1,071
Powder moisture, % 0.4 0.4
Gas consumption, SCF/ha (1000 Btu/SCF) 4,416 2,192
Power consumption (kWh) 40 30
Assumptions
Gas cost, $/M Btu $4.32
Electricity cost, $/kWh $0.07
Salaries per hour $15.00
Manpower required = 1 operator
The drying chamber would be maintained at a pressure the inlet temperatures are limited by the heat source used
slightly higher than ambient using a pressurized nitrogen and not by the spin flash process.
purge (17). The heater (5) would use either a steam coil or Other products test dried on a laboratory scale spin
a thermal fluid system with an external heater. flash dryer include the following:
A less expensive alternative to the closed-cycle ap-
proach is a "Lo-Ox" (low-oxygen) system where a low ex-
cess air burner is used in a direct-fired heater. The prod-
ucts of combustion are recirculated through the condenser, Feed Solids, Powder Moisture,
and the surplus gas is vented to atmosphere. The oxygen Product % %
level in such a system can be controlled to less than 5%. Iron oxide 70 2
(See also Figure 41.) Effluent treatment sludge 22 40
Lignin 49 15
Spin-Flash-Dried Products Gum 40 13
Chitosan gel 6 40
While Table 8 charts some typical products being dried on Crab meat paste 30 9
spin flash equipment, it should be noted that in some cases Dutched cocoa cake 70 2
Cost Benefits Dextrose Milk-cocoa
Diastase Molasses with filler
In comparison to a spray dryer, the spin flash dryer has a Diatomaceous earth
much shorter residence time and consequently is consid- Dietetic products Nitrates
erably smaller and requires less building space. Its ability Distillers waste
to dry to even higher solids than a spray dryer results in Olive paste
operating cost savings. Table 9 shows a detailed size and Egg white
cost comparison based on actual test drying of yellow iron Egg yolk Pancreas
oxide. Emulsifiers Papain
Enzymes Peanut milk
Pectin Soy flour
Conclusion
Penicillin Starch products
Despite its obvious size and cost advantages, there are Pepsin Stearic acid
many instances when a spin flash dryer cannot replace a Peptones Stearyl-tartrate
spray dryer. Typically, such cases occur when a free-flowing Phosphates Sulfonates
spherical particle of a particular size range is required or Pigments
when agglomeration is needed. Potassium sulfate Tannin extract
Potatoes Tapioca
There are, however, many situations in both the food
Potato waste liquor Tea extract
and chemical industries where the particular capabilities Proteins Thiamin
of the spin flash dryer to produce powders from paste war- Thymus
rant careful consideration of its use. Quaternary salts Tomato
Rennet Vegetable extracts
PARTIAL LIST OF PRODUCTS PROCESSED ON VARIOUS Vegetable proteins
Saponin
TYPES OF APV DRYERS
Seaweed extract Wetting agents
Spray Dryer Senna Whey
Sequestering agents Whey nonhygroscopic
Albumen Fat-enriched milk Silica-alumina gels Whole egg
Alcoholic extracts Fatty alcohol sulfonates Silicates Whole milk
Alfalfa Fish meat, hydrolyzed Skim milk Yeast
Alginates Fish pulp Sodium adipate Yeast autolysate
Amino acids Fish solubles Sodium phenate Yeast hydrolysate
Flavors Sorbate
Baby food Fruit juice Sorbose Zinc ammonium chloride
Bananas Fruit pulp fullers earth Soybean milk Zinc chromate
Beef extract Soybean protein Zinc stearate
Beer wort Garlic
Bile extract Gelatin Film Drum Dyers
Bouillon Glands
Brain Glauber salt Agar Dextrine
Butter Glazes Apple pectin
Buttermilk Glucoheptonate Avocado pulp Effluent
Glucose Essence
Calcium carbonate Gluten Baby food
Calcium salts Glyceryl monostearate Beef, comminuted Fat
Carbon, active Gum arabic Beef extract Fatty alcohol sulfates
Carboxymethylcellulose Beef protein (hyrolyzed) Fermentation waste
Carrageenan Hormones Beer concentrate Ferric ammonium syrup
Casein hydrolysate Hydrolysates Blood Ferrous sulfate
Caseinates Hypochlorites Buttermilk Fish food
Catalysts Fish stick liquor
Cellulose acetate Ice cream mix Calcium acetate Flavors
Cellulose hydrate Lactates Calcium carbonate Flour
Cheese Lactose Calcium propionate
Chelates Licorice Caramel Gelatin
Chlorophyll Lignin Cattle food Glauber's salts
Chocolate milk Liver extract Cellulose
Citrates Cereal (baby) Herbicide
Colors Magnesium carbonate Chicken offal Hydrolyzed protein
Cornstarch Magnesium oxide Cider less Maize gluten
Corn steep liquor Magnesium salts Corn syrup Mango flake
Corn syrup Magnesium sulfate Manure Single-cell protein
Cream Malted milk Meat extract Sorghum and maize
Malt extract Meat pieces Starch
Dextranes Mango Milk crumb Stearate
Dextrin maltose Meat extract Milk (skimmed) Stearic acid
Molasses Steep liquor Bread crumbs Dog biscuits
Stick liquor Breakfast cereals Dog food
Oat flour Sugar solution Filter board Pastilles
Oats Food concentrates Peanuts
Onion pulp Tapioca starch French fries Peas
Palm oil residue Vegetable extract Pectin
Pectin Vegetable protein Garlic Peppers
Phenylglycine casein Gelatin Pet food
Potato (waste) Wax Grapes Plums
Press liquors Whale solubles Potatoes
Protein (hyrolyzed) Wheat starch Iced biscuits Puffed cereals
Rice starch Whey Jellies Rice
Seaweed extract Yeast cream Sausage rusk
Semolina Yeast extract Meat Seaweed
Mints Soya protein
Thermoventuri Dryer Molding powders Sugar dough
Sugar- and/or honey-coated
Alginates Maize starch cereals
Alginic acid Nougat
Organic acids Turnip
Nuts
Bread crumbs Onions Wheat flakes
Pectin
Cocoa residue Potato
Cornstarch
Coumarin Spent grains BIBLIOGRAPHY
Sphagnum moss
Dark grains Starches
Demerara sugar Stearates Copyrighted APV Crepaco, Inc. Used with permission.
Dextrose Sulfur waste
Fishmeal Tartaric acid 1. D. Noden, "Industrial Dryers Selection, Sizing, and Costs," CPI
Flour Digest 8(1), 6-23, (1985).
Wheat germ 2. D. Noden, "Efficient Energy Utilization in Drying," dfi News
Glucose starch Wheat gluten 7(4), 8-14, (1985).
Groundnut residue Wheat starch 3. B. Bjarekull, "Spray Drying New Developments, New Econom-
Lactose Yeast ics," dfi News 8(2), 6-13 (1985).
4. B. Bjarekull, "Fluid Bed Agglomerization for the Production of
Coveyor-Band Dryer Free-Flowing Dustless Powders," dfi News 8(2), 6-13 (1985).
Almonds Cabbage 5. S. G. Gibson, "Spin Flash Dryers for Continuous Powder Pro-
Apples Carrots duction from Pastes and Filter Cakes," APV Dryer Handbook,
Apricots Celery Oct. 1985, pp. 36-42.
Assorted biscuits Chocolate milk crumb
Coconuts
Beans Corn grit APV CREPACO, INC.
Bran Lake Mills, Wisconsin
E
E. COLI 0157. See FOODBORNE DISEASES. developed in the late 1950s. The process involves dehairing
hides by alkaline or acid treatment, decalcifying hide coria;
grinding into small pieces; acidifying to produce a swollen
EDIBLE FILMS AND COATINGS slurry (4-5% solids); homogenizing; extrusion forming into
tubular casings (8-10% solids); feeding extrudates into co-
Edible films and coatings are generally defined as thin lay- agulating baths of brine or ammonium; washing casings
ers of edible material that are applied on (or within) food free of salts; adding plasticizers and cross-linking agents;
products to extend shelf life by functioning as solute, gas, and drying (1). Perpendicular shear is applied to the col-
and vapor barriers. Also, they can modify product appear- lagen fibers as they exit the extruder to disrupt their lam-
ance, improve structural integrity, act as carriers of food inar alignment to produce a more woven fiber structure. A
additives (eg, antimicrobials, antioxidants, and flavorings) collagen casing extrusion process developed in Germany in
and, in certain instances, partially or completely replace the 1930s employs collagen dispersions of higher solids
synthetic packaging materials. The terms films and coat- contents (>12%) (1). Such dispersions require substan-
ings are often used interchangeably. Generally, coatings tially higher extrusion pressures. This method has had
are formed on foods after application by dipping, brushing, limited acceptance outside Europe.
spraying, or tumbling, whereas stand-alone films are pre- As an alternative to preformed collagen casings, a tech-
formed by casting or extrusion and then placed on (or nology where the collagen casing is coextruded around the
within) foods. Relevant commercial applications range sausage meat batter was developed in the 1980s (2). The
from wax coatings for fresh produce, to extruded collagen collagen dispersion is prepared in situ and pumped to a
casings for sausages, to sugar coatings for bakery and special extrusion nozzle. The meat emulsion is pumped
confectionery products, to water-soluble pouches for pre- through an inner opening in the nozzle and the collagen
measured food additives. Interest in development, char- dispersion is applied to the emerging meat batter through
acterization, and application of edible films and coatings counterrotating concentric cones that orient collagen fibers
has recently intensified, resulting in voluminous peer- into a woven alignment. The continuous encased sausage
reviewed and patent literature on the subject. Several pro- rope is passed through a brine bath to dehydrate and set
tein, polysaccharide, and lipid materials derived from the collagen casing. The sausage rope is crimped into links,
plants and animals are known film-forming ingredients and the sausage is dried and smoked to further set the
with current or potential edible packaging applications. collagen casing. Coextruded sausage casings are more
Typically, protein- and polysaccharide-based films and tender than preformed casings and, therefore, have better
coatings require incorporation of low molecular weight ed- eating qualities, yet they remain more durable during
ible plasticizers such as glycerin, sorbitol, polyethylene grilling. The high initial cost of the coextrusion equipment
glycol, propylene glycol, and fatty acids. The present sum- has limited the acceptance of this method to large process-
mary is intended as a reference for various types of edible ing plants. Besides sausage casings, collagen-based edible
film-forming materials and not as an edible packaging ap- films for use on netted roasts, boneless hams, fish fillets,
plications guide. and roast beef also have been commercialized since the
late 1980s (3). Such films (trade name Coffi) can reduce
PROTEIN FILMS cook shrink, increase product juiciness, and allow for easy
removal of elastic stretch netting after heat processing.
Collagen Reportedly, both refrigerated and frozen/thawed round
beef steaks wrapped in collagen films prior to retail pack-
One of the earliest uses of edible films is the use of natural aging (permeable film overwrap) or vacuum packaging ex-
casings made from animal intestines to restructure com- hibited substantially less fluid exudate than unwrapped
minuted meat. Natural casings have the disadvantages of steaks (4).
low mechanical strength, inconsistent quality, and limited
availability. Therefore, natural casings have been largely Gelatin
supplanted by (artificial) collagen casings fabricated from
swollen collagen fibers. Sausage casings hold and shape Gelatin is obtained by partial hydrolysis of collagen
the meat batter while the meat protein is being heat-set. through alkaline or acidic treatments. It is an important
They have no real barrier properties; they allow moisture hydrocolloid used in a number of food, photographic, phar-
to pass when needed, and allow smoke and flavorings to maceutical, and technical applications (5). In particular,
enter the sausage. Compared with natural intestine cas- gelatin is used widely in pharmaceutical and dietary sup-
ings, fabricated edible collagen casings offer improved uni- plement industries as an encapsulating agent (edible bar-
formity, processibility, and sanitation. However, edible col- rier) in hard (two-piece) capsules, soft capsules (softgels),
lagen casings are somewhat tough and tend to split when and microcapsules (usually as coacervate with anionic
grilled. polysaccharides). However, the film-forming properties of
The currently used extrusion process for fabricating col- gelatin that have made it indispensable to the pharmaceu-
lagen casings from regenerated bovine hide corium was tical and photographic industries have not been utilized by
the food industry. This is mainly due to gelatin being too sage casings from casein have been prepared (23). Whey
easily hydrated and solubilized to form an effective barrier protein coatings have shown potential as oxygen barriers
in foods. for dry roasted peanuts (24).
anterior base of the dorsal fin to the anus and the total Indo-Pacific Ocean are distributed in both the southern
body length. The long-fin type has a proportion of 7-17%, and northern hemispheres. The northernmost boundary is
while the short-fin type has a proportion of 0-5%. Thirteen at about 45 N in Hokkaido, Japan, while the southern-
of the eel species belong to the long-fin category, three spe- most limit is at about 50 S in the Auckland Islands, New
cies belong to the short-fin type. Zealand. The two other species, the European eel and the
American eel, inhabit the Atlantic Ocean and abound in
Vertebral Number. Another taxonomic criterion for eel the temperate zones of Europe and North America, re-
types is the number of vertebrae. Eels have 100-119 ver- spectively (Fig. 1).
tebrae; the number varies among the different species. The
number even varies within each species, which increases
with higher latitudes. LIFE HISTORY
Color. Eels can be mottled or plain. There are seven The first successful attempt to understand the amazing life
mottled and nine plain species. cycle and unusual traits of the eel has generally been ac-
credited to two men who devoted most of their lives to
studying eels: Danish biologist Johannes Schmidt and his
Size. There is a considerable difference between female student Vilhelm Ege. The discovery of a leptocephalus by
and male eels. The growth of female eels in inland water Schmidt in 1904 started a 35-year study that helped es-
is much more superior than that of male eels. The females tablish a solid foundation to the ecological study of eels.
also stay longer in inland water before returning to the sea. Nevertheless, many questions concerning the life history
Eels can grow at maximum sizes of 27 kg and 200 cm. of eels still remain unanswered. Although the life history
of three species, European eel, American eel, and the Jap-
Head Shape. Eels are also classified according to the anese eel are well investigated, little is known about the
shape of their head. Those with a narrow head and thin, other species.
narrow lips are classified as narrow-head type while those Eels are catadromous migrants, that is, they spawn at
with broad head and thick, broad lips are classified as sea and spend most of their lives in inland waters. The
broad-head type (4,5). spawning ground and migration route vary with each spe-
cies.
Distribution
European Eel
Of the 16 species of eels, 14 are distributed in the Indo-
Pacific areas. Some of these eels inhabit the tropical zone, The European eel spawns at the Sargasso Sea, 22-30 N,
while others abound in the temperate zone. Eels in the 48-65 W, in the western Atlantic Ocean from early spring
Table 1. Major Details of the World's Anguilla Species
Maximum
size of
Dorsal fin females
length Vertebral number Color" kg cm Species Zone6 Distribution0
Long 110-119 P 6.0 125d A. anguilla Temp ATL Europe, North Africa
Long 103-111 P 6.0 125d A. rostrata Temp ATL United States, Canada,
Greenland
Long 112-119 P 6.0 I25d A. japonica Temp PAC Japan, Korea, Taiwan,
People's Republic of
China
Long 109-116 P 20.0 150 A. dieffenbachi Temp PAC New Zealand
Long 104-110 M 18.0 170 A. reinhardti Trop PAC Australia, New Caledonia
Long 100-110 M 27.0 200 A. marmoratae Trop PAC Africa, Madagascar,
Indonesia, People's
Republic of China,
Japan, Pacific Islands,
Sumatra
Long 101-107 M A. celebesensisf Trop PAC Philippines
Long 101-106 M A. ancestrali/ Trop PAC Celebes
Long 108-116 M 22.0 190 A. megastoma Trop PAC New Caledonia
Long 104-108 M A. interioris Trop PAC New Guinea, New
Caledonia
Long 103-108 P 2.0 90 A. borneensis Trop PAC Brunei
Long M 10.0 150 A. nebulosa
Long 106-112 A. n. nebulosa Trop IND Sri Lanka, Burma,
Sumatra
Long 107-115 A. n. labiata Trop IND South Africa
Long 100-106 P 5.0 125 A. mossambica Trop IND Africa
Short P 3.0 110 A. bicolor
106-115 P A. b. bicolor Trop IND South Africa,
Madagascar, Sri
Lanka, Burma,
Sumatra, Australia
Short 103-111 A. b. pacifica Trop PAC Brunei
Short 101-107 P A. obscura Trop PAC New Caledonia
Short P 2.5 95 A. australis
Short 109-116 A. a. australis Trop PAC Australia
Short 108-115 A. a. schmidti Temp PAC New Caledonia, New
Zealand
Source: Refs. 5 and 9.
"Color abbreviations are P = plain, M = mottled.
6
Zone abbreviations are Trop = tropical, Temp = temperate.
c
Distribution abbreviations are ATL = Atlantic Ocean, IND = Indian Ocean, PAC = Pacific Ocean.
d
A. anguilla. A. rostrata, and A. japonica are closely related (9).
e
A. marmorata is the most widely distributed species (9).
^Synonymous (3).
ECOLOGY OF ELVERS
The amount of catch for elvers in coastal waters seems to Figure 3. Estimated spawning ground and life cycle of the Jap-
be correlated with temperature. The maximum catch of anese eel: (a) Leptocephalus, 5.5 cm T.L., drifted by current; (b)
elvers in the upstream areas has often been found during elver (ascending) migrates from estuary to river; (c) adult (de-
or several days after daily seawater temperature reaches scending) migrates from river to spawning ground. Source: Ref. 7.
its lowest in winter. The lowest water temperature ever
recorded in an eel habitat is 15160C.
Maximum catch has also been observed to occur at the the American eel, and the Japanese eel. From a marketing
same time when salinity has leveled off and the flow of point of view, these species are similar in shape, growth,
seawater has reached its maximum. The elvers also be- and behavior (8).
come most active during this period at night.
The biological rhythm of elver activity was found to fol- Elver Collection
low the lunar cycle in the coastal waters. The peak catches
occur only once a month, about the time of the new moon. The collection of the elvers is the starting point of eel cul-
On the other hand, a semilunar rhythm of the elvers in the ture. Attempts to propagate eels artificially have not been
rivers was observed, namely, two peak catches occurred in successful to date. In 1974, the Japanese succeeded in in-
each lunar cycle, one around full moon, the other around ducing artificial spawning of the eel and hatching the eel
new moon. The semilunar rhythm of upstream elvers also eggs. But attempts to rear the elver during the first three
coincided with the spring tide (8). weeks of its life have not been as successful. Thus eel fry
are still sourced entirely from the wild-caught elvers.
CULTURE TECHNIQUES A growing concern within the eel culture industry in
recent years is the diminishing number of large seaward
Species Cultured running eels, as well as the elvers swimming upstream.
Of the different species of eels in the world, three are val- This has been attributed mainly to pollution in estuaries,
ued for its economic importance, namely, the European eel, rivers, and streams and the overfishing of elvers. To rem-
edy this, captured elvers are now widely used not only for The elvers have to be trained to take formulated feeds.
culturing eels for consumption, but also for restocking in The common method is to lower baskets containing tubifex
the lower reaches of rivers and streams. worms or minced meat of oyster and clam twice a day, in
Elvers are usually captured at nighttime. Light is used the early morning and in the late evening under a wooden
to attract them (Fig. 4) and they are caught in scoop nets enclosure lit by a 20-40 W lamp. Elvers do not feed at
in shallow water, in a fine-mesh net set across the width temperatures below 130C, thus temperatures must be kept
of the river, or in trap nets set in the estuaries (10). above 130C. Feeding time is gradually shifted to daytime.
Elvers are quite hardy; nevertheless, great care is taken Initially, elvers may not eat. In the long run, however,
when handling them to prevent mortality due to injury. they learn to eat and eventually, attain rapid growth. After
They are not handled directly. They are placed in boxes 100-150 days, a size of 100-200 fingerlings/kg is reached.
lined with wet muslin or hung in mesh cages in the river.
These boxes or cages are taken to eel farms within a few Feeding Management
hours. The high demand coupled with a supply shortage
Eels are carnivorous fish and thus require high animal pro-
has resulted in a phenomenal increase in the price of el-
tein input. The more animal protein that can be provided,
vers.
the greater the eels' weight will be. Most eel farmers feed
their eels with formulated feeds that are chiefly made of
CULTURE SYSTEMS fish meal with added carbohydrates, minerals, vitamins,
and other ingredients. Due to the high cost of these feeds,
Eels can be cultured both extensively and intensively. Most most eel farms supplement these with raw fish such as
eel farms, however, use the intensive culture system. This mackerel, sardine, and anchovy. Trash fish or scraps that
culture system is characterized by high stocking densities, are minced using electric grinders are also used widely as
stringent water-quality management, additional inputs feeds. Eels, however, convert formulated feeds more effi-
such as formulated diets to increase fish production, and ciently than they convert raw fish.
aggressive disease prevention. Feeding is done once a day, at about 7:00 A.M. during
summer and about 10:00 A.M. in winter. The usual feeding
Elver Rearing rate is 5-15% of the total weight of the eel for minced trash
fish and 1.0-3.5% for formulated feeds (11). Nevertheless,
There are various sizes and types of tanks being used in factors such as the previous day's feeding condition and
stocking elvers. The most commonly used, however, is the water and air temperature as well as water quality are
circular concrete tank, about 5 m in diameter and 60 cm considered when determining the feeding rate. Ideally,
in depth. Tanks are usually built under greenhouses and feeds should be consumed within 20-30 min.
heated to above 250C by thermostatically controlled elec- Precautions must be taken to insure that no unneces-
tric immersion heaters (10). This is to protect the elvers sary organic debris are allowed to fall into the ponds. Thus
from low temperatures. eel farmers do not just broadcast the feeds into the ponds.
The average stocking density of intensive culture is 1- Instead, a special feeding platform, usually shaded, within
2 kg of elvers/3.3m2. Sorting and restocking are usually the pond is designated for feeding, and the eels learn to
done after 20-30 days, when a significant difference in the swim toward the area each feeding time. Feeding areas are
size of eels is observed. The average density used for the preferably located where the oxygen level is high as this
second stocking phase is 1 kg offish/3.3 m2. Frequent sort- encourages the eels to eat well. Formulated feed is lowered
ing and restocking will bring about higher survival rate. on a perforated tray suspended just under the surface and
These will also help maintain uniform growth and provide lifted after feeding is done (Fig. 5). Raw fish, dipped for a
better feed conversion rates. few minutes in boiling water to soften the skin, are
threaded through the eyes and also lowered and raised
once eels have eaten all the flesh. Thus the only organic
matter that goes into the pond is that which the eels eat.
Different countries have different preferences and eating Figure 9. Eels being graded according to size.
habits, and thus have different ways of preparing and eat-
ing eels. In Europe, the main eel consumers are the Ger-
mans, Dutch, Danes, and Swedes. These consumers com-
monly prefer smoked eel, which ranks as an expensive and Cutting Methods
luxurious food. The British also eat eels, but prefer the There are generally two types of cutting, namely, Kansai
jellied type. style (cut abdominally) and Kanto style (cut dorsally).
In the Far East, the main eel-eating country is Japan, Newly cut eels are usually cleaned of slime by washing
where it is a custom to eat roasted eel (kabayaki) especially them in cold water and scraping. The eels are then gutted.
on the Ushinohi (a special eel-eating day near the end of This is done by slitting from the throat through either the
July). The Japanese believe that the eel is nutritious and belly (Kansai style) or up toward the back (Kanto style) to
can make up for overexhaustion during the summer. Eel the tail, about 2.5 cm beyond the anus. The guts are then
is also consumed widely in Taiwan, the People's Republic emptied and the backbone and head removed. The eel is
of China, Korea, and Hong Kong. washed thoroughly to remove traces of slime and blood.
Machines specifically designed to eviscerate eels efficiently
Preprocessing are also available.
Before eels are processed, they are graded according to size Preparations
(Fig. 9). One way of preparing them is by putting them in
a deep container and sprinkling them with salt. This treat- Fresh Eels. Fresh eels are cooked in several ways, such
ment removes their slime until they die of asphyxiation. as braising and steaming. Steaming, however, is the more
Another way is by putting them in fresh water and stun- popular method. In both Taiwan and Mainland China, eel
ning them with an electric shock (10). Or they may simply is either steamed with various vegetables and mushrooms
be put in cold storage overnight. In this way, eel activities or stewed with Chinese herbs, such as medlar, lovage, and
can be slowed down, and thus they can easily be handled dates. This herb-filled soup is considered as a revitalizing
for gutting or deboning. tonic soup for frail or disabled persons.
Smoked Eels. After the eels' are cut, they are brined in
a saltwater solution, then hot smoked. In this process, the
eels are dried and smoked. To allow uniform drying
throughout the thickness of the fish, the temperature dur-
ing smoking is increased gradually. The smoking process
may vary from country to country. The finished product is
then packed either in boxes or in cans (10).
FUTURE DEVELOPMENT
BIBLIOGRAPHY
Shell Membrane
Air cell
Cuticle Outer shell membrane
Spongy (calcareous) layer Figure 1. A schematic of the parts
Inner shell membrane
Mammillary layer of an egg. Source: Ref. 4.
so that the matured yolk can be dropped into the infundib- fatty acid composition can easily be modified by changing
ulum of the oviduct without the rupture of any blood ves- the fatty acid makeup in the feed. In most commercial eggs
sels in the follicular membrane. A blood spot in an egg is where the hens are fed a corn and soybean meal diet the
generally caused by incomplete formation of the suture fatty acids are about one-third saturated and two-thirds
line. mono- and polyunsaturated. Yolk color is controlled by the
The oviduct consists of five identifiable sections: infun- level of pigments, mostly xanthophyll, in the feed of the
dibulum, magnum, isthmus, uterus, and vagina. The in- hens.
fundibulum, or funnel, collects the yolk, or ovum, and by Some elements of the medical profession have empha-
peristaltic action moves it on to the magnum region, where sized the role of dietary cholesterol in human cardiovas-
the thick albumen is secreted and laid down in layers on cular problems. The negative effect on egg consumption
the yolk. In the isthmus the shell membranes are formed that this emphasis on cholesterol has had led to a number
around the yolk and thick albumen. The membranes, two of research attempts to reduce the cholesterol content of
in number, only loosely fit the enclosed material. Most of eggs. Genetically it has been possible to achieve only slight
the time that the egg is in the oviduct is spent in the uter- reductions. Selection of hens for small yolk size has met
ine section where thin albumen fills the shell membrane with some success. A review on altering cholesterol by
sack and the shell is laid down to form the rigid egg pro- feeding (5) concluded that dietary modifications resulted
tective layer. The shell color is determined by the breed of in only minor changes in the cholesterol content of egg
the hen. Generally, hens with red earlobes produce brown- yolk. Another report (6) states that including 1.5 to 3.0%
shelled eggs, and white-shelled egg producers have white of menhaden oil in the laying hen's ration results in a tem-
earlobes. The total time spent in the oviduct is usually porary reduction of about 50% in the cholesterol concen-
about 24 hs. Total time for the formation of the egg from tration in the yolk. The fatty acid composition of the eggs
the start of rapid growth of the ovule to time of laying var- was also modified in that the eicosopentenoic acid and do-
ies from 12 to 15 days. cosahexanoic acid (omega-3 fatty acids) content of the
yolks was significantly increased when the fish oil was in-
cluded in the hen's ration. Levels offish oil in excess of 3%
COMPOSITION OF THE EGG in the ration resulted in fishy flavored eggs.
The relative ease with which egg composition can be
The egg is composed of approximately 10% shell, 30% yolk, modified has led to the development of a variety of "de-
and 60% white or albumen. The egg is a very good source signer eggs." It has been reported that all vitamins and
of high-quality protein and many minerals and vitamins. minerals content of eggs, except for choline and zinc, can
The exact levels of the minerals and vitamins is deter- be adjusted significantly by dietary modification for the
mined by the level of each in the diet of the hen. An average hens (7).
chemical composition of eggs, including shells, is summa-
rized in Table 3.
The protein of egg white is complete; it contains all of PRODUCTION PRACTICES
the essential amino acids in well-balanced proportions.
The white is made up mainly of the proteins ovalbumin, As shown in Table 2, the majority of eggs at this time are
conalbumin or ovotransferrin, ovomucin, ovoglobulins, produced on large egg production farms. With this change,
ovomucoid, and lysozyme. The structure of the thick white the level of mechanization used in the production of eggs
is the result of a complex of ovomucin and lysozyme. has increased. Over 95% of all laying hens in the United
The important yolk proteins are ovovitellin and ovoliv- States and over 75% of all laying hens in the world are
etin. The lipid materials in the egg are all in the yolk. The kept in cages (8). Legislation has been introduced in many
Table 3. Chemical Composition of the Egg
Water Protein Fat CHO Ash
(%) (%) (%) (%) (%)
Edible portion
Whole egg 75.33 12.49 10.02 1.22 0.94
White 88.00 10.52 O 1.03 0.64
Yolk 48.80 16.76 30.87 1.78 1.77
countries and passed in a few that would ban the use of There are six size classifications of eggs in the United
cages for laying hens due to activities of animal welfare States. Table 4 gives minimum weight requirements for
groups. Full details on production practices are given by each of the sizes. On the processing line the sizes are seg-
North and Bell (8). regated by passing the eggs over a series of scales set so
that the jumbo eggs are removed from the line first and
SHELL EGG PROCESSING the peewees are removed last.
After the eggs have been mechanically placed in cartons
In a modern egg production unit hens are housed in cages or on trays, many processors spray the tops of the eggs with
with sloping floors so that eggs will roll from the cage onto a food grade mineral oil to preserve the interior quality of
an egg gathering belt. The eggs are transported by con- the egg during movement through market channels. The
veyor belts to a separate unit of the facility where they are oil partially seals the pores of the shell to reduce loss of
washed, inspected for defects by passing them over an in- gases from the egg and to reduce the rate of pH change of
tense light source (candling), sized, and packed into car- the albumen. As a further aid in maintaining quality, eggs
tons for retail or onto trays for bulk packaging. Throughout should be handled at refrigerated temperatures of less
the operation individual eggs are not touched by any work- than 70C (450F) throughout market channels, and consum-
ers. The cartons or trays are packed into master containers ers are advised to keep eggs in the refrigerator after they
by hand. purchase them. With good handling throughout market
Some countries ban the washing of eggs to be sold at channels and in the home, eggs will remain high quality
retail. In others, including the United States and Canada, for several weeks and in a usable condition for several
almost all eggs are washed in a detergent solution at a months. The factors that have the greatest effect on quality
temperature of about 450C (1130F) and then sanitized with loss in eggs are time, temperature, humidity, and han-
an approved sanitizing agent, frequently a chlorine-based dling.
compound. All of the washing should be done with water During the last decade a potential health risk in the
spray with or without brushes depending on the equip- usage of eggs has appeared. A new strain of Salmonella
ment. enteritidis is capable of infecting the reproductive system
After the eggs are washed and dried, they are conveyed of the hen, so that some eggs are produced with the S.
to the candling area of the processing line. Here there is a enteritidis in the egg at the time of production (10). The
strong light source under the eggs so that any defects such frequency of finding an egg positive for S. enteritidis in
as cracked shells, dirty or stained shells, or inclusions in market eggs has been estimated to be between 1 in 10,000
the egg might be detected and the defective eggs removed and 1 in 20,000. Most eggs are heated to over 6O0C (14O0F)
from the conveyor. Candling of eggs is used to segregate
eggs into the several grades that are found in the market-
place. The retail grades in the United States are AA, A,
and B. Quality factors used in grading include the shell Table 4. Weight Classes of Shell Eggs in the United States
(cleanliness and soundness), air cell (size), white (clarity Minimum Minimum
and firmness), yolk (visibility of the outline), and freedom Minimum average average
from defects. All grades of eggs are required to have a ounces ounces grams
sound, not cracked, shell. Other quality factors are judg- Size name per dozen per egg per egg
ment calls, with smallness of the air cell, freedom from Jumbo 30 2.5 70.0
stains or dirt on the shell, firmness of the white, and dim- Extra Large 27 2.25 63.8
ness of the yolk outline being considered most desirable. Large 24 2.0 56.7
For eggs that do not meet the grade standards two addi- Medium 21 1.75 49.6
tional groupings are provided: dirty and checked or Small 18 1.5 42.5
cracked. Details on the grading standards have been pub- Peewee 15 1.25 35.4
lished (9). Source: Ref. 4.
prior to eating, so the pathogen would be killed by cooking. ble to the potential incidence of S. enteritidis in the shell
Handling of eggs at refrigerated temperatures inhibits the eggs. The savings in costs of freezing and in time saved by
increase in numbers of bacteria during marketing and not having to thaw the products before using in food for-
holding in the home. With this threat to food safety from mulations are evident.
shell eggs, research has led to the development of systems The pasteurization of liquid eggs was practiced for a
for pasteurization of intact shell eggs to destroy all poten- number of years prior to the passage of the law making it
tial pathogens in the egg or on its shell (11). mandatory for all egg products in the United States. The
times and temperatures required for pasteurization in sev-
eral countries are listed in Table 7. All of these values are
CONVERSION OF SHELL EGGS TO LIQUID PRODUCT for liquid whole egg. Details of pasteurization have been
discussed (17).
An ever-increasing number of eggs are being broken at In the processing of egg white it is necessary to remove
commercial egg breaking plants. The early growth of the the reducing sugars before the liquid can be dried. In early
egg products industry has been reviewed (12). In the first work on dehydration of egg white the process included a
half of the twentieth century most of the egg breaking natural fermentation by whatever organisms were present
plants were located in the north central and western plains in the egg white. A patent was issued in 1931 covering the
states. Since 1960 many of the new breaking plants have use of lactic acid bacteria for egg white fermentation. The
been built in the southeastern states. The yield of liquid next development was the use a yeast, Saccharomyces ap-
products from a case (30 dozen) of large eggs is shown in iculatus, and then the use of an enzyme, glucose oxidase.
Table 5. Data in this table also include the yields of solids Each of these methods is still in use in some parts of the
that might be obtained if the egg products were dehydrated world.
by either spray drying, pan drying, or freeze drying. The natural egg products of white and yolk are also sup-
The growth of the egg products industry is summarized plied to the food processing industries in a number of
in Table 6. The shift from dried to liquid since 1970 was blends and modifications often with the addition of sodium
likely the result of mandatory pasteurization of all egg chloride or sugar. The chemical composition of some of the
products since 1971 (14). The shift to liquid from 1988 to egg products is shown in Table 8. The difference in com-
1990 was likely the result of ultrapasteurization and asep- position between pure yolk and commercial yolk should be
tic packaging of liquid eggs that will give more than 4 emphasized. The difference is due to the inclusion of a sig-
weeks usable shelf life for the liquid product (15). The nificant amount of albumen with yolk in the commercial
rapid expansion since 1986 is at least partially attributa- product.
Table 5. Yields of Liquid Egg and Egg Solids per 30-Dozen NUTRITIONAL AND FUNCTIONAL PROPERTIES OF EGGS
Case of Large Size Eggs
Complete nutritional data on eggs and egg products pre-
Liquid Solids pared in several ways have been summarized (3). An ab-
Kilograms Pounds Kilograms Pounds breviated listing of nutrients in whole egg, yolk, and white
White 13.8 30.4 1.67 3.68 is given in Table 9, As mentioned earlier, the content of
Yolk 6.1 13.5 3.12 6.87 various trace minerals, vitamins, and fatty acids in the egg
Whole egg 19.9 43.9 4.79 10.55 can be modified significantly by varying the diet of the hen.
The various uses for eggs in food products have been re-
Source: Ref. 13.
viewed (19). The functional properties include whipping,
emulsifying, coagulation, flavor, color, and nutrition. The
foam produced during whipping should give a large volume
Table 6. Processed Egg Product Production in the United and be stable. The whipping time required to get a maxi-
States (in millions of pounds) mum foam volume will vary for eggs of different qualities.
Year Liquid Frozen Dried Eggs with a high percentage of thick albumen require a
1960 44 362 176 longer time for whipping but the foam formed will be more
1965 44 368 216
1970 110 357 281
1974 301 367 73 Table 7. Minimum Pasteurization Requirements for
1977 394 348 75 Whole Egg Products
1980 422 331 81 Temperature ^^
1982 460 339 80 0 0
Country C F minutes Reference
1984 528 322 76
1986 632 337 89 United Kingdom 64.4 148 2.5 15
1988 797 371 106 Poland 66.1-67.8 151-154 3.0 16
1990 932 384 105 China (PRC) 63.3 146 2.5 16
1992 1,276 418 130 Australia 62.5 144.5 2.5 16
1994 1,689 428 133 Denmark 65-69 149-156.5 1.5-3.0 16
1996 2,033 406 139 United States 60 140 3.5 13
Source: Ref. 1. Source: Ref. 16.
Table 8. Approximate Composition of Selected Egg Products (per 100 g)
Composition
Product Calories Water Protein Lipid CHO Ash
Frozen eggs
Whole egg 158 74.57 12.14 11.15 1.20 0.94
White 49 88.07 10.14 Trace 1.23 0.56
Yolk, pure0 377 48.20 16.10 34.10 1.69
Yolk, commercial6 323 55.04 14.52 28.65 0.36 1.43
Yolk, sugared 323 50.82 12.92 25.50 9.49 1.27
Dehydrated eggs
Whole egg 594 4.14 45.83 41.81 4.77 3.45
Whole egg, stabilized 615 1.87 48.17 43.95 2.38 3.63
White, stabilized, flakes 351 14.62 76.92 0.04 4.17 4.25
White, stabilized, powder 376 8.54 82.40 0.04 4.47 4.55
Yolk 687 4.65 30.52 61.28 0.39 3.16
"Contains approximately 17% white.
Source: Refs. 3 and 18.
stable. Cakes made using very low quality eggs generally either longitudinally or horizontally, and the yolk is re-
do not have the volume of similar cakes made with higher- moved. The yolk is removed and mixed with a salad dress-
quality eggs. When egg white is dried, there is generally a ing and other ingredients to produce a filling for the de-
loss in whipping properties. To overcome the decrease in pression left in the white. Deviled eggs are a favorite for
foam volume, whipping aids such as triethyl citrate are hospitality suites or buffets.
frequently added to the dried egg white.
Scotch Eggs
PRODUCTION OF EGG-RICH CONVENIENCE FOODS This product was developed years ago but received very
little publicity until relatively recently. A hard-cooked egg
Reference 20 outlines procedures for the manufacture of a is wrapped in a thin layer of sausage meat. The sausage is
number of value-added egg products, some of which will be then cooked in a deep fat fryer. In producing this item the
described here. sausage used should be very low in fat to get better adhe-
sion of the surface of the hard-cooked egg. Scotch eggs are
Hard-Cooked Eggs a snack food item frequently sold from refrigerated vend-
The preparation of hard-cooked eggs has been a function ing machines and are also used for hors d'oeuvres by cut-
of kitchens for many years. In about 1970 the production ting the finished product into quarters or halves.
of hard-cooked eggs for sale to salad bars, restaurants, and
commercial food caterers was begun. The original products Diced Egg Products
were cooked in hot water, partially cooled, peeled, and
stored in a solution of citric acid and sodium benzoate. The Diced eggs were first marketed as a means of utilizing
concentration of the citric acid was initially 2% but has hard-cooked eggs that were not perfectly smooth. With the
been lowered over the last 28 years to from 0.5 to 0.8%. popularity of hard-cooked diced eggs on salad bars, the de-
The lower levels of acid produce eggs with softer cooked mand was greater than the quantity available from the
whites, much closer to freshly cooked eggs. imperfect hard-cooked eggs. At this point innovative pro-
Cooking of hard-cooked eggs is now being done either ducers separated yolks and whites as liquids and steam-
in steam or hot water. Peeling of eggs was primarily a hand cooked trays of the two liquids. The cooked yolk and white
operation aided by equipment to crack the shells. Equip- were then diced. The product thus prepared gave yolk
ment has been developed that strips the shell from a cubes that held together because of the residual albumen
cracked hard cooked egg so that efficiencies of production in commercially separated liquid yolk. The diced egg prod-
have been significantly increased. With improvements in ucts have been marketed as individually quick frozen ma-
packaging technology, some hard-cooked eggs are now terial in most instances. However, where market channels
marketed as a dry-packed, refrigerated product. It is esti- are short, nonfrozen, controlled atmosphere packaging is
mated that almost 1% of all eggs are now being marketed also being used.
as hard-cooked product.
Scrambled Eggs
Deviled Eggs
Scrambled eggs are prepared as fully cooked, freeze-dried
One use of hard-cooked eggs is the production of deviled products for the camper; as fully cooked, frozen items for
eggs. A hard-cooked egg is cut in half through the middle the microwaveable meal; and as frozen prepared liquid
Table 9. Distribution of Nutrients in Large Chicken Eggs mixes, packaged in cook-in-bag film. The basic formula for
(per egg, edible portion) scrambled eggs consists of about 70% whole liquid egg and
Whole egg Yolk" White 30% milk with seasonings of salt and pepper. The most
significant form of scrambled eggs is the frozen prepared
Weight per egg, g 50 17 33
Water, g 37.28 8.29 29.06
mix packaged in film. This product is used extensively in
Calories 79 63 16 hospitals and nursing home feeding because the cooked
Protein, g 6.07 2.79 3.35 product remains hot for an extended period in thefilmbag.
Lipid, g 5.58 5.60 Trace As some dieticians desire a reduced-cholesterol egg prod-
Carbohydrate, g 0.60 0.04 0.41 uct for nursing home feeding, it is possible to use a blend
Fiber, g O O O of whites and yolk with only enough yolk for color as the
Ash, g 0.47 0.29 0.18 egg source instead of whole liquid egg.
Minerals
Omelets
Calcium, mg 28 26 4
Iron, mg 1.04 0.95 0.01 The major difference between omelets and scrambled eggs
Magnesium, mg 6 3 3 is that in a true omelet no milk is included in the formula.
Phosphorus, mg 90 86 4 Water is used instead of the milk. Omelets are produced
Potassium, mg 65 15 45
Sodium, mg 69 8 50
for distribution as frozen product either fully cooked or as
Zinc, mg 0.72 0.58 0.01 a premix. The formulation of omelet mixes frequently in-
cludes diced ham, bacon bits, mushrooms, onions, green or
Vitamins red peppers, and a number of other vegetables.
Ascorbic acid, mg O O O
Thiamin, mg 0.044 0.043 0.002 Crepes, Pancakes, and Waffles
Riboflavin, mg 0.150 0.074 0.094
Niacin, mg 0.031 0.012 0.029
Each of these products has a formula including flour and
Pantothenic acid, mg 0.864 0.753 0.080 eggs. The crepe mixture is usually richer in eggs than the
Vitamin B6, mg 0.060 0.053 0.001 other two. Each of these products is fully cooked and frozen
Folacin, jug 32 26 5 for distribution. There are also dry mixes for preparation
Vitamin B12, ^g 0.773 0.647 0.021 of the products in the home.
Vitamin A, R.E. 78 94 O
Snack Foods from Eggs
Lipids
Saturated fatty acids, g 1.67 1.68 O A number of egg-rich snack foods have been proposed but,
14:0 0.02 0.02 O thus far, none have become significant users of eggs. A
16:0 1.23 1.24 O breaded, fried egg white ring that looks much like an onion
18:0 0.43 0.43 O ring was patented (21), and a procedure for producing an
Monounsaturated FA, g 2.23 2.24 O egg jerky flavored to taste like dried meat jerky was sug-
16:1 0.19 0.19 O gested (22). A cookie formulation was prepared so that
18:1 2.04 2.05 O
Polyunsaturated FA, g 0.72 0.73 O each cookie contained one egg equivalent. Another snack
18:2 0.62 0.62 O food that is quite common is yogurt. It is possible to make
18:3 0.02 0.02 O a yogurt-type product using egg albumen as a partial re-
20:4 0.05 0.05 O placement for the milk. In a sensory comparison of normal
Cholesterol, mg 213 213 O yogurt and the egg-substituted product, the latter was
judged superior for mouth-feel and smoothness.
Amino acids
A number of egg-rich drinks have been produced. The
Tryptophan, g 0.097 0.041 0.051 drink sold in greatest quantity is eggnog. This is produced
Threonine, g 0.298 0.151 0.149 as a dried product as well as the refrigerated liquid drink.
Isoleucine, g 0.380 0.160 0.204
Leucine, g 0.533 0.237 0.291
A number of fruit juices have been mixed with eggs to pro-
Methionine, g 0.196 0.171 0.130 duce drinks of orange juice and egg, apple juice and egg,
Cystine, g 0.145 0.050 0.083 and cranberry juice and egg. When preparing any of the
Phenylalanine, g 0.343 0.121 0.210 drinks in quantity, it is recommended that pasteurized liq-
Tyrosine, g 0.253 0.120 0.134 uid eggs be used. The prepared drinks should be kept at
Valine, g 0.437 0.170 0.251 temperatures below 50C (410F).
Arginine, g 0.388 0.193 0.195
Histidine, g 0.147 0.067 0.076
Alanine, g 0.354 0.140 0.215 MODIFYING THE COMPOSITION OF EGGS BY
Aspartic acid, g 0.602 0.233 0.296 PROCESSING
Glutamic acid, g 0.773 0.341 0.467
GIycine, g 0.202 0.084 0.125
Proline, g 0.241 0.116 0.126 The composition of egg products can be modified rather
Serine, g 0.461 0.231 0.247 easily by utilizing yolk, white, or whole egg in various
amounts. Much interest has been shown in reducing the
Note: Shell is 12% of weight of egg.
"Fresh yolk includes a small proportion of white.
amount of cholesterol in eggs. The cholesterol can be re-
Source: Ref. 3 moved from the yolk by using supercritical extraction
techniques with carbon dioxide as the extracting solvent. 15. H. R. Ball, Jr., et al., "Functions and Shelflife of Ultrapas-
Much of the research has been with dried egg yolk, but it teurized, Asceptically Packaged Whole Egg," Poultry ScL
is possible to remove more than 80% of the cholesterol from (Suppl. 1), 63 (1985).
the liquid yolk by supercritical extraction techniques (23). 16. "The Liquid Egg (Pasteurization) Regulations 1963," Statu-
tory Instruments, No. 1503, H. M. Stationery Office, London,
1963.
EGGS AS A SOURCE OF PHARMACEUTICAL PRODUCTS
17. F. E. Cunningham, "Egg Product Pasteurization," in W. J. Sta-
delman and O. J. Cotterill, eds., Egg Science and Technology,
Lysozyme makes up 3.5% of the egg white. A cation ex- 4th ed., Haworth Publishing, Binghamton, N. Y, 1995.
change system consisting of a macroporous, weak acid
18. O. J. Cotterill, and J. L. Glauert, "Nutrient Values for Shell,
resin can be used to recover most of the lysozyme (24). The Liquid/Frozen and Dehydrated Eggs Derived by Linear Re-
system can be designed as a continuous operation. It was gression Analysis and Conversion Factors," Poultry ScL 58,
found that the residual lysozyme-free egg white possessed 131-134 (1979).
superior whipping, gelling, and emulsifying properties 19. Sheng-Chin Yang, and R. E. Baldwin, "Functional Properties
compared with native egg albumen. Lysozyme-free albu- of Eggs in Foods," in W. J. Stadelman and O. J. Cotterill, eds.,
men has been approved for food product usage by federal Egg Science and Technology, 4th ed., Haworth Publishing,
agencies in the United States, providing the labeling is ap- Binghamton, N. Y, 1995.
propriate. Extracted lysozyme may be used in pharmaceu- 20. W. J. Stadelman et al., Egg and Poultry Meat Processing, Ellis
tical products or as an antibacterial agent in the preser- Horwood, Chichester, England, 1988.
vation of food products. 21. U.S. Pat. 4,421,770 (Dec. 20, 1983), J. M. Wicker and F. E.
Fertile eggs are used extensively in the production of Cunningham (to Kansas State University).
vaccines. Some recent work has shown promise for the egg 22. U.S. Pat. 4,537,788 (August 28, 1985), V. Proctor and F. E.
to be used as a means of producing antibodies by manip- Cunningham (to Kansas State University).
ulation of diet and management of the hen. 23. G. Zeidler, G. Pasin, and A. King, "Removing Cholesterol from
Liquid Egg Yolk by Carbon Dioxide-Supercritical Fluid Ex-
BIBLIOGRAPHY traction," in J. S. Sim and S. Nakai, eds., Egg Uses and Pro-
cessing TechnologiesNew Developments, CAB International,
1. USDA, Agricultural Statistics, U.S. Government Printing Of- Oxon, U.K.
fice, Washington, D.C., 1961-1997. 24. E. Li-Chan et al., "Lysozyme Separation from Egg White by
2. W. J. Stadelman, and O. J. Cotterill, Egg Science and Tech- Cation Exchange Column Chromatography," J. Food ScL 53,
nology, 3rd ed., AVI Publishing Westport, Conn., 1986. 425-427 (1986).
3. USDA, "Composition of Foods, Dairy and Egg ProductsRaw,
Processed, Prepared," Agricultural Handbook 8.1, USDA, WILLIAM J. STADELMAN
ARS, U.S. Government Printing Office, Washington, D.C., Purdue University
1976; revised, 1989. West Lafayette, Indiana
4. USDA, Egg Grading Manual, USDA, AMS, Agriculture
Handbook 75, U.S. Government Printing Office, Washington,
D.C., 1983 ELASTINS AND MEAT LIGAMENTS
5. E. C. Naber, "The Effect of Nutrition on the Composition of
Eggs," Poultry ScL 58, 518-528 (1979). Elastin and collagen are the principal components of con-
6. R. L. Adams et al., "Introduction of Omega-3 Polyunsaturated nective tissue. They form a network that is responsible for
Fatty Acids into Eggs," Abstracts of Papers of Southern Poul- the transmission of tension and the structure of muscle
try Science Society, Atlanta, Ga. (1989). and other tissues. Elastin forms a lesser proportion of con-
7. W. J. Stadelman and D. E. Pratt, "Factors Influencing Com- nective tissue than collagen and is not soluble during heat-
position of the Hen's Egg," World's Poultry ScL J. 45, 247-266
ing. The ratio of collagen to elastin in connective tissue is
(1989).
dependent on the tissue and its location. This ratio affects
8. M. A. North, and D. D. Bell, Commercial Chicken Production
Manual, 4th ed., Chapman & Hall, New York, 1990.
the tissue's mechanical properties and its physiological
functions (1). Elastin is present in muscle only in small
9. USDA, "Regulations Governing the Grading of Shell Eggs and
United States Standards, Grades and Weight Class for Shell
amounts, less than 3% of the total connective tissue. Mus-
Eggs," USDA, AMS, Poultry Division, 7 CFR, Part 56, 1987. culus semitendinosus, however, contains more elastin, up
10. R. G. Board and R. Fuller, Microbiology of the Avian Egg, to 37% of the total connective tissue. Elastin normally
Chapman and Hall, London. forms fibers and lamellae, is abundant in elastic ligaments,
11. W. J. Stadelman et al., "Pasteurization of Eggs in the Shell," and elastic blood vessels, and is found to a small extent in
Poultry ScL 75, 1122-1125(1996). the skin, lungs, and other organs.
12. J. W. Koudele, and E. C. Heinsohn, "The Egg Products Indus- Elastic tissue is often referred to as yellow connective
try of the United States. I. Historical Highlights, 1900-1959," tissue because of its color. It contains the elastin fibers with
Kansas Agric. Exp. Station Bull. 423, 1960, pp. 1-48. filamentous, refractive, and fluorescent with a blue-white
13. O. J. Cotterill and G. S. Geiger, "Egg Product Yield Trends appearance under ultraviolet light. Because of the large
from Shell Eggs," Poultry ScL 56, 1027-1031 (1977). number of nonpolar amino acids in the structure and their
14. USDA, "Regulations Governing the Inspection of Eggs and hydrophobic nature, the elastin fibers stain poorly with
Egg Products," USDA, AMS, Poultry Division, 7 CFR, Part acid or basic dyes but do stain selectively with phenolic
59, 1984. dyes such as orcein.
MORPHOLOGY is catalyzed by a copper-containing enzyme, lysine oxidase.
Therefore, the synthesis of elastin can be blocked by inhi-
The basic morphological component of elastin is filament bition of this enzyme through dietary copper depletion, or
made up of a linear sequence of globular structures with by /?-aminopropionitrile, the active lathyrogen of the sweet
a probable maximum diameter of 910 nm. Dehydrated pea. The synthesis is age dependent; the amount of des-
elastin may be 4-6 nm in diameter (2). The freeze-etching mosine and isodesmosine increase and the lysine content
technique reveals elastin's structure as a regular, three- decreases with advancing age. The elasticity of elastin is
dimensional network of filaments. The filaments cross due to the exposure of nonpolar sequences of its molecules
their neighbors every 8-12 globular subunits, giving rise to water during the stretching, followed by spontaneous
to a network with a large, less-dense central core (3). The refolding of the molecule on removal of the applied force.
filaments of elastin can be disordered and swollen when Elastin can be isolated as the residue remaining after
immersed in 25% glycerol for 8-10 days. The swollen elas- the extraction of tissue with 0.1 N NaOH at 980C for 45
tin shows a much higher affinity for stains. min (4). Elastin is heat stable to a temperature of 140-
15O0C and is insoluble in a wide range of hydrogen bond
CHEMISTRY AND BIOCHEMISTRY breaking solvents at temperatures up to 10O0C. It must be
processed with harsh enzymatic or chemical treatments in
Elastin can be determined from the amount of desmosine order to solubilize it. This includes KOH/ETOH solubilized
or isodesmosine found in the tissue. Its amino acid com- /c-2-elastin, oxalic acid solubilized a-elastin, elastase sol-
position is essentially identical as extracted from various ubilized elastin, and various salt-soluble forms of elastin
tissues and are not affected by the age of the animal (4). (9).
However, compositions differ from animal to animal. Elas- Using immunological techniques, two serologically dis-
tin contains 1-2% hydroxyproline. Almost 95% of its amino tinct elastin antibody fractions in antiserum prepared
acids are nonpolar (Table 1). The sulfur amino acids, tryp- against bovine ligamentum nuchae elastin were identified
tophan, and tyrosine are present in small amounts or non- (9). One is a species-specific fraction that bound only to
existent. In contrast to collagen, elastin does not contain bovine elastin. The other population of antibodies has af-
hydroxylysine. Elastin has about one-third of its amino ac- finity for elastin from porcine aorta, bovine ligamentum
ids as glycine, but their arrangement in the elastin mole- nuchae and aorta, rabbit and hamster lung, and human
cule is unknown. Desmosine and isodesmosine, unique cy- aorta. The elastin radioimmunoassay can be modified to
clic polymers, are made up of four lysine residues, which detect bovine or other elastins, depending on the choice of
connect two to four elastin molecules. This reaction re- radiolabeled antigen, in meat products. This assay also
quires the oxidative deamination of three lysine e-amino permits the study and quantification of elastin synthesis
groups which give an intermediate followed by condensa- and degradation in a wide range of meat-animal species
tion with the e-amino group of a fourth lysyl residue, and without having to raise specific antibodies to each one.
Table 1. Amino Acid Compositions of Elastins from Selected Tissues of Various Meat Animals
Residues per 1000 residues
Amino Acid Avian, insol0 Bovine, semitendinosus6 Sheep, vascular tissue0 Yellowfin tuna, dark muscle**
Asp 2 7.4 1.8 66.0
Hyp 22 12.4 0.0 6.0
Thr 3 8.2 9.2 51.0
Ser 5 8.3 9.0 53.0
GIu 12 17.1 20.4 134.6
Pro 128 110.9 105.3 65.1
GIy 352 325.9 241.1 128.5
Ala 176 223.1 288.7 91.7
VaI 175 145.8 111.7 55.9
Cys/2 1 17.6
Met 22.3
lie 19 26.5 17.5 38.2
Leu 47 61.4 57.5 82.9
Tyr 12 8.4 13.4 31.7
Phe 23 29.8 34.5 29.9
HyI 22 12.4 0.0
Lys 4 5.3 30.7 62.2
His 1 0.6 13.6 14.8
Arg 5 5.7 6.8 48.0
isodes 3 2.1a 29.36 0.5
Des 3 1.2a 7.26 0.3a
Source: aRef. 4, 6Ref. 5, cRef. 6, and <*Ref. 7.
The emission spectrum of elastin is similar to that of meat is put through a grinder and the bone chips and gris-
Type I collagen with peak excitation near 370 nm. Macro- tle are separated from the ground meat. For large-muscle
scopic ultraviolet fluorometry was used to measure the products, such as ham, the meat must be hand trimmed.
gristle contents, elastin, and collagen TyPe I of beef (10). The separated gristle with elastin and collagen tissue is
Fluorescence emissions were measured with a mono- discarded or chopped fine and used in emulsified products.
chromator and a photomultiplier tube. Intact tendons and It is used as a filler rather than functional proteins for
elastic ligaments had a strong fluorescence emission peak economic reasons.
around 440-450 nm and only weak fluorescence around Meat cuts with a high gristle, collagen, and elastin con-
510 nm. The 510:450 nm ratio was correlated to the tent are not used in large-muscle products. They are used
amount of gristle in comminuted meats. most often in emulsified products to minimize the tough-
ness problem of the gristle. However, elastin and collagen
tissues from gristle do not bind water or function as emul-
INDUSTRIAL APPLICATIONS sifiers in meat emulsion; therefore, emulsion breakdown
occurs more often in these products. To solve these prob-
The visible gristle in meat is from a number of sources, lems, a computer-based, least-cost formulations program,
including tendons (particularly from myotendon junc- which is widely used in the processed meat industry, has
tions), ligaments (such as the ligamentum nuchae in rib incorporated the connective tissue in individual meat cuts
roasts), perimysium (particularly in the pennate extensors as a quality constraint in the computer simulation of prod-
and flexors of the lower limbs), fasciae (such as the lum- uct formulations. But no effort has been made to separate
bodorsal fascia of the longissimus muscle), and intramus- the elastin or ligament contribution as a constraint in the
cular vessels (particularly arteries). All these sources con- computer program, because of the low content of elastin in
sist mainly of Type I collagen or elastin. Elastin-contained most meat cuts.
gristle retains its tensile strength after typical cooking pro- Unlike collagen, elastin does not swell at mild acid con-
cedures, such as roasting and broiling (11,12). Fresh meat ditions and has no film-forming properties. It is not used
cuts containing gristle are generally perceived as lower in gelatin production because of its poor water solubility
quality products, because of the unpleasant sensation of and gelation properties. It cannot be substituted for col-
gristle. However, the elastin concentration is not consis- lagen in regenerated collagen casing, or collagen film and
tently related to variations in the tenderness of muscles, tissue. Elastin also has little use in the processed meat
at least in the bovine species (13), nor is the total concen- industry because it functions poorly as a binder and emul-
tration of connective tissue components (collagen and elas- sifier. Because it is found in only small amounts in meats,
tin). Tenderness is actually more related to soluble colla- because it is uneconomical to separate it from other meat
gen and the overall fiber arrangement in the meat. tissues, and because it is poor nutritionally, elastin's tech-
Aging is the industrial practice of storing meat car- nological development for use in foods and other industries
casses above the freezing point for a certain period of time has been hindered.
to improve the tenderness. The changes are the result of
the physical breakage of muscle and collagen protein fibers BIBLIOGRAPHY
by rigor and enzymatic reactions. However, aging has no
apparent effect on the structure of elastin tissue and its 1. R. J. Bagshaw, E. Weit, and R. H. Cox, "Aortic Connective
physical properties. Tissue Content in White Leghorn Females," Poultry Science
Tissues with high elastin content, such as elastic liga- 65, 403 (1986).
ments, blood vessels, and lung, are removed in the slaugh- 2. C. Fornieri, I. P. Ronchetti, A. C. Edman, and M. Sjostrom,
tering operation. They are processed as offals with other "Contribution of Cryotechniques to the Study of Elastin Ul-
organs and by-products in the rendering industry as a pro- trastructure," Journal of Microscopy (Oxford) 126, 97 (1982).
tein source for animal feed. In this application, they may 3. M. Morocutti, M. Raspanti, P. Govoni, A. Kadar, and A. Rug-
be rendered at high or low temperature, depending on the geri, "Ultrastructural Aspects of Freeze-Fractured and
planned use of the fat. Fat is separated from the solids by Etched Elastin," Connective Tissue Research 18, 55 (1988).
centrifugation. The solids are dried and batched with other 4. H. R. Cross, G. C. Smith, and Z. L. Carpenter, "Quantitative
protein sources for optimum amino acid content and dis- Isolation and Partial Characterization of Elastin in Bovine
Muscle Tissue," Journal of Agricultural and Food Chemistry
tribution, and then used in animal feed. The make-up of
21, 716 (1973).
the feed is determined by a linear program based computer
5. J. A. Foster "Elastin Structure and Biosynthesis: An Over-
program which takes account of the amino acids, fat, car- view," in, Structural and Contractile Proteins. Part A. Extra-
bohydrate, vitamin, and mineral content required in feed cellular Matrix, L. W. Cunningham and D. W. Frederiksen,
formulations. eds. Academic Press, New York, 1982, pp. 559-570.
In the ready-to-eat processed meat industry, elastin tis- 6. J. R. Bendall, "The Elastin Content of Various Muscles of Beef
sues and meat ligaments retain their tensile strength and Animals," Journal of the Science of Food and Agriculture 18,
are not gelatinized under most heat-processing conditions. 553 (1967).
For this reason, elastin tissues in meat are removed, with 7. S. Kanoh, T. Suzuki, K. Maeyama, T. Takewa, S. Watabe, and
other gristle, by mechanical means, by hand or mechanical K. Hashimoto, "Comparative Studies on Ordinary and Dark
gristle removers. Grinders equipped with gristle and bone Muscles of Tuna Fish," Bulletin of the Japanese Society of Sci-
removers are widely used in the processed meat industry entific Fisheries (NIHON SUISAN GAEFFAI-SHI) 52(10),
for coarse-ground, nonemulsified products. In this case, the 1807 (1986).
8. J. N. Manning, P. F. Davis, N. S. Greenhill, A. J. Sigley, "Salt Butter and margarine are obvious examples of the op-
Soluble Cross-linked Elastin: Formation and Composition of posite type of emulsion, the water-in-oil emulsion. The
Fibers," Connective Tissue Research 13(4), 313 (1985).
aqueous phase is dispersed in the fat or oil and is now
9. R. P. Mecham and G. Lange, "Measurement by Radioimmu- known as the discontinuous or internal phase, as the lipid
noassay of Soluble Elastins from Different Animal Species,"
Connective Tissue Research 7, 247 (1980).
has become the continuous or external phase.
A gaseous phase can also exist and may be external, as
10. H. J. Swatland, "Fiber-Optic Reflectance and Autofluores-
in the case of an aerosol, or internal, as in whipped topping.
cence of Bovine Elastin and Differences between Intramus-
cular and Extramuscular Tendon," Journal of Animal Science Dual emulsions are commonly encountered; a cake batter
65, 158 (1987). is a good example of the latter. Air or leavening gasses are
11. A. M. Pearson and F. W. Tauber, Processed Meats, AVI Pub- dispersed in the fat, which is, in turn, dispersed in the
lishing Co., Inc., Westport, Conn. 1984. aqueous phase of the oil-in-water cake batter.
12. P. P. Purslow, "The Physical Basis of Meat Texture: Observa-
The viscosity of a food emulsion is a function primarily
tions on the Fracture Behavior of Cooked Bovine M. Semiden- of the external phase. It is generally lower when the ex-
dinosus" Meat Science 12, 39 (1985). ternal phase is aqueous, as in the case of milk, and higher
13. H. R. Cross, Z, L. Carpenter, and G. C. Smith, "Effects of In- when the external phase is lipid, as in the case of marga-
tramuscular Collagen and Elastin on Bovine Muscle Tender- rine. Several other factors can affect emulsion viscosity. In
ness," Food Science 38, 998 (1973). the case of an oil-in-water type of emulsion, packing or
clumping of the internal phase can affect yield value and
viscosity. An example of such an emulsion is mayonnaise.
RUDY R. LIN The internal dispersed phase (oil) occupies over 70% of its
Swift-Eckrich, Inc. volume, closely approaching its theoretical maximum
Downers Grove, Illinois
when the oil globules are of uniform spherical shape. Such
an emulsion exhibits little or no flow properties, and its
yield value and viscosity are such as to lead the causal
EMULSlFlER TECHNOLOGY IN FOODS observer to assume it may be a water-in-oil emulsion.
Oil-in-water emulsions can contain higher than theo-
Most foods consumed by humans are emulsions, in that retical limits of lipid internal phase (74%) if globules are
they contain either fats or oils dispersed in an aqueous misshapen due to compression, and viscosity can be fur-
phase, or they contain an aqueous phase dispersed in a fat ther affected by hydrogen bonding and van der Waals
or oil. An example of the prior emulsion would be milk; an forces. Surface charges supplied by components such as
example of the latter would be butter. phospholipids can reduce viscosity by imparting repel-
A food emulsion may be described as a multiple-phase lency.
system that contains at least two components that are nor- When the internal phase of an oil-in-water emulsion is
mally immiscible. Oil and water are examples of such in- low, as in the case of dairy products, ingredients such as
compatible components. The water or aqueous phase may colloids, including cellulose, starch, and algins, may be
contain many other ingredients that are truly soluble in added to increase viscosity. Homogenization of the lipid
the aqueous phase such as sugars and salts. It may also phase to attain more surface area per unit weight of dis-
contain colloidally dispersed components such as proteins perse phase will increase viscosity. Indeed, when homog-
and carbohydrate polymers such as cellulose. The fat or oil enization of dairy foods was introduced in the United
phase may contain other lipids such as phospholipids and States in the 1930s, it so improved perceived richness due
glycolipids, and certain vitamins, colors, and sterols. to increased surface area and resultant viscosity that an
The preparation by humans of food emulsions not found attempt was made to ban the process on the basis that it
in nature has been considered a culinary art and has been deceived the consumer. As an example, using typical ho-
practiced as an art for centuries. A perfect example of an mogenization procedures, milk with an average 8 ju fat
artful culinary emulsion has been mayonnaise. Such emul- globule is converted to 512 globules of 1 ju providing an
sions did not require long-term stability because they were eightfold increase in surface area.
consumed within a short period of time in the home or Most commercial food emulsions contain the disperse
restaurant. Such problems as freeze/thaw stability, long- phase in small globules in the range of 0.1 to 0.2 ju. With
term storage, the physical rigors of transportation, and water-in-oil emulsions such as margarine, the viscosity, or
high degree of aeration did not concern the chef of bygone plasticity, is a function primarily of the crystalline solids
eras. His emulsions would be considered crude by today's contribution of the fat, as well as its melting point.
standards. His emulsiona sauce, for examplewould be The aqueous phase included in the margarine lipid
acceptable if stable for only a few hours, as compared with phase is dispersed using a scraped surface crystallizer,
the months of stability required today in commercially pro- such as the votator, so that the water particles are as small
duced emulsions such as salad dressings. as possible. Large particles explode into steam when the
Milk and salad dressings are two of the primary ex- margarine is used for cooking with such violence as to
amples of one type of emulsionthe oil-in-water emulsion. cause spattering. A properly manufactured margarine will
The oil or lipid phase is also known as the disperse, dis- have the dispersed water particles in the 1 to 5 // range.
continuous, or internal phase. It is dispersed in the aque- Most oil-in-water emulsions such as dairy-type frozen
ous serum phase, also known as the external or continuous desserts, because of very efficient modern homogenizers,
phase. possess fat globules with a diameter of less than 0.5//. The
size of the fat globule will affect the light reflected to the Food emulsifiers can be manufactured by the esterifi-
viewers eyes in a simple oil in water emulsion. In fact, the cation of a polyol such as glycerine or sorbitol with a source
size of the oil globule can be estimated from the appear- of fatty acid. Glycerine can be directly esterified with a
ance of the emulsion as given in Table 1. fatty acid or, as is usually more economical, glycerine can
The physical stability of an emulsion, that is, the ten- be transesterified with a fat (glycerolysis). Both procedures
dency of the two phases not to separate, takes place in will produce a surface active glyceryl monoester such as
accordance with Stokes Law: glyceryl monostearate. The resulting monoester will be
surface active because it will possess the fat-loving stearic
acid moiety and the water-loving hydroxyl groups of the
unesterified polyol carbons within the same molecule
"=^^ (Fig. 1).
where V is the velocity of the sphere, r the radius of the Although glyceryl monoesters are the most commonly
sphere, rj the viscosity of the continuous phase, di the den- used surfactants in the food industry and are found natu-
sity of the continuous phase and d2, the density of the dis- rally occurring in most oil-bearing food (milk, nuts, olives,
perse phase, and g the force of gravity. In an oil-in-water wheat, etc), other alcohols and aldehydes may be used to
emulsion, the oil globules of lower density will tend to rise supply the hydroxyl groups. When a shortage of glycerine
through the more dense aqueous phase. They will rise developed during World War II, it was found that a mono-
more rapidly if they coalesce into larger globules, and their ester of sorbitol produced by hydrogenation of glucose
separation will be slowed by increased viscosity. could be substituted in most cases. Not only were such es-
When an oil is finely divided in a aqueous phase, a ten- ters found to be equivalent to those derived from glycerol,
sion is created due to the increased surface energy created they were usually superior. Sorbitol differs from glycerine
by division. The oil tends to coalesce to reduce this tension in that it contains six water-loving hydroxyl groups instead
by returning to the lowest free energy state. An emulsifier of three and is thus more hydrophilic (Fig. 2).
(surface active agent) will reduce this tension by adsorp- Other alcohols and aldehydes such as propylene glycol
tion at the interface between the two antagonistic phases, and sucrose may be used to supply the hydrophilic moiety
thus reducing the free energy (amphiphilic). of the surfactant. The hydrophilic character and functional
Some surfactants further stabilize food emulsions by in- value may be further enhanced by further esterification
hibiting coalescence due to contributing an electrical with organic acids such as lactic, citric, or acetic to produce
charge (usually negative) at the fat globule surface. The the diester. The esters can be made even more hydrophilic
likely charged globules repel one another, further reducing by ethoxylation (Fig. 3) or by esterification with polymers
the opportunity for coalescence. such as polyglycerol. Because of its amphiphilic character,
Most food emulsions produced today contain added sur- the surfactant will orient itself to the interface between the
face active agents (emulsifiers). Modern food processing lipid and aqueous phase. The more hydrophilic the emul-
procedures are designed to produce food with long-term
shelf life and to withstand the rigors of transportation, in-
cluding temperature extremes and mechanical abuse.
Added surfactants contribute significantly to long-term
emulsion stability. As an example, salad dressings that
would normally separate in a matter of hours are stable
and acceptable to the consumer after months of storage.
Most surfactants used in food processing are esters of
fatty acids, and although found in nature, they are in most
cases not present in the food after processing in sufficient
quantity to provide the desired emulsion stability. Emul- Figure 1. Glyceryl monostearate.
sifiers are characterized by the fact that they are ampho-
teric; that is, they posses both an oil-loving and a water-
loving moiety within the same molecule. Since they are
neither completely lipophilic (oil loving) nor hydrophilic Glycerine Sorbitol
(water loving) they proceed to the interface between both
components and orient themselves in a structure making
the fat and water more compatible.
Applications:
Dental paste
Flavor encapsulation
a. Cubic
Fluid
Isotropic Cubic
Cubic + H2O
Temperature (0C)
Lamellar
Dispersion
b. Lamellar
% Water (w/w)
promoting aeration of the batter. They are usually added 0.1% Glycerol monostearate
in hydrated paste or gel form (25-50% solids) to aid in dis-
persion. Naturally occurring surfactants such as phospho-
lipids from egg also contribute to emulsification of the
batter.
As early as 1925, it had been confirmed that the addi-
tion of eggs improved the whipping quality of ice cream
mixes (18). It was assumed that the albumin protein frac-
tion of egg was the principal aerating agent. In 1928 it was
demonstrated that egg albumin had no beneficial effect on
the ice cream mix and that the improved aerating quality
was being contributed by the yolk (19). It was later deter- Reflectance
mined that the improvement was due to the emulsification Percent overrun
imparted by phospholipids and lipoprotein in the yolk
(20,21). Inclusion of yolk in the mix was also shown to in-
crease the electrical charge (anionic) carried by the fat
globule (22).
In 1936 a patent was granted on the use of glyceryl
monostearate as an emulsifier and whipping aid for ice
cream (23). It was found that the monoester was as effec-
tive at 0.1 to 0.2% as egg yolk was at 0.5%. It was also
found that the use of the monoester provided an ice cream
that was drier and stiffer on freezing and thus extruded
and packaged with greater facility.
Surfactants based on saturated fatty acids were found Minutes in freezer
to be more effective as aerating agents when used as ice
cream emulsifiers, as compared with those based on un- Figure 7. Performance characteristics, ice cream emulsifier glyc-
saturated fatty acids (Figs. 7 and 8). The more hydrophilic eryl monostearate.
ethoxylated surfactants are more effective than those of
lower HLB value. Those approved for use in food contain
an average of 20 mol of ethylene oxide and have an HLB
in the 14 to 16 range. factant such as ethoxylated sorbitan monooleate resulted
In the production of whippable emulsions, such as ice in a synergistic effect in frozen aerated desserts whereby
cream or whipped toppings, it is desirable to obtain good the combination produced improved whippability and stiff-
volume and stiffness. Contrary to published hypothesis, it ness (26).
was demonstrated that a partial breakdown of the emul- As with cake batter foams, a-tending surfactants form
sion during whipping to produce agglomerated (but not co- strong protective films around oil globules and are espe-
alesced) fat globules provides maximum product stiffness cially effective in promoting agglomeration of fat globules
(24,25). It was found that the more hydrophilic ethoxylated in dairy-type emulsions. The a-tending surfactants are ad-
surfactants based on saturated fatty acids such as stearic sorbed onto the globule surface, interfering with strong
provided maximum whippability, whereas those based on protein bonding and making the protective protein film
unsaturated fatty acids such as oleic provided maximum more easily swept off the surface during whipping, result-
dryness and stiffness to the aerated product. A turbidi- ing in increased agglomeration of globules with resulting
metic procedure was used to prove that surfactants actu- firm texture and stiffness in whipped foams (eg, toppings).
ally accelerated the breakdown of the ice cream mix emul- Margarine is probably the simulated dairy product most
sion to provide agglomerated fat globules (Fig. 9) (24). widely consumed. It is a water-in-oil emulsion usually con-
Combining a lipophilic saturated surfactant such as taining 80% fat and 20% aqueous phase. A lipophilic emul-
glyceryl monostearate with a hydrophilic unsaturated sur- sifier system of 0.5 to 1.0% is used to stabilize the emul-
0.1% Glycerol monooleate sion, preventing leakage of the aqueous phase (weeping)
and reducing spattering when the margarine is used for
frying.
Surface-active agents with a high degree of unsatura-
tion are usually preferred for margarine, especially the
low-fat/high-aqueous types as they more tenaciously in-
corporate the high-level water into the oil phase.
Another category of simulated dairy products with a
large market is milk replacers for young animals. Such
emulsions are usually spray-dried in such a manner as to
retain the emulsion potential intact, and the emulsion re-
Reflectance forms instantly on rehydration.
The largest consumption of surfactants within the food
Percent overrun
industry is by the baking industry. Aside from the use of
surfactants for cake-batter emulsification previously dis-
cussed, surfactants are used in yeast-raised products such
as bread and rolls for the purpose of reducing the rate of
crumb firming, the principal factor associated with staling,
and to strengthen gluten (dough conditioning).
As long ago as 1852, the French chemist Boussingault
(27) proved that bread did not stale because of moisture
loss simply by hermetically sealing it in cans, where the
crumb firmed as rapidly as that of unsealed loaves. It is
now generally conceded that bread crumb firms primarily
Minutes in freezer owing to the retrogradation of the gelatinized wheat
starch. The linear amylose fraction (Fig. 10) retrogrades
Figure 8. Performance characteristics ice cream emulsifier glyc- almost immediately after the baked product cools, thereby
eryl monooleate. supplying physical structure to the baked food. It is not
further involved in an ongoing firming. The branched amy-
lopectin fraction (Fig. 10), however, continues to retrograde
slowly over a period of days, causing the crumb to become
firmer with aging.
Certain surfactants can retard crumb firming because
they are able to form complexes with the glucose polymers
of starch. Although these surfactants will form complexes
with both the straight-chain amylose and the branched-
chain amylopectin, it is now understood that it is most im-
portant to complex with the amylopectin since it is respon-
sible for the progressive firming of crumb. It has been
Turbidity as percent of original mix reading
1,6 Linkage
Nonionic: 1-monoglyceride
mercial GMS, for example, may contain as little as 65% ening phase of the cake formulation and contribute to the
stearate, if made from fully hydrogenated lard, or as much emulsification of the shortening in the water phase as well
as 87% stearate, if made from fully hydrogenated soybean as promoting incorporation of air into the fat phase. The
oil. The other principal saturated fatty acid will be pal- particular property of these emulsifiers that makes them
mitic, and because hydrogenation is practically never car- valuable in liquid shortening cakes is that they form a solid
ried out to the extent that all unsaturation is removed (io- film at the oil water interface, not only stabilizing the
dine value of zero), a small percentage of unsaturated (oleic emulsion but also keeping the lipid phase from preventing
and elaidic) acid is also usually present. Iodine values for air incorporation (protein-stabilized foam formation) dur-
powdered distilled monoglycerides (monoglyceride in a ing cake batter mixing.
beaded form that hydrates readily when incorporated in a
bread dough) are in the range of 19 to 36, and for plastic Sorbitan Derivatives. When the sugar alcohol sorbitol is
monoglycerides a typical range is 65 to 75. The unsatu- heated with stearic acid in the presence of a catalyst, two
rated fatty acids are a mixture of oleic and linoleic and the reactions occur: sorbitol cyclizes to form the five-membered
trans isomers of these acids. sorbitan ring and the remaining primary hydroxyl group
The product of the manufacture of ethoxylated mono- is esterified by the acid. The resulting sorbitan monostear-
glyceride (EMG) is somewhat random in structure. Mono- ate (Fig. 4) is oil soluble, has a rather low hydrophilic Ii-
glyceride is treated with ethylene oxide gas under pressure pophilic balance (HLB) value, and is the only one of the
in the presence of alkaline catalyst at elevated tempera- many sorbitan esters explicitly approved for food use in the
tures. Ethylene oxide polymerizes via a series of ether link- United States (sorbitan tristearate is marketed as a crys-
ages and also forms ether bonds with the free hydroxyl tal modifier, as a self-affirmed GRAS material). Other sor-
groups on the monoglyceride. The average number of eth- bitan esters of importance are the monooleate and the tri-
ylene oxide units per monoglyceride molecule is about 20 stearate. Any of the three esters may be reacted with
units (n = 20 in Fig. 3), distributed between two chains if ethylene oxide to give polyoxyethylene derivatives, as in-
the monoglyceride is doubly substituted. Chains may be dicated in Figure 4 which are water soluble and have a
attached to hydroxyls at both the two and three positions relatively high HLB. The monostearate derivative is
of the monoglyceride, although many more chains will be known as Polysorbate 60, the tristearate is Polysorbate 65,
located at the a (three) position than at the ft (two) position and the monooleate is Polysorbate 80. The remarks made
because of the difference in their chemical reactivities. The in connection with EMG regarding the length and location
exact distribution of polymer chain lengths and distribu- of the polyoxyethylene chains apply to these compounds.
tion between a and ft positions are functions of reaction The average number of oxyethylene monomers per sorbi-
conditions, for example, catalyst type and concentration, tan ester molecule is 20 (n = 20), and in the case of the
gas pressure, temperature, agitation, and length of reac- monoesters, chains of varying length (but with about 20
tion time. ethylene oxide units in aggregate) may be attached to more
The second group of monoglyceride derivatives, the at- than one hydroxyl group of the sorbitan ring (triester has
tending emulsifiers (lactylated monoglyceride, acetylated only one hydroxyl group available for derivatization).
monoglyceride, and PGMS), find their main use in cake Sorbitan monostearate is used in applications where fat
production. These emulsifiers are dissolved in the short- is the continuous phase, that is, in fat-based confectionery
Polyoxyethylene (20)
sorbitan monostearate
(Polysorbate 60)
Polyoxyethylene (20)
sorbitan tristearate
(Polysorbate 65)
Sorbitan monostearate
coatings, in bakery icings, and in coffee creamers. The poly- emulsifiers the most common ones are n = 1 (triglycerol),
oxyethylene derivatives have found wider usage. Polysor- n = 4 (hexaglycerol), n = 6 (octaglycerol), and n = 8 (deca-
bate 60 is used in a variety of applications where a high- glycerol) (in all cases n is an average value for the mole-
HLB emulsifier is required, and is used in fluid oil cake cules present in the commercial preparation). The polygly-
shortening systems (4,5,7), generally in combination with cerol backbone is then esterified to varying extents, either
GMS and PGMS. The various sorbitan derivatives are of- by direct reaction with a fatty acid or by interesterification
ten used in combination to obtain a specific desired HLB; with a triglyceride fat. Again, the number of acid groups
the regulations regarding the permitted levels of each esterified to a polyglycerol molecule varies around some
emulsifier in the final product are rather complicated: de- central value, so an octaglycerol octaoleate really should
tails can be found in 21 CFR. be understood as (approximately octa)glycerol (approxi-
mately octa)oleate ester. By good control of feedstocks and
Esters of Polyhydric Compounds. Polyglycerol esters reaction conditions manufacturers do manage to keep the
(Fig. 5) have a variety of applications as emulsifiers in the properties of their various products relatively constant
food industry (3,8). The polyglycerol portion is synthesized from batch to batch.
by heating glycerol in the presence of an alkaline catalyst; The HLB of these esters depends on the length of the
ether linkages are formed between the primary hydroxyls polyglycerol chain (the number of hydrophilic hydroxyl
of glycerol. In Figure 5 n may take any value, but for food groups present) and the degree of esterification. As ex-
Sucrose diester
Polyglycerol
monostearate
Amphoteric Emulsifiers
Lecithin. During the purification of crude oil extracted
from soybean, safflower, or corn germ a phosphatide-rich
gum is obtained that is treated and purified to give the
various commercial lecithin products available to the food
Sodium stearoyl lactylate (SSL)
processor today (12-14). The dark crude material is
bleached to give a more acceptable light brown color. Treat-
ment with up to 1.5% hydrogen peroxide gives the product
known as single-bleached lecithin, and further addition of
up to 0.5% benzoyl peroxide yields double-bleached lecithin
(14). Reaction with even higher levels of hydrogen peroxide
plus lactic acid hydroxylates unsaturated fatty acid side
Sodium stearyl fumarate chains at the double bond (yielding, eg; dihydroxystearic
acid from oleic acid) giving hydroxylated lecithin, which is
Figure 7. Sodium salts of two anionic emulsifiers. The third one, more dispersible in cold water than the other types and is
SDS, is shown in Fig. 1. more effective as an emulsifier for oil-in-water emulsions
(15). Normally some vegetable oil is added to the lecithin equipment. The structure is shown to indicate the chemi-
to reduce the viscosity to 7.5 to 10 Pa-s; this is called stan- cal nature of this group of surfactants and to complete the
dardized fluid lecithin and contains roughly one-third oil description of classes of emulsifiers and surfactant.
and two-thirds phosphatides.
Figure 8 shows the structure of the main surface active
components of lecithin. The phosphatidyl group is a phos- USES OF EMULSIFIERS
phate ester of diglyceride. The fatty acid composition of the
diglyceride is similar to that of the basic oil (16) so a num-
ber of different fatty acids are found, not just the stearic The regulatory status of these food additives falls into one
and oleic acids depicted. There is little phosphatidylserine of three groups. The first group, Section 172 additives, in-
present in soybean lecithin, and the other three derivatives cludes those additives that have been examined and
are found in approximately equal amounts. Phosphatidyl judged to be allowable for certain uses at concentrations
ethanolamine (PE) and phosphatidyl choline (PC) are am- not to exceed a set level. As an example, stearyl monogly-
photeric surfactants, whereas phosphatidyl inositol (PI) is ceridyl citrate (21 CFR 172.755) is allowed for use to sta-
anionic. The HLB values of the three species are varied, bilize shortenings containing emulsifiers. To use this ad-
with PC having a high, PE an intermediate, and PI a low ditive as a wetting agent in a dry gelatin dessert mix, the
value. The HLB of the natural blend is around 9 to 10, and manufacturer would have to submit a petition to the Food
emulsifier mixtures having this value will tend to form ei- and Drug Administration (FDA) seeking clearance for this
ther oil-in-water or water-in-oil emulsions, although nei- application and could not sell it for this purpose until such
ther one is highly stable. On the other hand, intermediate clearance was given. Several of the additives listed in Sec-
HLB emulsifiers are excellent wetting agents and this is a tion 172 are cleared for general use in foods and therefore
principal application for lecithin. may be used in any food where they are functional, at a
The emulsifying properties of lecithin can be improved level not to exceed that amount that produces the desired
by ethanol fractionation (15). PC is soluble in ethanol, PI functional effects.
is rather insoluble, and PE is partially soluble. Adding Sections 182 and 184 of 21 CFR deal with additives that
lecithin to ethanol gives a soluble and an insoluble fraction. are generally recognized as safe (GRAS) and thus can be
The phosphatide compositions of the two are (1) ethanol used in any food. In some cases the regulation allows use
soluble60%, PC; 30%, PE; 2%, PI; and (2) ethanol at any level that is consistent with good manufacturing
insoluble4%, PC; 29%, PE; 55%, PI (17). The soluble frac- practices, while for other additives a tolerance or maxi-
tion is effective in promoting and stabilizing oil-in-water mum use level is established. Section 182 (Substances
emulsions, whereas the insoluble portion promotes and Generally Recognized as Safe) lists additives that are rec-
stabilizes water-in-oil emulsions. At least one company ognized as safe based on a history of use without reported
(Lucas Meyer) is using this process to produce industrial safety problems. If an additive undergoes a specific de-
food-grade emulsifiers. tailed evaluation and its safety is affirmed, it is then
moved to Section 184 (Direct Food Substances Affirmed as
Cationic Emulsifiers Generally Recognized as Safe).
The relevant U.S., Canadian, and European Union reg-
Quaternary Ammonium Surfactants. Cationic emulsifiers ulatory references are listed in Table 2 for most food emul-
are not used as food additives. Some of them, such as the sifiers. In many cases the maximum permissible amount
quaternary ammonium compound cetyltrimethyl- of emulsifier is specified. In other instances, the manufac-
ammonium bromide (CTAB) (Fig. 1), have bactericidal turer is expected to use no more than the amount neces-
properties and are used for sanitation of food-processing sary to provide the desired technological effect.
Ethanolamine
Choline
Phosphatidyl
Pump Cervical
pharyngostomy
Nasogastric Gastrostomy
Nasoduodenal
Nasojejunal Jejunostomy
Figure 1. Tube feeding sites and devices. Source: Courtesy of Applied Therapeutics, Inc., Vancou-
ver, Washington.
pressure necrosis in the nose as well as inflammation of gravity or by a pump (a small portable pump is shown in
throat and esophagus. They may compromise the function Figure 1), into the feeding tube (110). Formula can be de-
of the esophageal sphincter, increasing the potential for livered by a continuous or intermittent administration
pulmonary aspiration. Large tubes may also interfere with schedule. A continuous schedule is preferred when tube
swallowing, discouraging oral consumption of liquid sup- feeding is initiated, when patients have not been fed for
plements. Most adults tolerate nasal tubes ranging be- several days, when patients are critically ill, and when
tween 8 and 12 F. High viscosity formulas or those supple- duodenal or jejunal feeding sites are used (105,107). Inter-
mented with fiber require at least a 10 F tube unless a mittent feedings given five to eight times a day can simu-
feeding pump is being used. Extremely small caliber tubes late a meal pattern. Ambulatory tube-fed patients fre-
(<6 F) require very low viscosity formulas such as elemen- quently use an intermittent or 16 to 18 h continuous
tal formulas. feeding schedule because it permits more freedom of move-
Once the tube is in place, formula is usually adminis- ment than does 24-h continuous feeding. Intermittent
tered at a slow rate and increased in increments depending feeding may also be preferable in patients with diabetes
on the condition of the patient until the patient's needs are because it simplifies insulin dosing. Most often delivery is
met. Formula can be poured into 500 or 1,000 mL rigid controlled by means of an enteral feeding pump thus en-
containers or bags. To provide the safest environment for suring an even and controlled flow of formula, but it is also
tube-fed patients, formulas are available in commercially possible to infuse by gravity or with the use of a syringe
prefilled containers that decrease the risk of bacterial con- (bolus feeding).
tamination from handling and reduce staff time. The for- Enteral feeding pumps have been improved greatly
mula flows from the container through a feeding set, by since first being introduced. Enteral feeding pumps work
via one of two mechanisms; rotary peristaltic or cassette Water quality in enteral nutritional processing is assured
technology. The rotary peristaltic pump works by looping through use of treated potable water supplies and water
the tubing of the administration set around the pumping quality monitoring programs.
mechanism and pressure against the tubing forces the for- Ingredients are added during the manufacturing pro-
mula out in a constant sequence of motions. The delivery cess at various points dictated by factors such as manu-
is regulated by a drop-counting sensor. The cassette pump facturing convenience and assurance of distribution of the
has a cassette that holds a specific volume of fluid that ingredient into the product. For example, it is most con-
works with a pumping mechanism to discharge precise vol- venient to add carbohydrate sources (eg, maltodextrins) to
umes at a specified rate. The cassette fits easily into place the water phase to assure dispersion. Incorporation of in-
and eliminates the need to loop tubing for proper pump gredients into the product varies from use of direct addi-
operation. Pumps have very sophisticated features and tion to use of pumps such as triblenders.
alarms. There are pumps that automatically flush the
feeding tube at set intervals; this has been proven to re- Liquids
duce tube clogging. Safety features and alarms vary by
The ingredients in the oil and water phases are blended
pump manufacturer; however, basic safety features and
together in a concentrated mixture, heated, and the pH
alarms include memory, free-flow alarm, no flow alarm,
adjusted to stabilize the protein (Fig. 2). This mixture is
and low battery alarm. Additional features may include
subjected to a combination of processes which are similar
select rate alarm, select run alarm, system self-check, lock-
to typical dairy processes: homogenization, pasteurization,
out, and hold.
UHTST (ultrahigh-temperature short-time sterilization),
Enteral feeding pumps are used to control the rate of
HTST (high temperature short time sterilization), de-
feeding delivery and provide increased safety in providing
aeration, and clarification. Heat-labile nutrients and fla-
enteral nutrition support. Controlling the rate of formula
vors are added after these processing steps. Samples are
delivery is imperative in the following patient care situa-
taken for measurement of pH and total solids at this point,
tions: (1) when feeding into the small bowel, (2) when feed-
and the mix is adjusted to final total solids and pH.
ing patients who are fluid restricted (eg, cardiac, renal),
Shelf-stable, liquid enteral products are commercially
(3) when feeding patients intragastrically who have a his-
sterilized using either retort or aseptic processes. In the
tory of gastroesophageal reflux or aspiration, or (4) when
retort process, the final product is filled in either metal,
feeding patients who may have delayed gastric emptying
glass, or plastic containers and sealed, normally under a
secondary to their underlying disease (eg, diabetes). En-
slight vacuum. The filled containers are subjected to rapid
teral feeding pumps can have very positive outcomes as
heating with superheated steam. In most cases, the con-
well as lower overall cost of patient care.
tainers are rotated or shaken to assure even distribution
of heat throughout the product. In the aseptic filling pro-
PROCESSING TECHNOLOGY cess, the product undergoes a UHTST treatment just prior
to filling. The containers and lids are independently
Enteral nutrition can be a patient's sole source of nutrition treated with a sterilant (eg, hydrogen peroxide) to assure
for extended periods. Therefore, high standards of care in sterility. The product is filled in the package in a sterile
the manufacturing process are necessary to assure consis- filling zone in the filler. Aseptic packages include plastic,
tent nutrient content and product sterility. Enteral nutri- glass, aluminum, steel, and fiberboard containers.
tion manufacturers maintain rigid specifications for ingre- In the case of both retort and aseptic sterilization pro-
dient quality, processing conditions, and package integrity. cesses, the manufacturer must establish that the product
The combination of specifications and documentation com- and package receive treatment that is adequate to reduce
prise a thorough quality assurance program to demon- pathogenic microorganisms in the finished product to a
strate the batch-to-batch consistency of the finished prod- nonviable level for the shelf life of the product. Typically,
uct. The specific processing parameters and quality the manufacturer subjects the product and package to test-
assurance programs used in the manufacture of enteral ing protocols to assure sterilization processes are ade-
formulas are proprietary, but are described in general quate. Before commercial release, the product is incubated
terms in this section. at typical storage temperatures to assure that no microbial
contamination occurs postprocess.
Ingredients
Powders
The ingredients for enteral nutritional products are se-
lected following examination of attributes such as nutri- Powdered products are sometimes the preferred form for
tional quality, safety for use, functional properties (eg, vis- certain products or specific settings. For a given volume of
cosity), and processing ease (eg, dispersibility in water). final reconstituted liquid product, powders have less bulk
Following receipt of ingredients at the manufacturing fa- and weigh less than processed liquid products and, there-
cility, a rigid testing, storage, and handling program are fore, are easier and less expensive to store and transport.
used to assure ingredient quality. The testing program in- Powders generally have a longer shelf life than liquid
cludes identity, microbiological and infestation testing, or- forms. Some products are available only as powders be-
ganoleptic testing, and nutritional potency. Storage con- cause certain components cannot be exposed to thermal
ditions are carefully monitored to assure that extremes of processing or are not stable for long periods in aqueous
temperature and moisture do not damage the ingredients. solution.
Protein
Dietary fiber
Fat soluble vitamins Protein Carbohydrate
Lecithin Dietary fiber Minerals
Filling,
sterilization
Two methods of manufacturing are commonly used for ture, or light. The product label, outer carton, and shipping
powdered enteral products: spray-drying and dry-blend- containers are also designed to provide protection to the
ing, either separately or in combination. Spray-dried prod- product and help increase the package's durability. Pack-
uct is UHTST or HTST processed as a concentrated liquid ages are subjected to physical tests to assure that the rig-
prior to the drying step. In the drying step over 95% of the ors of shipping and handling do not adversely affect the
water is removed to bring the powder moisture content to integrity of the package's hermetic seal.
a level that does not promote microbiological growth. Dry-
blending is a process where dry ingredients are mixed in Product Shelf Life
a chamber by rotating ribbons or plows. Dry-blending is
desirable when there is heat- or moisture-sensitive ingre- A minimum of a one year room temperature storage shelf
dients in the product formulation. Occasionally, base pow- life for enteral nutrition products is normally the require-
ders are spray-dried, followed by dry-blending of sensitive ment of institutional health care providers for reasons of
ingredients. convenience and storage. Assurance of the product's nutri-
The process of spray-drying or dry-blending can produce tional and physical quality and the package's durability
a powder that does not disperse easily in liquid. The pro- under normal storage conditions is accomplished by shelf
cess of agglomeration is used to improve powder dispers- life studies prior to product introduction. Ongoing product
ability in liquid by binding small, dense particles together monitoring programs provide assurance that the product
to provide a larger surface area to "wet." and package meet specifications throughout the product's
life cycle.
Packaging
Enteral products are packaged in glass, metal (steel and REGULATORY ACTIVITIES
aluminum), fiberboard, and plastic packages. Packaging
materials are selected for ease and cost of manufacturing, Enteral diets that are formulated simply as adult meal re-
convenience for the customer, and ability to protect the placements are considered to be foods by the U.S. FDA and
product from environmental conditions such as light, mois- are not regulated any differently than standard foods.
ture, and oxygen. Glass and metal containers offer excel- Webster's Dictionary defines food as "material consisting
lent protection from moisture or oxygen. Plastic containers essentially of protein, carbohydrate, and fat used in the
are normally multilayer with one or more of the layers pos- body of an organism to sustain growth, repair, and vital
sessing properties that act as a barrier to oxygen, mois- processes, and to furnish energy; also such food together
with supplementary substances (as minerals, vitamins, ber. Washington, B.C., U.S. Dept. of Health and Human Ser-
and condiments)." Like regular foods, enteral diets are for- vices, 1987, pp. 160-163.
mulated with items that are generally recognized as safe 5. J. E. Spiegel et al., "Safety and Benefits of Fructooligosac-
(GRAS) or items approved as food additives by the FDA. charides as Food Ingredients," Food Technol. 48, 85-89
The FDA has a role in approving or advising food man- (1994).
ufacturers regarding the health messages for conventional 6. A. C. Bach and V. K. Babayan, "Medium-ChainTrigylcerides:
foods. There are two opposing views about the potential An Update," Am. J. Clin. Nutr. 36, 950-962 (1982).
effects of regulating such messages: if health claims are 7. National Research Council, Recommended Dietary Allow-
ances, 10th ed., Washington, D.C., National Academy Press,
not allowed, then the public may not be informed of the
1989.
potential benefit of consuming certain foods. On the other
8. S. Mobarhan and L. S. Trumbore, "Nutritional Problems of
hand, allowing health messages on foods opens the door the Elderly," Clin. Geriatr. Med. 7, 191-214 (1991).
for false or exaggerated claims to be made. Recently, the
9. D. Cuthbertson and W. J. Tilstone, "Metabolism During The
policy of the FDA has been changing toward the allowance Post-Injury Period," Adv. Clin. Chem. 12, 1-55(1969).
of certain health messages. Regulations or food labeling 10. J. W Bane, R. E. McCaa, and C. S. McCaa, "The Pattern of
are detailed in two sections of the Code of Federal Regu- Aldosterone and Cortisone Blood Levels in Thermal Burn
lations (111). Patients," J. Trauma 14, 605-611 (1974).
The development of more specialized enteral formulas 11. G. M. Vaughn et al., "Cortisol and Corticotrophin in Burned
for specific diseases has placed these formulas under in- Patients," J. Trauma 22, 263-273 (1982).
creasingly intense secrutiny by the FDA. In 1988, the or- 12. D. W. Wilmore et al., "Hyperglucanemia After Burns,"Lancet
phan drug amendment created a new category of food 1, 73-75 (1974).
called medical food, which was defined as follows: "The 13. J. M. Shuck et al., "Dynamics of Insulin and Glucagon Se-
term medical food means a food which is formulated to be cretions in Severely Burned Patients," J. Trauma 17, 706-
consumed or administered enterally under the supervision 713 (1977).
of a physician and which is intended for the specific dietary 14. R. R. Wolfe et al., "Glucose Metabolism in Severely Burned
management of a disease or condition for which distinctive Patients," Metabolism 28, 1031-1039 (1979).
nutritional requirements based on recognized scientific 15. D. W. Wilmore et al., "Catecholamines: Mediator of the
principles, are established by medical evaluation" (112). Hypermetabolic Response to Thermal Injury," J. Trauma 15,
Implicit in this definition is the notion that disease condi- 697-703 (1975).
tions can change an individual's nutritional requirements 16. K. N. Frayn, P. F. Maycock, and H. B. Stoner, "The Relation-
or food intake leading to a deficiency or overabundance of ship of Plasma Catecholamines to Acute Metabolic and Hor-
a nutrient. Although the amendment did issue the defini- monal Responses to Injury in Man," Circ. Shock 16, 229-240
(1985).
tion of a medical food under the current federal regulations
that implement the Food, Drug, and Cosmetic Act, there 17. J. M. Daly et al., "Enteral Nutrition With Supplemental Ar-
ginine, RNA, and Omega-3 Fatty Acids in Patients After
is no procedural framework for the evaluation of medical Operation: Immunologic, Metabolic and Clinical Outcome,"
food products. This contrasts with the detailed regulations Surgery 112, 56-67 (1992).
for the development and approval of new drugs and food 18. R. O. Brown et al., "Comparison of Specialized and Standard
additives as well as the regulations for the formulation and Enteral Formulas in Trauma Patients," Pharmacology 14,
manufacture of infant formulas specified in the Infant For- 314-320(1994).
mula Act of 1980 (113). 19. F. A. Moore et al., "Clinical Benefits of an Immune-Enhanc-
ing Diet for Early Postinjury Enteral Feeding," J. Trauma
37, 607-615 (1994).
ACKNOWLEDGMENTS 20. J. M. Daly et al., "Enteral Nutrition During Multimodality
The authors would like to express their appreciation to Pamela Therapy in Upper Gastrointestinal Cancer Patients," Ann.
Anderson, Sheila Campbell, David Cockram, Lisa Craig, Joyce Surg. 221, 327-338 (1995).
Hall, Jeffrey Nelson, and Sean Moore for their invaluable contri- 21. K. A. Kudsk et al., "A Randomized Trial of Isonitrogenous
butions. Enteral Diets After Severe Trauma: An Immune-Enhancing
Diet Reduces Septic Complications," Ann. Surg. 224, 531-
543 (1996).
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113. Infant Formula Act of 1980, Public Law 96-359. timate of cost benefit.
Substrate
(a)
Figure 2. Determining Vmax and KM from experimental data using three different methods: (a)
HYPER computer program: Vmax = 58.55, KM = 17.44, Std. Dev. 1.65; (b) Lineweaver-Burk plot:
ymax = 49.60, KM = 12.85, Std. Dev. 2.54; (c) Hanes plot: Vmax - 58.96, KM = 17.56, Std. Dev.
1.66. Source: Data from Ref. 10.
Figure 3. General equilibrium model for reversible enzyme in- Proteases and Peptidases
hibition. Source: Ref. 1, p. 38.
Substrates. Protein substrates for proteases are most
often hemoglobin or casein and must be completely soluble
in buffer. Casein for protease assays is designated "nach
The measured rate at each point is vt. A plot is made of Hammarsten," while hemoglobin "for protease assay" is
XIvi versus X (Fig. 6b). From the y-axis intercept calculate usually of high quality. Casein precipitates below pH 6, so
the uninhibited rate; that is, I/intercept equals the true it is used at neutral to alkaline pH. Hemoglobin must be
rate due to enzyme concentration [e]. This method is useful denatured before use, either by treatment with acid (if the
for comparing enzyme amounts from different sources, and assay is at acidic pH) (16) or urea (neutral to alkaline pH
during enzyme purification until the inhibitor has been re- assay) (17). Gelatin, sometimes used in viscometric assays,
moved. is quite heterogeneous, so lot-to-lot reproducibility is a con-
cern.
SPECIFIC ENZYME ASSAYS Proteins may be derivatized to fit assay needs. Diazo-
tized protein allows measurement of solubilized peptide
Several assays for enzymes most commonly measured by with a visible-range colorimeter (18). If the amino groups
food scientists will be described. These are only examples freed during hydrolysis are quantitated using, for example,
No inhibitor Noncompetitive
Competitive
Competitive
Noncompetitive
Rate
Mixed
No inhibitor
No Inhibitor
Endogenous
Inhibitor
Rate
with a simple aqueous TCA solution (8). Quantitation may molysin for this substrate, so the reaction is kineti-
be direct (absorbance of filtrate at 275 nm) or colorimetric cally first order. In the cuvette place 1.5 mL sub-
(Folin-Lowry [28], bicinchoninic acid [29], or TNBS [3O]). strate, 1.4 mL buffer, and 0.1 mL enzyme, and
An example of a casein-based assay is the following (8). To measure the decrease in absorbance at 345 nm from
5 mL casein (12 mg/mL in 0.03 M phosphate buffer, pH 0.96 (zero time) toward an infinite-time value of 0.56.
7.5), add 1 mL enzyme solution and after 10 min reaction Plot log(absorbance - 0.56) versus time; the slope di-
add 5 mL of buffered TCA. After 30 min the mixture is vided by 2.303 gives the first-order rate for the re-
filtered and absorbance at 275 nm is measured. For Folin- action, which is directly proportional to the concen-
Lowry quantitation, to 1 mL of nitrate add 1 mL alkaline tration of enzyme. Preferably, a simple Basic
buffer (1M Na2CO3, 0.25 M NaOH), 0.4 mL copper reagent computer program (1) may also be used to calculate
(0.1% CuSO4 5H2O, 0.2% NaK tartrate), mix, and allow the first-order rate constant.
to stand 10 min. Then add 0.75 mL diluted phenol reagent
(Folin-Ciocalteau reagent diluted with 3 volumes H2O), Peptidase Assays. Carboxypeptidase is assayed by in-
mix, wait 10 min, and measure absorbance at 700 nm ver- cubation with an AT-acylated dipeptide, followed by mea-
sus an appropriate reagent blank. A plot of log absorbance surement of the amino group freed (32). Substrate solution
versus log protein is linear over the range 3 to 400 jug of is 1 mM dipeptide (eg, 35.6 mg Z-Phe-Gly per 100 mL) in
protein (eg, bovine serum albumin standard) (31). 0.025 M phosphate buffer, pH 7.2. To 200 juL add 50 juL
An assay using TNBS to measure freed amino groups enzyme, incubate for 1 h, stop by heating in boiling water,
(30) uses 7V,Af-dimethyl casein (20) (1 mg/mL) in buffer as and measure free amino groups by reaction with TNBS as
substrate. To 1 mL in reaction tube, add 0.1 mL enzyme described previously. Carboxypeptidase may also be as-
solution, incubate for the desired time, and heat the tube sayed continuously using Z-Gly-Phe in 0.05 M Tris buffer,
briefly in boiling water to stop the reaction. Add 1 mL 0.4 pH 7.5, following the decrease in absorbance at 224 nm
M phosphate buffer, pH 8.2 (containing 0.25% sodium do- (27).
decyl sulfate), 2 mL freshly made TNBS (1 mg/mL in wa- Aminopeptidase assays usually employ the /?-naphthyl-
ter), and incubate in the dark 1 h at 6O0C. Add 4 mL 0.1 N amide of an amino acid. After incubation the freed /?-
HCl, cool to room temperature, and measure absorbance naphthylamine is quantitated by diazotization (33). Sub-
at 340 nm. The reagent blank contains only buffer and strate stock solution is 2 mM amino acid naphthylamide
TNBS; a complete assay with zero incubation time gives in 0.01 N HCI. Buffer is 0.025 M phosphate, pH 7.2. Color
the correction for free amino groups in substrate and en- reagent is the diazonium salt Fast Garnet GBC (1 mg/mL)
zyme. in IM acetate buffer, pH 4.2, containing 10% (v/v) Tween
The absorbance change during the reaction of synthetic 20. To the assay tube, add 1.6 mL buffer, 0.2 mL substrate,
substrates with enzyme is recorded on a stripchart re- 0.2 mL enzyme, and incubate 3 h. Then add 1 mL color
corder, giving a continuous trace from which the initial ve- reagent, allow 5 min for color development, and read ab-
locity or the first-order reaction rate is obtained. Two as- sorbance at 525 nm.
says will be described as examples.
Carbohydrases
1. TAME a substrate for trypsin (23). The reaction so-
lution is 1.04 mM TAME (0.394 mg/mL) in 0.04 M Substrates. Starch, the substrate for amylases, consists
Tris buffer, pH 8.1, 10 mM in CaCl. To 2.9 mL, add of a linear polymer, amylose, and a highly branched poly-
0.1 mL enzyme solution and record the increase in mer, amylopectin. The ratio of these two components var-
absorbance at 244 nm. ies in starches obtained from different plant sources. They
2. FAGLA is a useful substrate for metalloproteases may be separated by treating a solution of gelatinized
such as thermolysin (26). To 100 mL 0.05 M phos- starch with thymol (34). In certain assays for a-amylase
phate buffer, pH 7.2, add 76.9 mg FAGLA to give a the use of one or the other fraction is preferable. If the
2.5 mM solution. This is well below the KM of ther- assay involves colorimetric quantitation of freed reducing
groups, the blank due to reducing ends of the substrate reagent: in 500 mL water dissolve 10 g NAOH, 10 g 3,5-
chain may be removed by reduction with NABH4 (5). dinitrosalicylic acid, 2 g phenol, 0.5 g Na2SO3, and 200 g
Soluble cellulose substrates for cellulase are the car- NaK tartrate, then make up to 1 L volume.
boxymethyl, hydroxypropyl, or hydroxyethyl derivatives A chromogenic substrate, p-nitrophenyl maltopentaose,
(35). These are available as commercial products but is used to assay this enzyme (41). /?-Amylase removes two
should be characterized before use to ensure comparability maltose units from the substrate, and a-glucosidase in the
between lots. Insoluble complexes of dyes with starch assay mixture then frees the chromogen. The reaction is
(36,37) or cellulose (38) are also available; enzyme activity stopped with alkaline buffer, and absorbance is read at 410
is assayed by measuring the amount of dye that is solubi- nm.
lized during an incubation period.
Small synthetic substrates, usually the p-nitrophenyl- Cellulase Assays. Cellulase activity may be monitored
glycosides, are available for some glycosidases (39). Spe- using the DNS reagent (47). Dissolve 11.4 g CMC (carboxy-
cific oligosaccharide derivatives have been used for assays methylcellulose) in 700 mL water with stirring, then add
of a-amylase and /?-amylase (40,41). 7 g citric acid monohydrate, 19.6 g sodium citrate dihy-
drate, 0.1 g merthiolate, and 0.1 g glucose and make up to
Amylase Assays. For ct-amylase (5), use 1 mL of a 1% 1 L. To 1 mL substrate, add 1 mL enzyme solution, incu-
solution of reduced starch in 0.02 M acetate buffer, bate 20 min at 5O0C, add 3 mL DNS reagent, heat 15 min
pH 4.7, containing 1 mM CaCl2. Add 1 mL enzyme solu- in boiling water, cool, and read absorbance at 540 nm. Cel-
tion, incubate for the time desired, then add 4 mL each of lulase activity may also be assayed by following the de-
Reagent A and Reagent B of the neocuproine system (42). crease in viscosity of a solution of CMC during incubation
Heat in boiling water 12 min, make up to 25 mL, and read with enzyme (48,49). This requires a great deal of care and
absorbance at 450 nm. Reagent A: in 600 mL water, dis- preparation and will not be discussed here.
solve 40 g anhydrous Na2CO3, 1Og glycine, and 0.45 g
CuSO4 5H2O. Make up to 1 L. Reagent B: dissolve 0.12 g Glycosidase. As an example of assays using nitrophenyl
neocuproine (2,9-dimethyl-l,10-phenanthroline-HCl) in glycosides, that for /?-galactosidase is given (50). In the re-
100 mL water. Store in a brown bottle. action tube, combine 50//L 0.1 M citrate buffer, pH 4.3, 50
Amylopectin forms a complex with I2 which absorbs at JLiL 0.4% bovine serum albumin in water, 50 //L 20 mM
570 nm. As it is hydrolyzed by a-amylase the color de- pNP-/?-galactoside in water, and 50 //L enzyme solution.
creases, the basis for a fixed end-point assay frequently After 30 min at 370C, add 2 mL 0.25 M glycine, pH 10, and
used in cereals-related industries (43). A continuous assay read the absorbance at 410 nm.
based on this phenomenon is the following (44). Suspend
1 g soluble starch in 10 mL water, then slowly add this to Xylanase. Interest has been growing recently in the use
50 mL boiling water. Boil gently for 2 min, cool, and make of xylanases in the food and feed industries. Xylans are
up to 100 mL volume. To 2.5 mL buffered iodine solution pentose polymers, present primarily in cell walls of plants
(32 mg I2, 330 mg KI, and 23.4 mg NaCl in 100 mL of 0.01 (an older name for them, based on this origin, is hemicel-
M phosphate buffer, pH 7.0), add 10 //L enzyme followed lulose). Both soluble and insoluble types are found. The
by 10 //L starch. Record the decrease in absorbance at 570 substrate for xylanases is usually derived either from a
nm. This assay was developed for pancreatic a-amylase; cereal grain (rye is the most abundant source) or wood
for cereal a-amylases, the buffer system would be 0.02 M (beech or larch gums). Assays may involve reducing-sugar
acetate, pH 4.7, 1 mM in CaCl2. techniques, viscometry, or chromogenic substrates (51).
a-Amylase is an endo glycosidase, hydrolyzing internal The chromogenic substrates are available in both soluble
bonds in a-1,4 linked glucose polymers (40). A colorimetric and insoluble (cross-linked) versions.
assay using a blocked substrate takes advantage of this Xylanases, like amylases, may have either endo or exo
fact. The substrate is maltoheptaose, with ap-nitrophenyl specificities (similar to a- and ^-amylases). Recently the
group attached to the reducing end and a blocking agent two types have been separated and shown to have different
(45) at the nonreducing end. a-Amylase cleaves this mol- kinds of improving actions in baked foods. Unfortunately,
ecule in the middle. The assay mixture also contains glu- the specific assays that differentiate them have not been
coamylase and a-glucosidase, which combine to hydrolyze published. Using a soluble xylan as substrate, the endo-
the short maltose (or maltotriose) derivative, freeing the xylanase would show a rapid decrease in solution viscosity
chromogen, p-nitrophenol. The reaction is stopped by the with a relatively slow increase in reducing groups, while
addition of Tris buffer at pH 10, and the absorbance due the exo-xylanase would display the opposite behavior.
to ionized p-nitrophenol is read at 410 nm. The comparison of results from a viscometric assay and a
^-Amylase hydrolyzes soluble starch to yield maltose, reducing-sugar assay would readily differentiate the two
which is quantitated by colorimetric reaction with DNS types.
(dinitrosalicylic acid) reagent (46). A 1% soluble starch so-
lution is prepared as already described, except that 10 mL Ester Hydrolases
0.16 M acetate buffer, pH 4.8, is added before adjusting to
100 mL total volume. Mix 0.5 mL substrate with 0.5 mL Lipase. Lipase acts on esters at the interface between
enzyme solution, incubate at 250C for 3 min, then add 1 water and oil (52); the substrate is a liquid vegetable oil
mL DNS reagent (50). Heat in boiling water 5 min, cool, (olive oil, soy oil) purified by percolation over a column of
add 10 mL water, and read absorbance at 540 nm. DNS activated alumina or silica gel. It is emulsified with the
help of vegetable gum or bile salt. The release of fatty acid For cresolase activity, mix 1.5 mL 0.05 M acetate, pH 4.8,
is monitored by addition of base to keep the pH constant 0.4 mL 1 mM p-cresol, 0.1 mL 1 mM 4-methylcatechol and
(continuous titrimetry, or pH stat, method) or by extraction 10 juLi enzyme. Record increase in absorbance at 291 nm.
and colorimetric measurement of the copper soap (53). For The change is due only to oxygenation; oxidation of di-
the latter assay, make substrate emulsion by adding 2 mL phenol to quinone produces no absorbance change at 291
vegetable oil solution (1% in absolute EtOH) to 100 mL nm. For catecholase activity, mix 1.6 mL buffer, 0.4 mL 1
0.025 M Tris buffer, pH 8.8, containing 0.6% sodium de- mM 4-methylcatechol, and 10 juL enzyme, recording the
oxycholate. To 5 mL substrate, add 0.1 mL enzyme, incu- decrease in absorbance at 280 nm.
bate 5 min, add 1 mL 1N HCI and 10 mL isooctane, shake,
and allow phase separation. To 5 mL of the upper (organic Lipoxygenase. Native lipoxygenase requires activation
solvent) layer, add 1 mL copper reagent (5% cupric acetate by hydroperoxydecadienoic acid, the product of its reaction
in water, pH adjusted to 6.1 with pyridine), shake vigor- with linoleic acid and oxygen; there is a lag period in the
ously for 90 s, and allow the phases to separate. Read the reaction if enzyme is simply mixed with a solution of sub-
absorbance at 715 nm of the upper phase. strate (58). The delay is removed by including a small
amount of product in the stock substrate solution (168 mg
Esterase. The best assay for esterase activity is the pH linoleic acid and 14 mg hydroperoxylinoleic acid in 100 mL
stat method. The substrate in water or salt solution is ad- ethanol) (59). For assay, to 2.9 mL 0.2 M borate buffer, pH
justed to the desired pH, enzyme is added, and base is con- 9.0, add 50 juL substrate stock, followed by 50 //L enzyme
tinually added to keep the pH constant. The plot of base solution. Mix and record the increase in absorbance at 235
consumption versus time gives the rate of the reaction. For nm.
a spectrophotometric assay the system is lightly buffered
at the desired pH, an indicator dye is included, and the Ascorbic Acid Oxidase (AAO). A simple spectrophoto-
change in absorption is measured. An assay for pectin metric assay for AAO is based on the loss of absorbance at
methylesterase (54) uses 0.5% citrus pectin in water ad- 265 nm when ascorbate is oxidized to dehydroascorbate
justed to pH 7.5, an indicator/buffer system of 0.01% brom- (60,61). To 2.8 mL buffer (0.025 M citrate, 0.05 M phos-
thymol blue in 3 mM phosphate buffer, pH 7.5, and enzyme phate, pH 5.6), add 100 juL substrate solution (0.05% as-
in the same buffer. To 2 mL of pectin solution, add 0.15 mL corbate, 1% NA2EDTA, neutralized), 50 juL 1% bovine se-
indicator/buffer and 0.83 mL water. Record absorbance at rum albumin solution, and finally 50 //L enzyme solution.
620 nm briefly to establish a baseline, then add 20 juL en- Record the rate of disappearance of absorbance at 265 nm.
zyme and record the rate of absorbance change due to es-
Catalase, Peroxidase. For peroxidase, the reaction mix-
teratic action. The system (without enzyme) is titrated
ture is 0.01 M phosphate, pH 7.0, containing 25 mg/L H2O2
with galacturonic acid to establish the correspondence be-
and 2.5 g/L pyrogallol (62). After adding enzyme, record
tween absorbance change and acid concentration.
the increase at 430 nm due to the formation of purpuro-
gallin. The reaction of catalase with H2O2 is a first-order
Phosphatase. Phosphatase activity is monitored by col- reaction (63). Hydrogen peroxide has a broad absorption
orimetric quantitation of P1 (inorganic phosphate) formed band in the far ultraviolet; molar absorbance is 120 at 200
(55). An example is the assay for acid phosphatase using nm and 30 at 250 nm. To 2 mL assay solution (0.05 M
glucose-6-phosphate (G-6-P) (56). Substrate is 0.2 M ma- phosphate, pH 7.0, containing 2 g/L H2O2), add 1 mL di-
leate buffer, pH 6.7, containing 60 mM G-6-P, 8 mM KF, luted catalase solution and record the ultraviolet absorb-
and 8 mM EDTA. To 1 mL, add 1 mL enzyme extract, in- ance. Plot log absorbance versus time; the slope divided by
cubate 20 min at 370C, and add 1 mL cold 10% TCA to 2.303 equals the first-order rate constant, which is directly
stop. To 1 mL, add 2 mL P1 reagent, hold 20 min at 450C, proportional to the amount of catalase in the assay (or use
and read absorbance at 820 nm. Reagent A: 10% (w/v) a computer program to calculate the rate constant).
ascorbic acid in water. Reagent B: 4.2 g ammonium molyb-
date tetrahydrate in 1 L 1 N H2SO4. P1 reagent: 1 part A Other Enzymes
plus 6 parts B, made fresh daily, and kept in an ice bath
until used. Lysozyme. Hydrolysis of bacterial cell walls by lyso-
zyme causes the cells to lyse; a turbid suspension of cells
will slowly clear. The turbidimetric assay (64) uses a sus-
Oxidases
pension of Micrococcus lysodeikticus (0.5 g/L) in 0.06 M
Polyphenoloxidase. Polyphenoloxidase enzymes (eg, ty- phosphate, pH 6.2. To 1.5 mL, add 0.5 mL 0.3 M NaCl and
rosinase) catalyze two reactions: (1) oxygenation of a 1 mL enzyme, place the cuvette in a colorimeter, and record
phenol to o-diphenol (cresolase) and (2) oxidation of a di- % transmittance (not absorbance) at 540 nm. A plot of %T
phenol to o-quinone (catecholase). Substrates commonly versus time is linear from about 10 to 40%, and the rate
used for assays are p-cresol (4-methylphenol), L-tyrosine %T/min is proportional to enzyme in the range of O to
(4-hydroxy phenylalanine), and p-coumaric acid (4- 10 jug.
hydroxycinnamic acid). The corresponding diphenols are 4-
methylcatechol, L-Dopa, and caffeic acid. Rates are moni- BIBLIOGRAPHY
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53. D. Y. Kwon and J. S. Rhee, "A Simple and Rapid Colorimetric as an apple or orange, depends, to a large extent, on the
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tometric Assay for Plant Pectin Methylesterase," J. Agric. grain, these enzymes begin the process of breaking down
Food Chem. 34, 440-444 (1986). carbohydrate and protein stored in the seed in order to
55. P. S. J. Chen, T. Y. Toribara, and H. Warner, "Microdetermi- provide energy and amino acids necessary for the synthesis
nation of Phosphorus," Anal. Chem. 28, 1756-1758(1956). of new plant parts. While necessary for plant growth, these
56. A. Rossi et al., "Properties of Acid Phosphatase From Scutella enzymes can have quite detrimental effects when flour
of Germinating Maize Seeds," Phytochemistry 20, 1823-1826 from germinated wheat kernels is used in the production
(1981). of foods, particularly in baked goods.
57. M. H. Keyes and F. E. Semersky, "A Quantitative Method for In ripening fruits, analogous enzymes begin a similar
the Determination of the Activities of Mushroom Tyrosinase," process of cellular breakdown that leads to characteristic
Arch. Biochem. Biophys. 148, 256-261 (1972). loss of firmness normally associated with overripe, less de-
58. B. Axelrod, T. M. Cheesbrough, and S. Laakso, "Lipoxygenase sirable produce. The freshness of fruits and vegetables is
from Soybeans," Methods Enzymol. 71, 441-451 (1981). often judged by the color and texture of the produce such
59. M. J. Gibian and R. A. Galaway, "Steady-State Kinetics of as, for example, the bright green color and firm texture of
Lipoxygenase Oxygenation of Unsaturated Fatty Acids," Bio- fresh peas, beans, or peppers. When many products such
chemistry 15, 4209-4214 (1976). as these ripen, their color changes to red, orange, yellow,
60. E. Racker, "Spectrophotometric Measurements of the Meta- brown, or even black. This is due, to a large degree, to
bolic Formation and Degradation of Thiol Esters and Enediol endogenous enzymes, some of which degrade the green
Compounds," Biochim. Biophys. Acta 9, 577-578 (1952). chlorophyll, thus changing the color of the product. Other
61. T. Tono and S. Fujita, "Determination of Ascorbic Acid by enzymes such as lipoxygenase attack triglycerides forming
Spectrophotometric Method Based on Difference Spectra. II. free radicals and hydroperoxides. These free radicals can
Spectrophotometric Determination Based on Difference Spec- also lead to loss of green color due to oxidative degradation
tra of L-Ascorbic Acid in Plant and Animal Foods," Agric. Biol. of chlorophyll and also changes in reds and orange colors
Chem. 46, 2953-2959 (1982).
due to reactions with carotenoid compounds. Oxidative re-
62. B. Chance and A. C. Maehly, "Assay of Catalases and Perox- actions from these compounds can also lead to nutritional
idases," Methods Enzymol. 2, 764-775 (1955).
damage in the food product through detrimental action on
63. R. M. J. Parry, R. C. Chandan, and K. H. Shahani, "A Rapid vitamins as well as some proteins. Other color changes are
and Sensitive Assay of Muramidase," Proc. Soc. Exp. Biol.
also found to result from enzymatic browning reactions in-
Med. 119, 384-386 (1965).
volving polyphenol oxidase (see "Browning Reactions
Color and Flavor") (1).
CLYDE E. STAUFFER Texture is also affected by endogenous enzymes that hy-
Technical Food Consultants drolyze cellular material, most of which is composed of
Cincinnati, Ohio various forms of carbohydrate material. Most commonly
found in plants, these include cellulose, hemicellulose,
starch, pectic material, and lignin. These carbohydrates
ENZYMES IN FOOD PRODUCTION are involved in cell structure of most plants and are re-
sponsible for the firm texture in young, preripe fruits and
The use of enzymes in the formulation and processing of vegetables.
food products is frequently thought of in terms of the ad- Meat color is also influenced by endogenous enzymes
dition of commercially available enzymes from an indus- involved in oxidation-reduction reactions that alter the ox-
trial source, that is, using enzymes as additives from an idation state of several forms of myoglobin as well as the
external or exogenous source. However, it should be rec- amount of available oxygen. Changes in the oxidation state
ognized that virtually all food materials are, or were, living of oxymyoglobin and deoxymyoglobin can lead to produc-
organisms and, as such, may contain a number of enzymes tion of metmyoglobin, which is responsible for the brown
normally utilized in the metabolic pathways of the organ- coloration in meat (1).
BAKED GOODS these hydrolytic enzymes than will low-moisture products
such as crackers. In bread processing, the dough may con-
Although a number of cereal grains may be used in the tain approximately 35 to 40% moisture, and the final
production of baked goods, the primary source for such baked product retains much of that moisture. Since pro-
products is wheat. Wheat is utilized in the production of cessing involves a lengthy proofing period as well as the
baked goods such as breads, cakes, rolls, and pastries. The bake time, the presence of such high levels of water (most
enzymes of greatest interest for this discussion will be with a water activity [aw] of 0.95-0.98) may lead to exten-
those involved in protein and carbohydrate metabolism, sive hydrolysis if significant levels of endogenous enzymes
specifically, the amylases, pentosanases, and proteases. are present.
Amylases are starch-degrading enzymes that act on the In the dough stage, only that portion of the starch (both
linkages between the glucose monomers making up the amylose and amylopectin) that is physically damaged in
starch polymer. In starch, these linkages are either a-1,4 the milling process is susceptible to amylolytic attack. De-
or a-1,6 glucosidic bonds connecting adjacent glucose res- pending on the type of wheat, the amount of starch damage
idues. /?-Amylase (EC 3.22.1.2) is an exo-type hydrolase may vary from about 3 to 8%. The amylase enzymes can
that is able to hydrolyze only the penultimate a-1,4 bond, attack the damaged starch and will release some water
each cleavage producing a molecule of maltose. a-Amylase that was associated with the starch; however, the effect on
(EC 3.2.1.1) is an endo-type hydrolase that, while specific the dough consistency will be relatively minor. However,
for the a-1,4 glucosidic bond, is capable of hydrolyzing such the starch will gelatinize during the baking process as the
bonds anywhere along the internal portion of the glucose internal temperature of the loaf reaches about 60 to 650C
chain, producing small amounts of glucose as well as many (1040F). Both amylase enzymes may then rapidly degrade
different glucose oligomers. The difference between the the gelatinized starch. However, it should be noted that
two enzymes is important because they have different ef- endogenous amylase enzymes are relatively unstable
fects on the rheology of a starch system. /?-Amylase has above 650C, and so are less effective as the temperature
relatively little effect on the molecular weight of the starch increases. The overall effect of the starch-degrading en-
molecule because it removes only one maltose at a time zymes will depend on the amount of endogenous enzyme
from starch molecules having molecular weights as large present and how long it has to act on the gelatinized starch.
as several million. a-Amylase, however, can drastically al- It was thought for many years that a-amylase was the
ter the molecular weight because it can hydrolyze any- enzyme from sprouted wheat that was most responsible for
where along the chain. That is, it can hydrolyze an internal the detrimental effects observed during baking of high-
a-1,4 glucosidic bond about in the middle of the glucose moisture bread products, but this is not the case. The most
chain and immediately reduce the molecular weight by damaging of the hydrolytic enzymes in such a process are
half. This action can greatly affect (decrease) the viscosity the proteases. Sprouted wheat contains proteolytic en-
of the starch system. zymes that can act on the protein fraction throughout the
Under ideal harvest conditions, wheat is in a dormant dough stage and into the baking stage. The result of ex-
storage stage and contains comparatively few active en- cessive hydrolysis by proteolytic enzymes is a loss of gluten
zymes. There may be significant amounts of /?-amylase, but structure. This is manifest as a slack dough that has lost
a-amylase levels are quite low. Thus, the amount of poten- the viscoelasticity characteristic of a well-developed wheat
tially detrimental endogenous starch-degrading enzyme in flour dough. The finished product will have poor volume
the sound wheat kernel is low. However, it is not unusual, and texture characteristics. If hydrolysis proceeds to an
particularly in the Pacific Northwest, that harvest condi- extreme, all gluten structure may be lost, resulting in a
tions are not ideal. The most serious consequence from the very sticky, slack semiliquid. Some effects of these enzymes
standpoint of enzyme content is when harvest is preceded may be observed even when the degree of sprouting is rela-
by humid, rainy conditions. In this environment, the seed tively low. An assay for this type of enzyme would serve as
breaks its dormancy and begins to grow. This phenomenon a good diagnostic indicator of the quality of the flour used
is commonly referred to as "sprouting" in the grain indus- in an industrial food process.
try. This growth requires that the stored carbohydrate and In low-moisture baked products such as crackers where
protein be utilized for energy and synthesis of new plant the final moisture content of the product is only about 3%,
parts. Thus, enzymes such as those which hydrolyze car- endogenous enzymes usually have less potential for det-
bohydrate and protein material are synthesized and act on rimental effects. Because the processing conditions require
the stored material in the plant seed. It is the plant seed less time compared with breads, and water bakeout in the
that is then processed into a food material such as wheat oven during baking is more rapid, starch-degrading en-
flour. zymes usually have relatively little effect. The rapid loss
Whether the endogenous enzymes are a factor in util- of water in the initial stage of baking leads to more rapid
izing the food material depends on a number of factors. increases in the temperature of the dough piece, thus tend-
First, how extensive was the sprouting? It may range from ing to inactivate the enzymes faster. In addition, because
slight, in which case little enzyme was synthesized, to ex- the available water is driven off rapidly, the starch gelat-
tensive, in which case a large amount of carbohydrase and inization temperature increases such that relatively little
proteinase enzymes have probably been formed. Second, starch is gelatinized in most cracker products. Thus, the
what are the processing conditions for the manufacture of amylolytic enzymes have much less of an opportunity to
the food material? In general, high-moisture products such hydrolyze the starch in its most susceptible condition. Pro-
as breads will be much more susceptible to the action of teolytic enzymes may have an effect even in low-moisture
products, but this will depend on proof time (long or short), clude starch, cellulose, hemicellulose, pectins, and lignins.
since they will normally be rapidly inactivated in the bak- Several endogenous pectin-degrading enzymes contribute
ing process. to the softening of many fruits and vegetables. Pectin
Unsprouted wheat flour also contains endogenous pro- methylesterase (EC 3.1.1.11) hydrolyzes the methyl ester
tease enzyme(s). These enzymes are activated only at rela- from the methylated galactose units of pectin to form pectic
tively low pH (<4.0) and so are not normally active in most acid and methanol. In the presence of sufficient calcium
baked product processes. However, processing of fer- ion (Ca +2 ) a complex is formed that can actually lead to an
mented products such as soda crackers utilize long periods increase in firming of the plant tissue. However, this re-
during which lactobacilli-based fermentation leads to low action can also lead to some problems in the fruit juice
pH in the sponge stage. These low-pH endogenous prote- industry (see "Fruit juices"). Another enzyme, polygalac-
ases can be an important processing factor under these turanase, splits the a-1,4 glycosidic bond between adjacent
conditions, softening the dough and helping to "mellow" galacturonosyl units. There are actually several forms of
the final cracker dough-handling characteristics. Many this enzyme, an endo-acting form (EC 3.2.1.15) and two
chemically leavened cracker doughs have relatively basic exo-acting forms, EC 3.2.1.67 and EC 3.2.1.82 (2), which
pH values, so the endogenous low-pH proteases will not be release D-galacturonic acid. These enzymes lead to exten-
activated. sive degradation of the substrate carbohydrate, leading to
Lipoxygenase enzymes in cereals, especially soybeans significant loss of structural integrity and a concomitant
and wheat, may have significant consequences, both good loss of firmness in the product. There is also a pectate lyase
and adverse. The desirable effect is that of bleaching the (EC 4.2.2.10) found, so far, only in microorganisms, which
carotenoid pigments, resulting in whiter products made also splits the galacturonosyl chain at the a-1,4 glycosidic
from the flour. This is a desirable attribute in products linkage leading to a loss of structural integrity. Although
such as white bread and rolls. The amount of the lipoxy- not strictly an enzyme endogenous to the plant, the micro-
genase enzymes is greater in soy compared with wheat; organisms containing the enzyme may often be found to be
thus, wheat flour may be supplemented with soy flour to present, thereby affecting the processing conditions in the
achieve the bleaching effect. The downside to this activity absence of added commercial enzymes.
is that too much lipoxygenase activity may lead to oxida- Another common plant cell wall constituent is cellulose.
tion of native flour lipids, producing an undesirable rancid Cellulases (EC 3.2.1.4) are found in many plants, primarily
flavor/aroma characteristic. The type I lipoxygenase en- in trees, but also in fruits and vegetables. This enzyme acts
zyme acts only on free fatty acids while type II lipoxygen- on the /M ,4 glucosidic bonds found in cellulose. Though
ase can act on triglycerides as well. cellulose is closely related to starch in being a polymer of
The pentosan fraction of the flour is an important func- glucose monomers, amylase enzymes cannot hydrolyze cel-
tional participant in the formation of the dough. Though lulose, and cellulases have no effect on starch. This is due
normally only about 2 to 3% of the flour, it is capable of to the different geometry of the /?-l,4 bond in cellulose as
absorbing up to 25% of the moisture in the dough. Hydro- compared with the a-1,4 bond found in starch. The loss of
lysis of the pentosan fraction would have a significant ef- firmness attributable to the enzyme found in fruits and
fect on dough viscosity. However, at present, while pento- vegetables is still unconfirmed, but cellulases of microbial
sanase activity has been detected in germinated wheat, the origin, often found with the plant, are known to be effective
levels appear to be quite low and of relatively little prac- at hydrolyzing plant cellulose.
tical significance in terms of processing effects. Exogenous Pentosans, sometimes referred to as hemicellulose, are
pentosanases, available commercially, may be used to polymers of xylose, arabinose, or both. Generally the ma-
greatly alter dough viscosity by destroying the water- terial is an arabinoxylan with /M ,4 linkages between the
holding capacity of the pentosan network. backbone xylose units. These polymers are commonly
Flour may also be used in nonbaking applications. For found in higher plants and are particularly important in
example, flour is often added to soup as a thickening agent. cereal products because the pentosan polymer is capable
Endogenous enzymes, which may be present in that flour, of absorbing very large amounts of water, thus affecting
are normally inactivated during the retorting step in the formulations. There seems to be relatively little endoge-
manufacture of the soup. If the flour is sound (unsprouted) nous pentosanase enzyme active in cereals.
containing relatively low levels of hydrolytic enzymes, the
enzymes have little effect prior to retorting, and the de-
BEVERAGES
sired thickening effect is maintained in the canned soup
for long periods. However, if a sprouted wheat flour is used
Alcoholic
in this application, the endogenous enzymes can, prior to
retorting, hydrolyze both starch and protein components, Beer is a virtually universal libation of quite ancient ori-
producing a thin, watery soup consistency. gin. The methods used today are cleaner and more effi-
cient, but the fundamental approach remains similar to
that developed thousands of years ago. By accident or de-
FRESH FRUITS AND VEGETABLES sign, brewing beer represents one of the first systematic
uses of enzyme technology in the production of a food prod-
As mentioned in the "General" section, most plants contain uct.
various forms of carbohydrate, either as part of their cel- The basic goal of brewing is to convert carbohydrate to
lular structure or as components of their "flesh." These in- alcohol and protein to peptides and amino acids. Most of-
ten, the source of these substrates is the seed of the barley marily cellulose, hemicellulose, and pectic material. These
plant, though other seeds are also used. In many areas of compounds tend to cause a number of production prob-
Africa, for example, grain sorghum seed is utilized in the lems, most of which are addressed by the addition of ex-
brewing process. As described for wheat kernels, these ogenous enzymes. This is the usual approach because most
seeds also store energy as starch and amino acids as pro- fruits intended for human consumption are harvested
teins. The first step in the brewing process involves "malt- prior to achieving biological ripeness in order to maintain
ing" of the barley seed. This is a process of controlled ger- the characteristics (color and firmness) desired by the con-
mination resulting in the synthesis of hydrolytic enzymes. sumer. The native enzymes, which would be expressed
The barley kernels are steeped in water under controlled with advanced ripening, are not available. Thus, the prob-
temperature to a moisture content of about 45% and then lems of clouding and poor filtration associated with the
allowed to germinate, usually on large floor areas where presence of pectic material and cellulose and hemicellu-
good aeration is maintained by turning and mixing the losic compounds are normally treated with microbially de-
grain. After a suitable period at controlled temperature rived enzymes added as processing aids.
(about 15-2O0C) the germinated grain is dried at 35 to One interesting problem, normally characteristic of or-
4O0C for about 12 hours and subsequently ground to a ange juice, is the loss of cloud stability in the juice. Orange
course powder (3). This material then contains much in- juice is normally produced by pressing the juice from the
creased levels of hydrolytic enzymes, primarily amylase fruit. Rather than being clear, the juice is meant to be an
and protease activity, which are essential to the brewing opaque liquid. The insoluble material that accompanies
process. the juice as the fruit is pressed contributes desirable color,
As described previously in the baking section, the am- opaqueness, and flavor characteristics. Loss of this cloud-
ylase enzymes (both alpha and beta) hydrolyze starch- iness is associated with the action of an endogenous en-
producing sugars (maltose and glucose) and some oligosac- zyme, a pectin methylesterase (EC 3.1.1.11), which de-
charides. With the addition of yeast (normally a strain of esterifles the pectin to pectic acid. The ionized pectic acid
Saccharomyces) in a process known as "pitching," the glu- is then able to form a complex with normally present cal-
cose is converted to alcohol and CO2 according to the well- cium ions (Ca+2), which results in a gel-like complex. This
known equation: complex will precipitate over time as an undesirable layer
of sediment leaving a clarified juice above it. There are
C6H12O6 - 2CO2 + 2CH3CH2OH several approaches to preventing this troublesome condi-
tion. One involves the heating of the juice to a temperature
Yeast utilizes a maltase enzyme to convert the maltose to sufficient to inactivate the offending pectin methylester-
glucose. Thus, this step in the brewing process is facili- ase. This approach, however, has a deleterious effect on the
tated through the action of endogenous enzymes from both flavor components of the juice and thus represents an ap-
the barley seed as well as a series of enzymatic steps util- proach of last resort. A more common and less detrimental
izing enzymes endogenous to the yeast. solution is the addition of an exogenous polygalacturonase
The same basic process of converting carbohydrate to (EC 3.2.1.15), which depolymerizes the pectic acid prior to
alcohol is utilized in the production of distilled spirits. significant formation of the calcium complex (2).
Such products have an ethanol content of about 20% and Although the formation of this calcium-pectic acid com-
higher (beer having about 3-6% and wine having about plex presents problems for the orange juice industry, it can
10-15% alcohol). While the variety of such alcoholic bev- be used to advantage in other circumstances. For example,
erages is quite large, those derived from cereals will be the many vegetables tend to lose their firmness after harvest,
focus of this discussion. Many different cereal grains, in- particularly after canning. The addition of calcium chloride
cluding wheat, rye, barley, corn, and others, are used in to canned tomatoes results in firming of the fruit. The firm-
the production of alcohol spirits. The source grains are ing has been attributed to the formation of the calcium-
ground, mixed with water, and heated to affect the gelat- pectic acid complex. This phenomenon has been used to
inization of the starch. The conversion of the starch to achieve desirable firming in many vegetables as well, in-
sugar is then accomplished by the addition of a malt con- cluding potatoes, peppers, and beans.
taining high levels of saccharifying enzymes (a- and /?-
amylase). The "mash" is mixed and stirred under con-
DAIRY FOODS
trolled conditions producing high levels of fermentable
maltose and glucose. The mash is heated to inactivate the
enzymes, cooled and fermented. This mixture is then dis- Cheeses are derived from the milk of cows, goats, and other
tilled to produce the elevated alcohol content characteristic ruminant animals. The textural characteristics of cheeses
of such beverages. Again it is the use of the endogenous are determined, to a large extent, by the methods of curd
malt enzymes that are central to the production of these manufacturing, but the flavors and aromas of cheeses are
products. developed primarily in the ripening process. Cheese rip-
ening is an enzymatic process involving enzymes endoge-
Fruit Juices
nous to the milk, to the ruminants from which the milk is
taken, and to microorganisms that are an essential part of
Fruit juices are another category of beverage in which en- the cheese-making process.
dogenous enzymes may play a role in the production pro- Milk protein is composed primarily from a set of pro-
cess. Unlike cereals, the polysaccharides of fruits are pri- teins collectively called casein. These proteins form an as-
sociation in milk to form micelles that remain suspended. ficult to assess otherwise. The following are several ex-
These suspended micelles, along with fat globules and cal- amples of the use of endogenous enzymes as indicators
cium phosphate, give milk its characteristic opaque white of the effectiveness of a processing step, often involving
color. The first step in making cheese is the formation of a heat treatments to inactivate organisms or enzyme ac-
curd. Usually, the curd results from treatment of whole tivity.
milk with acid or with enzyme to precipitate the casein
fractions. Traditionally, this curd formation was accom-
plished using rennin (EC 3.4.23.4), an enzyme from the Pasteurization of Milk
stomach of ruminants. The enzyme has a restricted spec- The purpose of pasteurization is to destroy potentially
ificity such that the hydrolysis proceeds to the extent nec- harmful microorganisms in the milk through a process of
essary to precipitate the milk protein without causing ex- rapid heating to about 850C for a very short time (several
tensive further protein hydrolysis. A commercially seconds). It is sometimes difficult to determine whether
available substitute for rennin derived from microorgan- the processing has effectively eliminated the targeted mi-
isms is called rennet. Other commercially available pro- croorganisms. One way to assess the effectiveness of the
teases may be used, but many cause too much hydrolysis, treatment is to test the viability of the organisms. This,
resulting in the formation of "bitter peptides" that contrib- however, is a lengthy process not well suited for remedial
ute undesirable flavor characteristics. Protease treatment heating. It happens that endogenous milk alkaline phos-
accomplishes the concentration of the milk protein into a phatase (EC 3.1.3.1) is heat inactivated in a temperature
dense curd, but it also initiates reactions that contribute range similar to that required to destroy the potentially
to flavor development. This flavor development is en- harmful organisms. Thus, a simple colorimetric test (5) for
hanced by protease enzymes from the milk itself, primarily alkaline phosphatase can quickly indicate whether the
plasmin (EC 3.4.21.7), as well as enzymes endogenous to temperature of the milk has been raised sufficiently to in-
microorganisms used in the cheese process. These micro- activate the enzyme and, by inference, the microorgan-
organisms may be bacterial and/or fungal depending on isms.
the specific cheese.
A number of processes occur during ripening, all en-
zyme mediated, which contribute to textural and flavor Blanching of Vegetables
characteristics. They can be described by three categories
of enzymatic activity. A more detailed description of each Vegetables are often placed in boiling water to inactivate
of these stages may be found in Reference 4. First, proba- certain hydrolytic enzymes that would otherwise cause
bly the most important enzymatic process involves prote- detrimental effects in terms of flavor and/or texture. Al-
olysis of the milk protein by rennin, plasmin, and micro- though certainly less a problem in the home, the proper
organism-derived enzymes. Proteolysis results in the degree of heating required to inactivate these enzymes,
formation of peptides, amino acids, thiols, and other com- while not adversely affecting texture is critical to indus-
pounds, all of which contribute significantly to the flavor tries involved in the longer-term storage of such products
of the cheese. in cans or bottles. Inadequate blanching in this case can
A second lipolytic enzymatic process also contributes to result in seriously degraded product by the time the con-
the essence of cheeses. Although some lipolysis may lead sumer opens the container for consumption of the product.
to a perceived rancidity in some cheeses, the free fatty ac- Thus, it is important to know when a sufficient amount of
ids released by lipase (EC 3.1.1.3) activity do influence fla- heating has been achieved. A convenient way to assess the
vor positively as well. For the most part, the lipases in- blanching process is to look at the activity of endogenous
volved are endogenous to microorganisms, although there peroxidase (EC 1.11.1.7). While complete inactivation of
is some evidence for participation of milk lipases as well. peroxidase is not desirable, the proper degree of blanching
Esterases (EC 3.1.1.1) are also thought to contribute to the is achieved when about 5 to 10% of the peroxidase activity
process by hydrolyzing mono- and diglycerides to ester remains. The assay method usually utilized for this test
compounds that are known to provide various flavor and involves the use of gulacol and is based on the colorimetric
aroma attributes. determination of the enzymatic product tetragulacol (6).
A third process involves glycolysis, in which the lactose This methodology has been used to assess the degree of
in milk is enzymatically converted to lactic and other acids blanching in products such as peas, corn, beans, and other
through microorganism metabolism. The acids contribute vegetables.
significantly to the character of the cheese. In modern
cheese making, these enzymatic reactions are accelerated Oat Rancidity
by the addition of exogenous esterases and lipases to pro-
duce stronger flavors in a shorter period of time while pro- Oats contain lipolytic enzymes, the action of which can
viding addition control over the process. lead rapidly to rancidity. In this case, as discussed for vege-
tables, heat inactivation of those lipolytic enzymes is often
used to extend the shelf life of oats and products formu-
ENDOGENOUS ENZYMES AS PROCESSING INDICATORS lated with oats. Since the assay of the lipolytic enzymes is
problematic, endogenous oat peroxidase activity serves as
Enzymes present in food materials may be used as di- a more convenient indicator of sufficient thermal inacti-
agnostic indicators of processing steps that would be dif- vation of the lipolytic enzymes.
Soybean Treatment Other Flavor Reactions
Soybeans are very high in protein and are therefore used Members of the plant genus Allium, which includes on-
to supplement other foodstuffs that are lower in protein ions, shallots, garlic, and leeks, have strong, often irritat-
quantity as well as quality. However, soybean meal is usu- ing redolence that is the result of endogenous enzymatic
ally heated to alter the bitter flavor and to inactivate some activity. The characteristic odor of these plants is gener-
antinutritional components such as trypsin inhibitors as ally unnoticeable in the whole, undamaged bulb because
well as lipoxygenase activity. Applying too much or too lit- the enzyme involved, allinase, is compartmentalized and
tle heat in this process can produce undesirable effects. unable to catalyze the odor-causing reaction. When tissue
The endogenous urease enzyme (EC 3.5.1.5) is used as a damage occurs, such as slicing the onion or garlic bulb,
convenient assay (7) to indicate the correct degree of ther- the enzyme is released and proceeds to react, producing
mal treatment. the thiol compounds responsible for the offending (to
some) aroma. For more detailed discussion of similar re-
actions in related food materials, the reader is referred to
BROWNING REACTIONSCOLOR AND FLAVOR Reference 8.
Maillard Browning
BIBLIOGRAPHY
Several types of chemical reactions can affect color and fla-
vor in food products. The Maillard reaction is a nonenzy- 1. J. R. Whitaker, "Enzymes," in O. R. Fenema, ed., Food Chem-
matic reaction between a sugar and an amino function, istry, 3rd ed., Marcel Dekker, New York, 1996, pp. 431-530.
often one on an amino acid. Although the reaction itself 2. W. Pilnik and G. J. Voragen, "The Significance of Endogenous
can proceed without the participation of an enzyme, the and Exogenous Pectic Enzymes. In Fruit and Vegetable Pro-
reaction is influenced by the concentration of the reactants, cessing," in P. F. Fox, ed., Food Enzymology, Vol. 1. Elsevier
which in turn may be influenced by the presence of exo- Applied Science, London, United Kingdom, pp. 303-333.
proteases and exo-amylases. Thus, endogenous enzymes 3. T. Godfrey, "Brewing," in T. Godfrey and J. Reichelt, eds., In-
such as /?-amylase, a carboxypeptidase, or a leucineami- dustrial EnzymologyThe Application of Enzymes in Industry,
nopeptidase can contribute to Maillard browning in food The Nature Press, New York, 1983, pp. 221-259.
products, baked goods in particular. These reactions lead 4. P F. Fox and J. Law, "Enzymology of Cheese Ripening," Food
to significant color formation (evidenced by the color of the Biotechnol. 5, 239-262 (1991).
crust on a loaf of bread) as well as many flavor character- 5. D. A. Schiemann and M. H. Brodsky, "Studies of Scharer's
istics. Original Method for Alkaline Phosphatase in Milk With a Mod-
ification Utilizing an Organic Buffer," J. Milk Food Technol. 39,
191-195 (1976).
Enzymatic Browning
6. P. Varoquaux et al., "Automatic Measurement of Heat Destruc-
Another source of color in foods comes from a reaction usu- tion and Regeneration of Peroxide," (in French) Lebensm. Wiss.
ally referred to as enzymatic browning. This reaction is Technol. 8, 60-63 (1975).
mediated by polyphenol oxidase (EC 1.10.3.1). This en- 7. K. Brocklehurst, "Electrochemical Assays: The pH-Stat," in R.
zyme is able to interact with a large number of phenolic Eisenthal and M. J. Danson, eds. Enzyme Assays: A Practical
compounds and thus had been referred to by several names Approach, Oxford University Press, Oxford, U.K., 1992, pp.
including tyrosinase, catecholase, polyphenolase, and cre- 191-216.
solase. The basic oxidation reaction normally results in the 8. R. C. Lindsay, "Flavors," in O. R. Fenema, ed., Food Chemistry,
formation of an unstable quinone, which then proceeds 3rd ed., Marcel Dekker, New York, 1996, pp. 723-765.
through a number of steps to form melanins. Melanins are
brown to black in color and are responsible for undesirable
spots on many fruits and vegetables such as bananas, ap- GENERAL REFERENCES
ples, mushrooms, and potatoes. Because of the widespread
presence of polyphenol oxidase and the damage it causes H.-D. Belitz and W. Grosch, Food Chemistry, Springer-Verlag,
in many food products, numerous methods have been de- New York, 1987.
veloped to try to prevent this reaction from occurring. S. Schwimmer, Sourcebook of Food Enzymology, AVI Publishing,
Clearly, eliminating as much oxygen as possible will help. Westport, Conn., 1981.
In addition, reducing agents such as ascorbic acid, sodium C. Zapsalis and R. A. Beck, Food Chemistry and Nutritional Bio-
sulfite, and thioi compounds can also help by reacting with chemistry, John Wiley & Sons, New York, 1985.
the quinone compound. These reactions do not, however,
inactivate the enzyme itself, so when the oxidizing agents PAUL R. MATHEWSON
are depleted, the browning reaction may still proceed. Un- Food Technology Resource Group
der the proper conditions, ascorbic acid can inactivate Park City, Utah
polyphenol oxidase reacting with an active-site histidine
residue. Likewise, thiol compounds can also affect the en-
zyme activity by chelating the required metal cofactor
(Cu + + )(l). See also ENZYMOLOGY.
ENZYMOLOGY
Ymax = Km In ^- + [(S) - (S1)]
V^f/
Enzymes can be denned as proteins with very specific
powers of catalysis. The enhancement in reaction rate is where S and St are the substrate concentrations at zero
very high and may be as much as 1014-fold in some in- time and time t, respectively. This equation is particularly
stances. Although all enzymes are proteins, some require useful in industrial situations where a reaction is allowed
an additional small molecule, called a coenzyme or cofactor to proceed to near completion or equilibrium.
(cofactors can be metal ions or small organic molecules), to
function. The role of enzymes in cells means that growth,
maturation, storage, processing, and consumption- APPLICATIONS IN FOOD PROCESSING
digestion of food all depend on various enzyme activities.
In plants, enzymes are responsible for changes associated a-Amylase (EC 3.2.1.1) catalyzes random hydrolysis of a
with ripening, including alterations in color, flavor, and 1-4 linkages in amylose and amylopectin to form straight-
texture. Enzymatic changes continue after harvesting of and branched-chain dextrins, oligosaccharides, and mono-
plants and also after the death of animals, for example, in saccharides. Bacteria a-amylase is used to partially hydro-
the conversion of muscle to meat. These changes affect sub- lyze or "thin" gelatinized starch, often prior to further
sequent food quality. In many cases the action of endoge- degradation to glucose syrups. The enzyme from Bacillus
nous enzymes is arrested or controlled by processing and spp. is very thermostable and is used at 85 to 1050C. The
storage. enzyme can also be used to hydrolyze starch in sugar cane
Enzymes are also widely used to provide desirable juice and in the brewing mash.
changes in food quality attributes through changes in the Fungal a-amylases, derived from Aspergillus niger and
chemical structure of food components. Enzymes have sig- A. oryzae are much less heat stable. They produce large
nificant advantages over chemical catalysts, of which the amounts of maltose and maltotriose and some glucose.
most important are specificity and the ability to work at Their principal applications are production of maltose syr-
moderate temperatures. As a consequence, side reactions ups used in jam and confectionery, as brewing aids to im-
are minimized, and undesirable changes caused by harsh prove fermentability of the mash and in removal of starch
conditions are averted. Enzymes have traditionally been haze in beer, and in supplementation of endogenous OL-
obtained from their natural sources: animals, plants, and amylase in bread flour to enhance the rate of fermentation
microorganisms. Advances in molecular biology have led by yeast and reduce dough viscosity, thereby improving
to the cloning and expression of enzymes from many loaf volume. Fungal a-amylase has largely replaced malt
sources into microorganisms (primarily yeasts and fungi) a-amylase previously used in these applications.
that are efficient producers and regarded as safe hosts. The fl-Amylase (EC 3.2.1.2) splits off ^-maltose from the non-
value of enzymes used in food processing is already several reducing ends of starch molecules. In the case of amylo-
hundred million dollars per annum and will likely expand pectin, this produces /Mimit dextrins since the enzyme can-
as new applications are discovered or improved enzymes not bypass the /?-l-6 branch points. Complete hydrolysis of
become available, for example, by genetic engineering to liquified starch produces about 80% maltose and 20% dex-
improve operating characteristics such as the pH-activity trins. Unlike fungal a-amylase, /?-amylase does not pro-
profile or thermostability. duce maltotriose. The enzyme is produced from cereal or
microbial sources and is used for production of maltose
KINETICS syrup from starch, and in both brewing and baking to pro-
duce maltose for fermentation by yeast to CO2 and to al-
The activity of an enzyme is determined by many factors, cohol.
including enzyme, substrate, and cofactor concentrations; Amyloglucosidase (glucoamylase) (EC 3.2.1.3) is an exo-
ionic strength; pH; and temperature. For conversion of amylase that catalyzes the stepwise hydrolysis of a 1-4
substrate (S) to product (P) by an enzyme (E) the reaction linkages in starch, thereby releasing glucose molecules
scheme can be simply represented as from the nonreducing end. It is used mainly to produce
glucose syrups from liquified starch previously treated
ks &cat
E + S^ES^E + P with a-amylase. Since the a 1-6 linkages in amylopectin
are also slowly hydrolyzed, the final conversion to glucose
where ES is the enzyme-substrate complex, Ks is the dis- reaches 95 to 97% w/w with the remainder being mostly
sociation constant, and Kcat is the turnover number/rate maltose and higher saccharides. The glucose produced is
constant for the breakdown of ES. usually used as a syrup, crystallized out, or converted to
The initial reaction velocity (V) is then given by the fructose by glucose isomerase. The enzyme can also be
Michaelis-Menton equation used to hydrolyze residual oligosaccharides in high-
fructose corn syrup and in the analysis of the starch con-
= kcai(E)(S) tent of foods. Glucoamylase is produced commercially from
K^ + (S) Aspergillus or Rhizopus spp. It is typically used to process
liquified starch at 6O0C. Immobilization of the enzyme has
where Km is the substrate concentration at which V equals been widely studied to provide the benefits of a continuous
one-half the maximum velocity (Vmay)- Integration of the process. However, the soluble enzyme is relatively cheap
equation with respect to time gives so it continues to be used mostly in that form.
Catalase (EC 1.11.1.6) specifically catalyzes the decom- glucose oxidase. Commercial preparations are derived
position of hydrogen peroxide to water and oxygen. In the from A. niger or Penicillum spp. Its main uses are to re-
dairy industry, a low concentration of H2O2 (up to 0.05% move glucose from foods and as an antioxidant to prevent
w/w) is used to "cold pasteurize" milk destined for cheese changes in color and flavor, particularly during food stor-
making, and to preserve milk and whey in some instances age. It is used for removal of glucose from egg whites and
where refrigeration is not practical. The H2O2 is then de- whole eggs. Significant browning and off-flavor develop-
stroyed by catalase. Commercial sources include beef liver ment due to Maillard reactions occurs if eggs are not de-
and A. niger. The enzyme is frequently used in conjunction sugared prior to drying. Other applications include re-
with glucose oxidase (see later) to remove H2O2 produced moval of either dissolved or headspace oxygen from citrus
by that enzyme. drinks, canned soft drinks, beer, and wine, thereby pre-
Cellulase (EC 3.2.1.4) is the name given to a complex of venting oxidative deterioration, and as an antioxidant in
several enzymes that, acting together, hydrolyze cellulose mayonnaise and production of gluconic acid. It is often the
into /?-dextrins and glucose. The native structure of cellu- method of choice for assay of glucose since it is highly spe-
lose is a major impediment to enzyme action, so pretreat- cific and sensitive.
ment by milling, or with alkali or steam, is often necessary Invertase (/?-fructofuranosidase, EC 3.2.1.6) hydrolyzes
to make the substrate accessible. The fungus Trichoderma sucrose into an equimolar mixture of glucose and fructose.
reesie is a good source of cellulase. It contains (1) endocel- Although the same result can be achieved by acid hydro-
lulases that randomly split internal ft 1-4 linkages to pro- lysis, the syrup produced by enzyme action is more pure
duce dextrins and cellobiose, (2) exocellulases that act from and free from discoloration. Invert sugar syrup has several
the nonreducing end of the polymer to produce cellobiose, advantages over sucrose syrup: it is slightly sweeter, it
and (3) cellobiase (or /?-glucosidase) that converts cellobiose does not crystallize at higher concentrations, and the
to glucose. The latter is especially important since it re- sweetness intensity is stable in acidic foods. Until the ad-
lieves end-product inhibition of the other enzymes by cel- vent of high-fructose corn syrup, it was used extensively to
lobiose. Cellulase is used primarily to turn cellulosic replace sucrose in jams and confectionery.
wastes into glucose that can be fermented to ethanol. It is Other applications of invertase include its use in the
also used on a small scale to degrade cellulose in foodstuffs. production of liquid or soft centers in chocolate-coated su-
ft-Glucanase (EC 3.2.1.6) hydrolyzes ft 1-3 or ft 1-4 crose candies, in recovery of scrap candy, in artificial honey,
bonds in /?-D-glucans. The products are oligosaccharides and as a humectant to hold moisture in foods. Invertase is
and glucose. The enzyme is used primarily in brewing, produced commercially from yeasts, usually Saccharo-
where it is added, along with other enzymes, to malted myces or Candida spp., and is relatively cheap to produce.
barley at the mash stage. The /?-glucanase degrades and Consequently, it is used as a soluble enzyme and there is
solubilizes barley gums (/?-glucan polymers), including little commercial impetus for its application in an immo-
those contributed by dying yeast cells, which would oth- bilized form.
erwise increase the viscosity of the wort. These residual Lactase (/?-galactosidase, EC 3.2.1.23) hydrolyzes lac-
glucans can contribute to haze problems in the final prod- tose into glucose and galactose. Small quantities of oligo-
uct. Commercial sources of /?-glucanase include Bacillus saccharides containing galactose may also be formed as by-
subtilis and A. niger. products. Compared with lactose, the main products are,
Glucose isomerase (EC 5.1.3.5) catalyzes conversion of in combination, three to four times more soluble, about
glucose to fructose, thereby increasing sweetness and twice as sweet, easier to ferment, and directly absorbed
value. The enzyme is actually a xylose isomerase, which from the intestine. Applications of lactase take advantage
also acts on glucose and requires magnesium as a cofactor. of these changes (2).
The reaction is readily reversible and at equilibrium, a Hydrolysis of lactose in milk makes the milk more di-
fructose/glucose ratio of 52/48 is achieved. However, in gestible for those who are lactose intolerant (especially in-
practice it is uneconomical to take the conversion beyond fants) due to low levels of intestinal /?-galactosidase. It also
42% fructose, when the syrup is isosweet with glucose on prevents crystallization of lactose in concentrated or frozen
a solids basis. The product (high-fructose corn syrup) is milk products, such as ice cream. Cheese whey is a major
produced at a rate of several million tons per annum and disposal problem, mostly because of its high lactose con-
has displaced sucrose and glucose syrups from many prod- tent. After separating the valuable whey protein, the lac-
ucts, especially in soft drinks in the United States. tose can be hydrolyzed by soluble or immobilized lactase.
The enzyme is produced commercially from several mi- The product is then concentrated to give a stable, sweet
crobial sources including Bacillus, Actinoplanes, and syrup, which may be used in a variety of foods or fermented
Streptomyces spp. and is readily immobilized by a variety to ethanol (3).
of methods (1). Lactases produced commercially from yeasts such as
Glucose oxidase (EC 1.1.3.4) catalyses the reaction: Kluyveromyces marxianus have a neutral pH optimum and
are used in milk processing. Lactases from molds such A.
niger or A. oryzae have an acid pH optimum and are more
glucose + O2 - gluconic acid + H2O2.
suitable for whey processing. Lactoses are readily immo-
bilized on a variety of supports for industrial use and for
It is often used in conjunction with catalase, which analysis of lactose in dairy products.
breaks down H2O2, thereby sparing the glucose oxidase Lipases (EC 3.1.1.3) hydrolyze ester linkages of triglyc-
from denaturation as well as providing oxygen for use by erides to give free fatty acids, diglycerides, monoglycerides,
and eventually glycerol. The enzyme is widely distributed storage. This can be prevented by use of the substrate an-
in food tissues and belongs to the general class of esterases. alogue 4-hexylresorcinol (5).
Lipase action has traditionally been regarded as a problem Proteases hydrolyze peptide bonds in proteins and poly-
in food science because the fatty acids produced may be peptides to produce smaller peptides and amino acids.
unpalatable or susceptible to oxidation. This is a particular Many proteases also have esterase activity. These enzymes
problem in stored cereals such as wheat and rice and in vary widely in their substrate specificity and optimum pH
milk, where the release of short-chain fatty acids from milk range. Enzymatic hydrolysis of protein is employed in a
fat by endogenous lipase leads directly to off-flavors. How- number of industries to create changes in product taste,
ever, it is recognized that lipase action is also responsible texture, and appearance as well as in waste recovery. Plant
for some of the desirable flavor in matured cheeses. Con- proteases such as papain and ficin have broad substrate
sequently, impure preparations (containing both lipase specificity and good thermal stability. They are used to ten-
and esterase activities) are produced from molds such as derize meat, to chillproof beer, and also to recover protein
Mucor, Rhizopus, and Aspergillus spp. for use in acceler- hydrolyzate from scrap fish and bones. Animal proteases
ated cheese ripening, often in conjunction with proteases. are generally more specific than the plant proteases. Tryp-
Concentrated cheese flavors produced in this fashion can sin has been used to inhibit the development of an oxidized
be used in a variety of snack products. Lipase can also be flavor in stored milk and to solubilize heat-denatured whey
used in directed transesterification of fats to improve func- protein (6). Pepsin is used primarily as an extender for calf
tional properties and uses. rennet. Fungal proteases from A. niger and A. oryzae are
Pectinases are a group of enzymes that act on various use to modify gluten in bread flour, so as to reduce dough
pectic substances (pectins) in higher plants. There are viscosity and improve color, texture and loaf volume. Bac-
three major types of pectinase: polygalacturonase (PG), terial proteases from Bacillus spp. are widely used in bis-
pectin lyase (transeliminase) (PL), and pectin esterase cuit, cookie, and cracker dough since hydrolysis of gluten
(PE). PG (EC 3.2.1.15) splits glycosidic bonds within yields very elastic doughs that can be spread thinly with-
(endo-) or at the end of (exo-) the pectin molecule. Endo- out rupture. Other uses of microbial proteases include
PG action leads to a large decrease in viscosity of pectin modification of soy and other food proteins to give im-
solutions. PL (EC 4.2.2.10) also splits endoglycosidic bonds proved functionality, decolorization of red blood cells to fa-
but the transelimination reaction yields a C4-C5 double cilitate use of waste blood plasma protein from animal
bond on the nonreducing end. PE (EC 3.1.1.11) cleaves slaughter and production, and modification of gelatin from
methanol from carboxyl groups, yielding low-methoxy pec- collagen. Recently there has been interest in using prote-
tin and polygalacturonic acid. ases in reverse to synthesize peptides. An example of this
Since pectin is a major structural element in and is the use of the enzyme thermolysin to produce the dipep-
between plant cell walls, alteration of the size or esteri- tide sweetner aspartame (7).
fication of pectins can change the texture of fruits and Pullulanase (EC 3.2.1.41) and isoamylase (3.2.1.68) act
vegetables during ripening and storage. Endogenous pec- specifically on the a 1-6 bonds of amylopectin in liquified
tinases may soften texture during ripening. However, deg- starch to produce maltose and maltotriose. These enzymes
radation of pectin can be inhibited by antisense RNA tech- improve the yield of mono- and disaccharides from starch
nology and this has been successfully exploited in when used in conjunction with other amylases. Pullulan-
tomatoes (4). Microbial pectinases are often responsible ase is produced commercially from Klebsiella pneumonia
for postharvest rotting and decay. However, fungal pectin- and is used in brewing to remove limit dextrins and allow
ases, mostly from Aspergillus spp. are widely used as pro- the production of specialty beers such as "high alcohol" or
cessing aids, mainly for extraction and clarification of "low calorie."
fruit juices. Rennet is obtained from the fourth stomach of un-
Polyphenol oxidase (PPO) (EC 1.10.3.1) is also known weaned calves and contains several enzymes including
as phenolase tyrosinase, or catecholase. The enzyme is pepsin and chymosin (EC 3.44.3). Chymosin is an acid pro-
widely distributed in plants and fungi and in some mam- tease used in cheese making to coagulate the casein in
mals. In fruits and vegetables it is separated from phenolic milk. It catalyzes very specific and limited proteolysis of k-
substrates in the intact tissue. However, on cutting or casein, thereby destabilizing the casein micelle and caus-
other injury and exposure to oxygen, phenolase activity re- ing subsequent formation of curd. Calf rennet is expensive
sults in rapid browning due to polymerization of the qui- and is increasingly being replaced by microbial proteases
nones to give brown pigments (melanins). with a high ratio of milk-clotting activity to general pro-
Enzymatic browning is a major problem in handling teolytic activity. Suitable proteases have been obtained
and storage of fresh produce. However, in foods such as tea, from Endothia parasitica, Mucor meihei and M. pusillus.
coffee, and cocoa and in dried fruits such as raisins and Microbial proteases are now used in about one-half of all
dates, it improves color and flavor. Methods for control of cheese production worldwide. Their main disadvantage is
enzymatic browning include: inactivation of the enzyme by that they tend to be heat stable and cause proteolysis in
heat, sulfites, or proteases; use of acidulants to lower pH whey products. However, a second generation of modified
and inhibit the enzyme; and use of chelators to remove the microbial rennets with lower stability is now available.
copper that is essential for activity and exclusion (or re- The gene for chymosin has now been successfully cloned
moval) of oxygen by appropriate packaging or glucose ox- and expressed in several microorganisms (8). Products
idase activity. Polyphenol oxidase activity in shrimp and from this source may well replace both traditional and mi-
other Crustacea leads to blackening during harvest and crobial rennets in the near future.
BIBLIOGRAPHY strating that food spoilage could be caused by bacteria and
other microorganisms.
1. S. A. Barker and G. S. Fetch, "Enzymatic Processes for High- Patents for the preservation of milk after evaporation
Fructose Corn Syrup," in A. Laskin, ed., Enzymes and Immo- in a vacuum were granted to Gail Borden by the United
bilized Cells in Biotechnology, Benjamin/Cummings, Menlo States and England in 1856. Although these patents ap-
Park, Calif., 1985, pp. 93-105. plied to concentrating milk without the addition of sugar,
2. R. R. Mahoney, "Lactose: Enzymatic Modification," in P. F. Fox, Borden's first commercial process was for the manufacture
ed., Advanced Dairy Chemistry, Vol. 3, Chapman and Hall, of sweetened condensed milk. The original vacuum equip-
London, United Kingdom, 1997, pp. 77-105. ment developed by Borden is now on display at the Smith-
3. J. Barry, "A New Source for Alcohol," Food Manufacture 58, sonian Institution.
63-67 (1983). Borden produced sweetened condensed milk at Wassaic,
4. G. Tucker, "Improvement of Tomato Fruit Quality and Pro- New York, in 1861. By 1865, new plants were opened in
cessing Characteristics by Genetic Engineering," Food Science Brewster, New York, and Elgin, Illinois. In 1866, Charles
and Technology Today 7, 103-108 (1993). A. Page and his three brothers built Europe's first com-
5. A. J. McEvily, R. Iyengar, and W. S. Otwell, "Sulfite Alternative mercial sweetened condensed milk plant in Switzerland.
Presents Shrimp Melanosis," Food Technol. 45, 80-86 (1991). They later built plants in England and in the United
6. J. C. Monti and R. Jost, "Solubilization of Cheese Whey Protein States.
by Trypsin and a Process to Recover the Active Enzyme from In 1884, a U.S. patent was issued for "an apparatus for
the Digest," Biotechnol. Bioeng. 20, 1173-1185 (1981).
preserving milk," and in 1885, the world's first commercial
7. K. Nakanishi and R. Matsuno, "Enzymatic Synthesis of Aspar- evaporated milk plant was opened in a converted wool fac-
tame," in R. D. King and P. S. J. Cheetham, eds., Food Biotech-
tory in Highland, Illinois, where evaporated cream was
nology, Vol. 2, Elsevier Applied Science, London, United King-
dom, 1988, pp. 219-249. manufactured and sold.
The first advertisement for evaporated milk appeared
8. D. Jackson, "Cost Reduction in Food Processing Using Biotech-
nology," in S. K. Harlander and T. B. Lubuza eds., Biotechnol- in 1893, calling the product "a perfect instant food." In
ogy in Food Processing, Noyes Press, Park Ridge, N.J., 1986, 1894, the first recipe booklet for evaporated milk was dis-
pp. 285-295. tributed, and by 1895, the product was popular both in
western mining areas of the United States, where fresh
milk was scarce, and in the South, where there was little
GENERAL REFERENCES refrigeration. Consumers quickly recognized the value of
evaporated milk as a safe, wholesome, and convenient food
P. S. J. Cheetham, "The Application of Enzymes in Industry," in as well as a nutritional ingredient for cooking that had the
A. Wiseman, ed., Handbook of Enzyme Biotechnology, 2nd ed., added benefit of storage stability.
Ellis Horwood, Chichester, United Kingdom, 1985, pp. 274-
373.
P. F. Fox, ed., Food Enzymology, VoIs. 1 and 2, Elsevier Applied
Science, London, United Kingdom, 1991. THE PRODUCT
T. Nagodawithana and G. Reed, eds., Enzymes in Food Processing,
3d ed., Academic Press, San Diego, Calif., 1993. Evaporated milk is a canned whole milk concentrate to
G. A. Tucker and L. F. J. Woods, eds., Enzymes in Food Processing,
which a specified quantity of vitamin D has been added
2nd ed., Blackie Academic and Professional, London, United
Kingdom, 1995. and to which vitamin A may be added. It conforms to the
Food and Drug Administration (FDA) Standard of Identity
(21 CFR 131.130), having a minimum of 6.5% milkfat,
RAYMOND R. MAHONEY 16.5% of nonfat milk solids, 23.0% total milk solids, and
University of Massachusetts 25 IU vitamin D per fluid ounce. Related evaporated milk
Amherst, Massachusetts
products are evaporated nonfat milk, evaporated lowfat
milk, evaporated filled milk, and evaporated goat milk.
Standards of Identity do not exist for these related evap-
See also ENZYMES IN FOOD PRODUCTION. orated milk products. Their typical compositions are the
following:
EVAPORATED MILK Evaporated nonfat Less than 0.5% milkfat, 20.0% total milk
milk solids, 25 IU vitamin D and 125 IU
HISTORY vitamin A per fluid ounce added
Evaporated lowfat 2.0% milkfat, 18% nonfat milk solids,
milk vitamins A and D added
Evaporated milk, like other processed canned foods, orig- Evaporated filled 6.0% vegetable fat, 17.5% nonfat milk
inated with the experiments of the French scientist Nich- milk solids, vitamins A and D added
olas Appert. Appert, whose work on food preservation be- Evaporated goat Not less than 7.0% milkfat and 15.0%
gan in 1795, was the first to evaporate milk by boiling it milk nonfat milk solids, vitamin D added
in an open container and preserve it by heating the product
in a sealed container. Fifty years later, Louis Pasteur laid Table 1 shows the nutritional content of evaporated,
the scientific foundation for heat preservation by demon- evaporated nonfat, and evaporated lowfat milks.
Table 1. Nutritional Content per One-Half Cup Table 2. Evaporated Milk Production
Evaporated Milk
Evaporated milk
Original Nonfat Lowfat Year Evaporated milk and related products"
Calories 170 100 110 1975 20,796,000
Protein ( g ) 8 9 8 1976 20,362,000
Carbohydrates (g) 12 14 12 1977 18,347,000
Fat (g) 10 Less than 1 3 1978 17,340,000
1979 17,110,000
Percentage of U.S. Recommended Daily Allowance (U.S. RDA) 1980 15,500,000
1981 15,840,000
Protein 20 20 20
1982 15,05O5OOO
Vitamin A 4 10 10
Vitamin C a a a 1983 14,300,000 16,612,000
1984 13,700,000 15,892,000
Thiamine 2 2 2
1985 14,360,000 16,537,000
Riboflavin 20 20 20
a a 1986 12,996,000 14,881,000
Niacin
1987 12,966,000 14,759,000
Calcium 30 30 30
Iron a a a
1988 13,357,000 15,164,000
1989 12,451,000 14,193,000
Vitamin D 25 25 25
1990 13,169,000 14,895,000
Phosphorus 25 25 25
1991 11,313,000 12,776,000
"Contains less than 2% of the U.S. RDA of these nutrients. 1992 12,153,000 13,595,000
1993 11,561,000 13,114,000
1994 10,585,000 11,771,000
1995 10,847,000 12,462,000
PRODUCT PROCESSING 1996 9,853,000 11,271,000
1997 10,656,000 12,204,000
1998 10,275,000 11,843,000
A typical processing scheme for evaporated milk begins
with high quality, fresh whole milk, which is standardized Notes: Figures reported in cases; 48-tall equivalent. Product weight/case
to produce the exact composition desired in the final prod- since 1985: 40 Ib.
"Includes evaporated milk plus evaporated nonfat milk, evaporated lowfat
uct (addition or removal of cream or nonfat milk). The milk, and evaporated filled milk. Data not available before 1983.
product is heated, concentrated under reduced pressure in
an evaporator, homogenized, and cooled. Vitamins (A or D,
or both) are added, and the final composition is verified.
Final standardization is accomplished, when necessary. GENERAL REFERENCES
After cans are filled and sealed, they are sterilized in a
three-phase continuous system consisting of preheater, re- C. W. Hall and T. I. Hedrick, Drying of Milk and Milk Products,
tort, and cooler, cooled; labeled; and packed for shipment. 2nd ed., AVI, Westport, Conn., 1971.
In the United States, evaporated milk is packed in 5-, 12-, E. H. Parfitt, "The Development of the Evaporated Milk Industry
20-, and 97-fluid ounce lead-free cans. in the United States," Journal of Dairy Science 39, 838 (1956).
R. Seltzer, The Dairy Industry in America, Magazines for Industry,
New York, 1976.
INDUSTRY PRODUCTION U.S. Food and Drug Administration, Department of Health and
Human Services, "Evaporated Milk," Code of Federal Regula-
Table 2 reflects U.S. production of evaporated milk and tions 21, 131.130(1999).
related products during the period 1975 to 1998. The data
are based on manufacturers' production reported to the
American Dairy Products Institute. Before 1983, data were WARREN S. CLARK, JR.
not collected on the production of related evaporated milk American Dairy Products Institute
products. Chicago, Illinois
EVAPORATION temperature liquid. This necessary lower boiling tempera-
ture can be maintained by operating a second effect of
The primary objectives of evaporation, as a unit operation evaporation at a lower pressure than the first, usually un-
in food processing, are to reduce the volume of the product der a vacuum. The same principles can be extended to
by some significant amount with minimum loss of nutrient more than two effects in industrial applications.
components, and to preconcentrate liquid foods such as Steady-state mathematical models with equations that
fruit juice, milk, and coffee before the product enters a de- represent heat and mass transfer may be used for design
hydration process, thus saving energy in subsequent purposes. Steam requirement, heat transfer surface area,
operations and reducing handling (transport, storage, and and system capacity (production rate) can be determined
distribution) costs. Evaporation is accomplished by boiling for a given degree of concentration and processing time. A
liquid foods until the desired concentration is obtained, as double-effect evaporator, with feed and steam or vapor
result of the difference in volatility between the solvent streams moving in counterflow arrangement (Fig. 1) will
and solutes. In the food industry, the solvent to withdraw be used here to illustrate the theory.
is almost always water (1). Evaporation increases the sol- For the first effect, mass balance that relates solids en-
ids content of a food and hence preserves it by a reduction tering and leaving the evaporator gives
in water activity; however, the flavor and color of a food
=
may be changed during the process. The technical simplic- Th2X2 TTIiXi (1)
THEORY
0 = -CT (13)
\ ju2 I
Table 1 gives formulas for local heat-transfer coefficients
according to different investigators.
Experimental product-side heat-transfer coefficients hp
were determined (9) for thin-film wiped-surface evapora-
tors, which are extensively used for concentrating high-
viscosity or heat-sensitive products. Product degradation
is minimized by vigorous agitation and continuous removal
Temperature difference (Tsurface- Tbu[k) of liquid films on the heat-transfer wall. The correlation
obtained for the transition-flow regime (Re = 100-1,000)
Figure 2. Typical boiling curve illustrating various regimes of was
boiling near heated surfaces, a, natural convection; b, nucleate / \-2.93
boiling; c, transition boiling; d, film boiling. Source: Reprinted with Nu = 0.0483Rea586Pr1-05Fr-118 ^ (14)
permission from Ref. 4. W
Table 1. Local Heat-Transfer Coefficients
Flow regime A *i Exponent for Re Notes
Laminar (Re < 20-30) 0.69 0 -0.33 Nusselt theory
Wavy laminar (Re < 1,000-3,000) 0.61 4> -0.223
Turbulent (Re > 1,000-3,000) 0.067 0 - Pr 0.2 Colburn theory based on pipe friction
0.030 0-Pr 0.33
0.19 0-Pr 0.067
0.0078 $ Pr 0.4 Pr -5
0.0122 < Pr 0.33 Pr -5
Source: Ref. 8.
which is valid for liquid feed rate of 58-87 kg/h and agi- evaporation and 30% for skim milk evaporation (13). In-
tation speed of 150-500 rpm. The correlation obtained for creased fouling is caused by a nonuniform distribution of
the turbulent-flow regime (Re > 1,000) was liquid to individual heating tubes in falling-film evapora-
tors such that some groups of tubes have more deposit than
/x-0.753
Nu - 4.137Re0-283Pr3-325Fr-032M- (15) the others.
Vii,/ Steam economy, defined as the mass of water evapo-
rated per unit mass of steam utilized, is often used as a
which is valid for liquid feed rate of 87-133 kg/h and agi- measure of evaporator performance. A similar definition
tation speed of 500-1,300 rpm. The authors found that un- could be used if another condensing vapor (ammonia,
stable operation of the evaporator occurred when the speed Freon, or diphenyl) is employed as the heating medium.
of the wiper blades was below 150 rpm, and rapid increase Steam requirement for double-effect is computed di-
in hp was observed for rpm range 250-350. Under similar rectly from solving the heat and mass balances presented
conditions of evaporation, heat-transfer coefficients were earlier. Equations 1-6 can be used to compute the heat-
lower for high-viscosity liquids. transfer surface area after the overall heat-transfer coef-
A detailed expression for the overall heat-transfer co- ficients U1 and U2 have been evaluated for both effects. The
efficient in multiple-effect falling-film evaporators was usual procedures for computing steam requirement in-
worked out (10). This coefficient U was given as a function volve assumptions, such as equal heat flux, equal heat-
of the enthalpy and temperature of the liquid and vapor transfer area, or equal temperature gradient in each effect
phases, local heat-transfer coefficients, and mass fractions of the system.
of solute in the inlet and outlet liquid streams. The fun- For plants with increasing number of effects resulting
damental mathematical model of multiple-effect evapora- in decreased potential temperature difference in each ef-
tors was further applied (11) along with an accurate esti- fect, the boiling point rise is of importance when calculat-
mate of U and fouling factor Rd to design a five-effect ing the temperature program of an evaporation plant. For
evaporation unit capable of treating the input citrus juice well-defined solutions such as water, the elevation of boil-
flow rates indicated in (Figure 3). Results of the calcula- ing points is proportional to the molar concentration of the
tions are shown in Table 2 for orange and lemon juices that solute, thus
were concentrated from 11.7 to 65Brix, and from 9.3 to
40Brix, respectively.
According to one study (12), factors influencing the rate A = ^f^ (16)
A
of heat transfer can be summarized as
Food liquids are normally more complicated and the boil-
1. Temperature difference between the steam and the ing point rise has to be determined experimentally. For
boiling liquid. milk, the following values have been given (8):
2. Fouling of evaporator surfaces.
3. Boundary film thickness. Concentration % DM 16 27.5 39 49 62 69 73
0
Temperature C 0.5 1 1.5 2 3 4 5
Factors influencing the economics of evaporation include
The Duhring plot for sucrose for various conditions are pre-
1. Loss of concentrate due to foaming and entrainment. sented in Figure 4.
2. Energy expenditure.
EQUIPMENT
The total evaporation depends on the steam consump-
tion and the specific surface area of the evaporator. Capital Evaporators are basically heat exchangers, that transfer
costs increase with the size of the evaporator whereas en- heat from steam or other heating medium to the food. Va-
ergy cost decrease with it. If the fouling of the heating sur- pors produced must be separated. The selection of an evap-
face is expressed as specific product losses and is reduced orator should include the following factors (12):
from 1.0 to 0.2 kg thin milk/m2, for modern evaporators
with a specific surface area of 0.12-0.14 m2(kg/h), the pro- 1. Production rate (kilograms of water removed per
duction costs will decrease by about 40% for whole milk hour).
2. Degree of concentration required (percentage dry
solids in the product).
Raw citrus fruits 3. Heat sensitivity of product in relation to the resi-
a) 20000 (82% moisture) dence time and temperature of evaporation.
b) 10000 (83% moisture)
4. The requirement for volatile recovery facilities.
Waste 5. Ease of cleaning.
Washing and sorting
6. Reliability and simplicity of operation.
7. Size of evaporator.
8. Capital and operating costs.
Peel oil recovery Cowe 9. Product quality.
Mist flow
Liquid food
Condensate lnfeed
vent (dilute product) Figure 7. Flow regimes and temperature distribution in a climb-
ing-film evaporator. Source: Reprinted with permission from Ref.
Outlet 16.
(concentrated product)
Figure 5. Calandria evaporator. Source: Reprinted with permis- the two-phase flow, causing high pressure loss and boiling
sion from Ref. 14. point elevation. To this effect, it has been recommended
that tubes between 8 and 12 m in length and with a di-
Vapor ameter between 30 and 50 mm be used (16).
Product distribution in the upper part of the calandria
can be done in two ways; dynamic distribution or static
distribution. Dynamic distribution may be done by a full-
cone nozzle in which the kinetic energy of the liquid is used
Thin film to atomize the fluid into droplets and distribute them on
of liquid the upper tube sheet. This distribution device, although
simple and economic, does not guarantee even distribu-
Vapor tion. Static distribution devices (Fig. 9) are generally pre-
ferred. Even distribution is achieved by having uniform
liquid static pressure over all openings in the base of a
predistribution bowl, giving uniform wetting of all tubes.
The system adapts readily to varying feed conditions by
Product
Preheater
Vapor Consentrate
Condensate
Feed
Feed
Demister
Condensate
Concentrate
Vapor
Figure 10. Mechanical thin-film evaporator. Source: Reprinted
with permission from Ref. 15.
Feed inlet
Steam
Condensate
Rotor assembly Figure 12. Centri-term evaporator. Source: Reprinted with per-
mission from Ref. 18.
Steam
vent
Product
Fresh
juice
Figure 14. Schematic of a 5-effect, 7-stage Stages Juice flow Barometric condenser Pasturizer/heater HHeater
TASTE Evaporator. Source: Reprinted Effects Vapor flow Flash cooler Condensate out
with permission from Ref. 24.
vapor recompressors have more or less the same limited chanical vacuum pump. Its advantage over a mechanical
flexibility as thermal recompressors. This applies particu- vapor recompression system is that the volume of vapor
larly to the high-speed radial turbo compressor, which being compressed is much reduced at a given evaporator
reaches its surge limit if the actual vapor flow is too small, temperature. However, the refrigerant must be com-
thus rendering the system unstable (16). Mechanical re- pressed through a wider temperature range because an
compressors are complicated in design, and need careful additional heat exchanger is required.
maintenance and supervision of mechanical vibration.
Auxilliary Equipment
Refrigerant Cycle Evaporators. Figure 18 shows a sche- Preheaters. After feeding the product into the evapo-
matic system of juice concentration using a technique that ration plant via a float balance tank and feed pump, the
combines a vapor compression refrigeration cycle with the first process step is to preheat the product. In general, liq-
evaporation system (25). Condensing water vapor boils liq- uid food is stored at between 5 and 2O0C for quality pres-
uid refrigerant to form a refrigerant vapor, which is then ervation; therefore, it must be preheated to at least the
compressed to a higher temperature level and acts as a evaporation temperature of the first effect, most commonly
heat source to boil the liquid being concentrated (19). The between 40 and UO0C. Three types of preheater are used:
evaporator, for simplicity, is shown as a single-effect design plate, spiral tube, and straight tube heat exchangers (16).
with means for recirculating the juice. Variations may em- If there are solid particles in the product, a plate heat ex-
ploy multiple effects. The pressure in the system can be changer should not be used, because the particles may
maintained by a relatively small steam ejector or a me- block the narrow product passages. The same problem may
Steam Steam
Cold water
Vent
Separator
Separator
Separator
Separator
Separator
Fresh
juice Product
Figure 15. Schematic of a 4-effect, 5-stage plate evaporator. Source: Reprinted with permission
from Ref. 24.
Barometric
condenser
Cold
High-pressure water Booster ejector or High-pressure
steam thermo-compressor steam
Exhaust to
atmosphere
To hotwell
Water vapor
Evaporator
Steam
High-pressure
steam
Condensate
Separator
also occur with protein-containing products, due to the for- small pressure loss, and short residence time. Because a
mation of deposits if the preheating temperature exceeds fine mist of concentrate is produced during vigorous boiling
the denaturalization temperature. Secondary flows devel- and carried over in the vapor, separators should be de-
oped in the spiral tube leads to higher heat-transfer coef- signed to minimize entrainment. Large pressure loss is to
ficients than straight tube, and a reduced tendency to foul. be avoided lest extra heating surface must be installed in
The disadvantages are that inspection and replacement of the next effect. The many different separators in use can
the tube is very difficult. Straight tube preheaters are es- be classified according to three operating principles: grav-
pecially useful as intermediate preheaters following first ity separator, baffle separator, and centrifugal separator.
step preheating with plate heat exchanger, where product
of high concentration is required, and where equipment Condensers. Surplus vapor produced in evaporation can
inspection is essential. be condensed and reused where possible. Condenser cool-
ing water is normally provided from a cooling tower or the
Separators. Separators are used to separate the mixture city main; in certain cases, it may be extracted from rivers,
of vapor and concentrated product produced in the calan- lakes, or the sea. The tasks of a condenser are to maintain
dria. A separator should have high separation efficiency, the heat balance of an evaporation plant, to stabilize the
Mechanical temperature in each effect, and to produce and maintain
vapor vacuum.
compressor
EFFECT ON FOODS
Liquid refrigerant
Refrigerant vapor return
Cold water
Auxiliary heat Water vapor
exchanger condenser Hot water
shell-and-tube
To
vacuum
pump or
Hot refrigerant gas
steam
Hot Evaporator ejector
Water vapor
water Cold
Trap Expansion
valve
Condensate
Refrigeration: Separator
compressor
Figure 18. System of concentration Concentrate
using refrigerant cycle evaporators. Juice feed
Source: Reprinted with permission Recirculating line
from Ref. 25.
A. K. LAU
University of British Columbia
Vancouver, British Columbia Steam
Canada
Condensate
EVAPORATORS: TECHNOLOGY Product
AND ENGINEERING
Figure 1. Jacketed batch pan.
TYPES OF EVAPORATORS
In the evaporation process, concentration of a product is early 1960s, it also enjoyed wide use in the concentration
accomplished by boiling out a solvent, generally water, so of corn syrups.
that the end product may be recovered at the optimum With a batch pan evaporator, product residence time
solids content consistent with desired product quality and normally is many hours. Therefore, it is essential to boil at
operating economics. It is a unit operation that is used ex- low temperatures and high vacuum when a heat-sensitive
tensively in processing foods, chemicals, pharmaceuticals, or thermodegradable product is involved. The batch pan
fruit juices, dairy products, paper and pulp, and both malt is either jacketed or has internal coils or heaters. Heat-
and grain beverages. It also is a unit operation, which, with transfer areas normally are quite small as a result of vessel
the possible exception of distillation, is the most energy- shapes, and heat-transfer coefficients tend to be low under
intensive. natural convection conditions. Heat transfer is improved
Although the design criteria for evaporators are the by agitation within the vessel. Low surface areas together
same regardless of the industry involved, the question al- with low HTCs (heat-transfer coefficients) generally limit
ways arises as to whether evaporation is being carried out the evaporation capacity of such a system. In many cases,
in the equipment best suited to the duty and whether the large temperature differences cannot be used for fear of
equipment is arranged for the most efficient and econom- rapid fouling of the heat-transfer surface. Relatively low
ical use. As a result, many types of evaporators and many evaporation capacities, therefore, limit its use.
variations of processing techniques have been developed to
take into account different product characteristics and op- Tubular Evaporators
erating parameters. Natural Circulation. Evaporation by natural circulation
The more common types of evaporators include the fol- is achieved through the use of a short tube bundle within
lowing: the batch pan or by having an external shell and tube
heater outside the main vessel as illustrated by Figure 2.
1. Batch pan
2. Natural circulation
3. Rising film tubular To condenser
or vacuum
4. Falling film tubular
5. Rising-falling film tubular
6. Forced circulation
7. Wiped film Steam
8. Plate equivalents of tubular evaporators
Product
out
Batch Pan
Next to natural solar evaporation, the batch pan as shown
Feed
in Figure 1 is one of the oldest methods of concentration.
It is somewhat outdated in today's technology but still is
used in a few limited applications such as the concentra-
tion of jams and jellies where whole fruit is present and in
processing some pharmaceutical products. Up until the Figure 2. Natural circulation.
24. J. G. Filho, A. A. Vital! and F. C. P. Viegas, Energy Consump-
tion in a Concentrated Orange Juice Plant. J. Food Process
Eng. 7, 77-89, 1984. Condenser
25. HVAC Systems and Applications, Amer. Soc. Heating, Refrig-
eration and Air Conditioning Engineers, 1987.
26. J. W. G. Porter and S. Y. Thompson. "Effects of Processing on
the Nutritive Value of Milk," Vol. 1 Proc. Fourth International
Conference on Food Science and Technology, Madrid, 1976.
A. K. LAU
University of British Columbia
Vancouver, British Columbia Steam
Canada
Condensate
EVAPORATORS: TECHNOLOGY Product
AND ENGINEERING
Figure 1. Jacketed batch pan.
TYPES OF EVAPORATORS
In the evaporation process, concentration of a product is early 1960s, it also enjoyed wide use in the concentration
accomplished by boiling out a solvent, generally water, so of corn syrups.
that the end product may be recovered at the optimum With a batch pan evaporator, product residence time
solids content consistent with desired product quality and normally is many hours. Therefore, it is essential to boil at
operating economics. It is a unit operation that is used ex- low temperatures and high vacuum when a heat-sensitive
tensively in processing foods, chemicals, pharmaceuticals, or thermodegradable product is involved. The batch pan
fruit juices, dairy products, paper and pulp, and both malt is either jacketed or has internal coils or heaters. Heat-
and grain beverages. It also is a unit operation, which, with transfer areas normally are quite small as a result of vessel
the possible exception of distillation, is the most energy- shapes, and heat-transfer coefficients tend to be low under
intensive. natural convection conditions. Heat transfer is improved
Although the design criteria for evaporators are the by agitation within the vessel. Low surface areas together
same regardless of the industry involved, the question al- with low HTCs (heat-transfer coefficients) generally limit
ways arises as to whether evaporation is being carried out the evaporation capacity of such a system. In many cases,
in the equipment best suited to the duty and whether the large temperature differences cannot be used for fear of
equipment is arranged for the most efficient and econom- rapid fouling of the heat-transfer surface. Relatively low
ical use. As a result, many types of evaporators and many evaporation capacities, therefore, limit its use.
variations of processing techniques have been developed to
take into account different product characteristics and op- Tubular Evaporators
erating parameters. Natural Circulation. Evaporation by natural circulation
The more common types of evaporators include the fol- is achieved through the use of a short tube bundle within
lowing: the batch pan or by having an external shell and tube
heater outside the main vessel as illustrated by Figure 2.
1. Batch pan
2. Natural circulation
3. Rising film tubular To condenser
or vacuum
4. Falling film tubular
5. Rising-falling film tubular
6. Forced circulation
7. Wiped film Steam
8. Plate equivalents of tubular evaporators
Product
out
Batch Pan
Next to natural solar evaporation, the batch pan as shown
Feed
in Figure 1 is one of the oldest methods of concentration.
It is somewhat outdated in today's technology but still is
used in a few limited applications such as the concentra-
tion of jams and jellies where whole fruit is present and in
processing some pharmaceutical products. Up until the Figure 2. Natural circulation.
The external heater has the advantage that its size is not
dependent on the size or shape of the vessel itself. As a
result, larger evaporation capacities may be obtained. The
most common application for this type of unit is as a re- Steam
boiler at the base of a distillation column.
Falling Film Tubular. Following development of the ris- further enhanced by generating flash vapor at this point.
ing film principle, it took almost a further half century for The falling film evaporator does have the advantage that
a falling film evaporation technique to be perfected (Fig. the film is "going with gravity" instead of against it. This
4). The main problem was to design an adequate system results in a thinner, faster moving film and gives rise to
for the even distribution of liquid to each of the tubes. Dis- even shorter product contact time and a further improve-
tribution in its forerunner, the rising film evaporator, was ment in the value of HTC.
easy as the bottom bonnet of the calandria always was The rising film unit normally needs a driving force or
pumped full of liquid, thus allowing equal flow to each temperature difference across the heating surface of at
tube. least 250F to establish a well-developed film, whereas the
While all manufacturers have their own techniques, falling film evaporator does not have a driving force limi-
falling film distribution generally is based on the use of a tation. This permits a greater number of evaporator effects
perforated plate positioned above the top tube plate of the to be used within the same overall operating limits, in
calandria. Spreading of liquid to each tube sometimes is other words, if steam is available at 2.5 psig corresponding
to 22O0F and the last effect boiling temperature is 12O0F,
the total available AT is equal to 10O0F. This would limit
a rising film evaporator to four effects, each with a AT of
To condenser 250F. It would be feasible, meanwhile, to have as many as
or vacuum ten or more effects using the falling film technique.
Dilute
liquor
inlet Rotor
assembly
Condensate
outlet Joint gaskets
Feed in Head
Vapor and condensate
discharge to separator
Feed
Product from
separator
Vapor and
product to
separator
Condensate
outlet
Figure 9. Falling film plate evapo- Final product
rator. to separator
Capacities
For evaporation capacities of up to about 60,000 Ib/h of
water removal, the possibility of using either a plate or
tubular system should be considered. The capital invest-
ment is relatively close, but the lower cost of installing a
plate evaporator together with its compactness, expenda-
bility, and reduced building requirements generally makes
Figure 12. Corrugated plate pattern. it extremely attractive. Above 60,000 Ib/h evaporation, the
Vacuum
Steam or
hot water
Product
Feed out
Circulation
rate (GPM)
Heat transfer
area (ft)
Absorbed BHP
One Pass Three Pass
Single Equipment $491,280 $540,960 Triple
pass Absorbed BHP 272 396 pass
Recompressor
High pressure
steam
3A
1st Effect 2nd Effect Effect
Condensate
to receiver Condenser
Condensate
receiver
Chilled
water in
Concentrate Feed
cooling tank
Cooling
water
Vacuum
Condensate
Waste
condensate
Product
8O0F
power even when all the gas and oil has been exhausted possible, the pressure boost across the compressor is lim-
or is too expensive to use. ited. In the majority of cases, this pressure boost will cor-
Briefly examining the thermodynamics involved with respond to a saturated temperature rise in the region of
MVR, the Figure 20 schematic shows an evaporator with 150F or less.
a liquid boiling point of 2120F (atmospheric pressure). All In this example, there is a pressure boost of 4.5 psi
of the water vapor that is boiled off passes to a compressor. across the compressor. Assuming that there is a pressure
In order to keep the energy input to the system as low as low of 0.5 psi in the system, the effective pressure on the
flow
Enthalpy 1169 Btu/lb
Pressure 19.2 psia
Compressor
Work Effective steam economy 970 -*- 18 = 54
18 Btu/lb Efficiency of drive & compressor 65 - 72%
Inefficiency due to by-pass 5 -> 10%
Desuperheat /.Actual effective steam economy 32 -^35 Effects
spray
Evaporator
Condensate
Density
Gram/milliliter Pounds/gallon 8.33
Pounds/ft3 62.42
Thermal conductivity
Kilocalorie/(hr)(m)(C) Btu(h)(ft)(F) 0.6719
W/(m)(C) 0.5778
Viscosity
Centistokes Centipoise Specific gravity
Dynamic viscosity pound-mass (ft)(s) Centipoise 1488.2
Kinematic viscosity cm2/s Centistokes 100
Pressure
Kilopascal psi 0.14504
Bar 14.504
Inches Hg absolute psia 0.4912
Atmosphere 14.696
Torr 0.01908
mmHg 0.01908
Enthalpy
Calorie/gram Btu/pound-mass 1.8
Work /Energy
(Kilowatt)(hr) Btu 3412.1
(Horsepower )(hr) 2544.4
Calorie 0.003968
Heat-transfer coefficient
Kilocalorie/(h)(m2)(C) Btu(h)(ft3)(F) 0.2048
W/(cm2)(C) 1761.1
Summary
Film evaporators offer the dual advantages of low resi-
dence time and low temperature difference that help as-
sure a high product quality when concentrating heat-
sensitive products. In comparing the different types of film
evaporators that are available, falling film designs provide
the lowest possible AT and the falling film plate evaporator
provides the shortest residence time. Figure 21. Rising-falling film plate evaporator in final stages of
fabrication.
PLATE-TYPE EVAPORATORS
To effectively concentrate an increasing variety of products a frame resembling that of a plate heat exchanger. The first
that differ by industry in such characteristics as physical product passage is a rising pass and the second, a falling
properties, stability, or precipitation of solid matter, equip- pass. The steam plates, meanwhile, are arranged alter-
ment manufacturers have engineered a full range of evap- nately between each product passage.
oration systems. Included among these are a number of The product to be evaporated is fed through two parallel
plate-type evaporators. feed ports and is equally distributed to each of the rising
Plate evaporators initially were developed and intro- film annuli. Normally, the feed liquor is introduced at a
duced by APV in 1957 to provide an alternative to the tu- temperature slightly higher than the evaporation tem-
bular systems that had been in use for half a century. The perature in the plate annuli, and the ensuing flash distrib-
differences and advantages were many. The plate evapo- utes the feed liquor across the width of the plate. Rising
rator, for example, offers full accessibility to the heat- film boiling occurs as heat is transferred from the adjacent
transfer surfaces. It also provides flexible capacity merely steam passage with the vapors that are produced helping
by adding more plate units, shorter product residence time to generate a thin, rapidly moving turbulent liquid film.
(resulting in a superior quality concentrate), a more com- During operation, the vapor and partially concentrated
pact design with low headroom requirements and low in- liquid mixture rises to the top of the first product pass and
stallation cost. transfers through a "slot" above one of the adjacent steam
These APV plate evaporation systems are available in passages. The mixture enters the falling film annulus
four arrangementsrising-falling film, falling film, Para- where gravity further assists the film movement and com-
vap, and Paraflashand may be sized for use in new pro- pletes the evaporation process. The rapid movement of the
duce development or for production at pilot plant or full- thin film is the key to producing low residence time within
scale operating levels. the evaporator as well as superior heat-transfer coeffi-
cients. At the base of the falling film annulus, a rectan-
Rising-Falling Film Plate gular duct connects all of the plate units and transfers the
evaporated liquor and generated vapor into a separating
The principle of operation for the rising-falling film plate device. Steam and condensate ports connect to all the
evaporator (RFFPE) involves the use of a number of plate steam annuli (Fig. 22).
packs or units, each consisting of two steam plates and two The plate evaporator is designed to operate at pressures
product plates. As shown in Figure 21, these are hung in extending from 10 psig to full vacuum with the use of any
Vapor
Steam Inlet Steam Discharge Steam
Steam section section section section section
Separator
Feed Steam
spacers
Head Gaskets
Condensate
outlet
Concentrate
Figure 22. Rising-falling film plate evaporator arranged for one complete pass.
number of effects. However, the maximum pressure differ- Where suspended solid level is low and feed can be
ential normally experienced between adjacent annuli dur- passed through 50 mesh screen
ing single effect operation is 15 psig. This, and the fact that
the pressure differential always is from the steam side to A "junior" version of the evaporator is available for pilot
the product side, considerably reduces design require- plant and test work and for low-capacity production. If nec-
ments for supporting the plates. The operating pressures essary, this can be in multieffect-multistage arrangements
are equivalent to a water vapor saturation temperature such as the system illustrated in Figure 23.
range of 2450F downward and thus are compatible with
the use of nitrile or butyl rubber gaskets for sealing the Falling Film Plate
plate pack. Incorporating all the advantages of the original rising
Most rising-falling film plate evaporators are used for falling film plate evaporator system with the added bene-
duties in the food, juice, and dairy industries where the low
residence time and 100-20O0F operating range
temperatures are essential for the production of quality
concentrate. An increasing number of plate evaporators,
however, are being operated successfully in both pharma-
ceutical and chemical plants on such products as anti-
biotics and inorganic acids. These evaporators are avail-
able as multi-effect and/or multi-stage systems to allow
relatively high concentration ratios to be carried out in a
single pass, nonrecirculatory flow.
The rising-falling film plate evaporator should be given
consideration for various applications.
Paravap
The operating principle of the Paravap represents an ap-
plication of the thin film, turbulent path evaporation pro-
Figure 25. Single-effect R86 Paravap.
Product Heating
or cooling
liquid
Figure 24. Typical product and steam plate unit for falling film
plate evaporator. Figure 26. Small plate gap and high-velocity flow pattern.
very low. The final product, however, may be extremely
viscous after separation from the vapor.
Advantages include low residence time to minimize
thermal degradation, low rates of fouling, and economical
operation.
Typical applications: concentrating soap to final product
consistency; concentrating apple puree from 25 to 40 brix,
grape puree to 50 brix, cherry puree to 60 brix, fruit juices
to 95% solids, and sugar or corn syrup solutions to over
97%; solvent stripping duties such as hexane from oil (See
also Figs. 25 and 27.)
Paraflash
Operating under a suppressed boiling, forced circulation
principle, the APV Paraflash is used to concentrate prod-
ucts subject to fouling too excessive for film evaporators.
Unlike the Paravap, vaporization does not occur within the
heat-exchanger plate pack. Instead, liquor flashes as it en-
ters a separator, crystallization takes place, and a sus-
pended slurry results. Suppressed boiling combined with
high liquid velocities deters scaling on the heat-transfer
surface, minimizes cleaning downtime, and promotes
longer production runs.
The Paraflash can be used in single or multiple effects
for such products as grape juice (tartrate crystals), coffee, Figure 27. Single-effect, forced circulation Paraflash.
wheat starch, distillery effluent, and brewer's yeast (sus-
pended solids). (See Fig. 27).
Cooling
water
Feed Process
condensate
Steam
condensate Product
Condenser Excess
vapor
Cooling Centrifugal
water compressor
Cooling Desuperheat
water
Feed
Process Process
condensate condensate Product
Figure 28. (a) Single-effect evapora-
tor, (b) Single-effect MVR evaporator.
rator is 17.50F before losses are considered. Table 4 evaporators can be calculated with a (AT (excluding losses)
shows the total temperature differences for a number of in the range of 60F.
conditions. By increasing the AT available and decreasing the AT
required, it also became possible to design multipleeffect
Centrifugal Compressors MVR evaporators. Figure 29 illustrates a double-effect
MVR system with a forced-circulation finisher operating
The relatively high volume of vapor encountered in evap-
across all effects. With this arrangement, the flow to the
orators requires the use of centrifugal compressors in
compressor is reduced and the finisher, operating at the
most cases. Initially, centrifugal compressors on steam
higher concentration, takes advantage of the full AT avail-
were limited to a compression ratio of 1.4, which, in turn,
able.
limited the available temperature difference to between
13 and 17.50F depending on boiling temperature. Only
Fans
film evaporators could use MVR since there was not
sufficient temperature difference to consider forced- The next development in MVR design was an apparent
circulation designs. Furthermore, products having signifi- reversal of prior advances.
cant boiling point elevation were excluded for this tech-
nique.
Two trends developed in recent years, however, have
increased MVR capabilities and applications.
First improved design allows centrifugal compressors to Table 4. Saturated JT(0F) at Various Compression Ratios
run at higher speeds, increasing compression ratios ap- Boiling temperatures
proximately to 2.0 to 1. Consequently, a (AT of 27-360F 0
Compression ratio 13O F 17O0F 2120F
now can be obtained and thus, MVR can be used with
forced-circulation systems and for the evaporation of prod- 1.2 6.9 8.0 9.3
ucts with boiling-point elevations. 1.4 12.9 15.0 17.5
Secondly, advances in evaporator design allow the 1.6 18.2 21.2 24.7
operation of film evaporators with a lower (AT), thereby 1.8 23.0 26.8 31.2
2.0 27.3 31.9 37.2
minimizing energy requirements. For some products, film
Centrifugal
Superheater compressor
Finisher
As the required AT across a film evaporator decreased, approximately 15,000-lb/h capacity. This generally is a
it became possible to provide that AT by using a fan. This finishing-type evaporator.
produces a compression ratio on the order of 1.2 to 1, pro- In some cases, two compressors will be arranged in se-
viding approximately 7 or 80F AT (before losses) for evap- ries as is shown in Figure 30. Here, the bulk of the evap-
oration. The MVR system previously discussed and shown oration is done in a single effect MVR system having a
in Figure 30 is typical of fan use. It should be noted that centrifugal compressor. Some of the compressor discharge
the fan MVR technique can be used only on single-effect vapor then is further compressed in a blower in order to
film evaporators handling product without significant boil- operate a finishing evaporator.
ing point elevation. Where the heat-transfer coefficient of
the product is low, it sometimes is better to make use of Estimating Compressor Power Requirements
the higher AT available from a centrifugal compressor.
Where fans can be used, however, the horsepower re- To calculate estimated power requirements for an MVR
quirement usually is less than in centrifugal compressor compressor power and AT values for both centrifugal com-
designs. Furthermore, fans do not require that the inlet pressors and fans have been plotted in Figures 31 and 32,
vapor be superheated. Instead, this is done either by a respectively. These values compare reasonably well with
separate heat exchanger using steam or by recycling some installed MVR systems.
of the compressor discharge vapor to the compressor suc- Table 5, meanwhile, compares the power requirements
tion. for different MVR designs. Note that it is possible to cal-
It is, incidentally, a common practice to use a fan evap- culate an equivalent steam economy by converting horse-
orator to concentrate a product up to a point where a large power to Btu/h and multiplying by 2545. This value then
AT is required and then to switch to a small steam or MVR is divided by the latent heat to arrive at the equivalent
finishing evaporator for final concentration. steam used.
Superheater Rotary
compressor
Centrifugal compressor
temp.
Compression
ratio
Compressors
Boiling Boiling Boiling
temperature temperature temperature
13O0F 17O0F 2120F
examined. This analysis involves Table 6 as well as the 22O0F. These values can be used to estimate the energy
steam and MVR evaporator schematics shown in Figures requirements for an evaporator operating at these condi-
28a and 29b. tions.
The first two columns of Table 6 give the properties of Looking first at the steam evaporator shown in Figure
saturated water vapor 14.7 psia, 2120F and at 17.2 psia, 29a, water at 17.2 psia, 22O0F has an enthalpy (heat con-
Boiling
temp.,
Compression
Saturated AT across fan (0F)
ratio 1.2
Fans
Boiling Boiling Boiling
temperature temperature temperature
13O0F 17O0F 2120F
Figure 32. Horsepower versus AT for fans. Note: Vapor assumed to be superheated 1O0F by ex-
ternal steam.
Table 5. Comparison of Typical MVR Designs (Approximate)"-6
Single effect fan Double effect centrifugal Triple effect centrifugal
Compression ratio 1.2 1.6 2.0
Total AT available, 0F 6.9 18.2 27.3
Vapor to compressor, Ib/h 60,000 30,000 20,000
Horsepower/1000 Ib h vapor flow 5.79 17.38 26.57
Total horsepower 374.4 521.4 531.4
Equivalent Btu 884,133 1,326,963 1,352,413
Equivalent steam, Ib/h 870 1315 1347
Equivalent steam economy 69 45.6 44.5
Average AT per effect before losses, 0F 6.9 9.1 9.1
"Boiling temperature 13O0F; evaporation rate 60,000 Ib/h.
b
Note: In this example, the fan horsepower is lower than either of the centrifugal designs, but the lower AT required the greater the surface area.
Table 6. Properties of Water Vapor In the case of the MVR evaporator, however, the vapor
Pressure, psia 14.7 17.2 17.2 at 17.2 psia, 22O0F (enthalpy 1153.4 Btu/lb) is produced
State Saturated Saturated Saturated from vapor at 2120F, 14.7 psia (enthalpy 1150.5 Btu/lb).
Temperature, 0F 212 220 243 Theoretically, only 2.9 Btu/lb of energy must be added.
//-enthalpy vapor, Btu/lb 1150.5 1153.4 1164.6 The compressor, a fan in this case, operates such that
Latent heat, Btu/lb 970.3 965.2 the entropy of the discharge vapor be at least as high as
^-enthalpy liquid, Btu Ib 180.2 188.2 the entropy of the inlet vapor. Since inefficiencies in the
S-entropy Btu/lb 1.7568 1.7442 1.7596 compression cycle will result in an exit entropy above that
of the inlet entropy, the temperature of the existing vapor
and energy input to the compressor must be increased.
Figure 33 is an enthalpyentropy diagram for water
tent) of 188.2 Btu/lb while steam at the same conditions vapor. The vapor at 14.7 psia, 2120F, is shown at point A.
has an enthalpy of 1153.4 Btu/lb. The difference between During compressions the entropy remains constant (ide-
the vapor and liquid is the latent heat or 965.2 Btu/lb. In ally) or increases (actually). With typical efficiencies for
other words, in order to produce one pound of steam at this duty, the discharge temperature may be expected to
22O0F, 17.2 psia, from water at 22O0F, 17.2 psia, the addi- rise to 2430F where the enthalpy is 1164.6 Btu/lb. The en-
tion of 965.2 Btu/lb of energy is required. ergy input from the compressor is 14.1 Btu/lb.
Superheat
available for
generating
excess vapor
Compressor
input 14.1
11.2 Btu/lb
energy
Btu/lb
compression
Ideal
H-enthalpy Btu/lb
Enthalpy Supersaturated
difference vapor
at condensing
temperatures
2.9 Btu/lb
Vapor
liquid
mixture
richer in the solute depends on the factors in equation 1: A process whereby components of a food material are
contact time, mass-transfer coefficient for the specific sys- concurrently extracted while being made soluble by micro-
tem, area of the solid exposed to the solvent, and concen- bial and chemical action complicates leaching. A good ex-
tration driving force. Diffusion in the solid is most often ample of this type of process is the batch hydrolysis of
the rate-controlling factor. Table 1 shows examples of typ- minced fish flesh processing waste by enzyme action. The
ical commercial processes in which a food is leached by a water-insoluble components are changed into soluble (di-
solvent to remove a specific solute. Note that the product gested) materials. The resultant water-based protein so-
or products can be the removed solute (eg, leaching sugar lution can be dried to produce a high-quality protein prod-
beets, vegetable oil, etc), the solid material remaining after uct for both animal and human consumption. This
extraction (eg, decaffeinated coffee, cleaned vegetables, technique is a good means for using the tremendous
etc), or both the remaining solid and solute (eg, fish oil and amounts of unused industrial fish, by-catch, underutilized
protein concentrate). edible species, and waste from processing whole fish (4).
A diagram of a semicontinuous solid-liquid extraction
system is shown in Figure 1. The pure solvent enters the
LIQUID-LIQUID EXTRACTION
extractor and leaves rich in solute while the solid that has
been placed in the extractor decreases in solute soluble Liquid-liquid extraction operations are like solids leaching
components. The rate of reaction decreases during the pro- except the food, solvent, and solute are all in the liquid
cess as the solid is depleted in solute. Because fresh solvent state. Most commercial processes are normally operated on
is passing over the solid, the extraction can continue until a continuous basis. Table 2 shows the solvent, solute, and
essentially all solute is removed from the food. If the pro- product produced from extracting some liquid raw mate-
cess is made continuous by conveying the solid into and rials. As shown in Figure 3, the ordinary extraction process
out of the reactor in one stage, the extraction normally will involves countercurrent flow to maintain the maximum
not be complete because the solid-solvent exposure time driving force. However, the relationship between the liq-
is reduced and equilibrium is not reached. Throughput can uids sometimes makes a cocurrent operation more advis-
be increased and extraction can be more complete when
able.
two or more extractors are used in series. Usually, a series
of batch-continuous reactors are connected and fresh sol-
vent is used for each reactor while the solid is moved down
the reactor series. Figure 2 shows this multiextraction pro-
cess in which three reactors are in series. If the remaining Pure Solute-rich
solid is one of the end products, it is necessary to remove solvent solvent
the residual solvent. Often this secondary process turns Solid
out to be another extraction process such as steam strip-
ping. If the solvent is water, the normal process is to re-
move it from the solid by a drying operation.
Pure Solute-rich
solvent solvent
Solid
Pure Solute-rich
solvent solvent
Solid
Figure 1. Batch solid-liquid extraction (leaching). A, Incoming
pure solvent; A, outgoing solvent rich in solute (B); B5 solute Extracted
leached from solid (C); C, original solid rich in solute (B); C, ex- solid
tracted solid depleted of solute with retained solvent (A); t, ex-
traction time. Figure 2. Batch-continuous three-phase solid-liquid extraction.
3. G. M. Pigott, "Marine Oils," in Y. H. Hui, ed., Baileys Industrial
Oil and Fat Products, Vol. Ill, 5th Ed., John Wiley & Sons, New
York, 1996, pp. 225-254.
4. G. M. Pigott, "The Status and Future of Aquatic Food Research
in the United States," Proceedings of the International Seafood
Research Meeting, Dept. of Chemistry of Fishery Resources,
Figure 3. Continuous liquid-liquid extraction. A, Incoming food Mie University, Tsu, Mie, Japan, September 30, 1994.
product rich in solute (S); A, outgoing food depleted of solute (S); 5. D. D. Duxbury, "High-Quality Flavor and Color Extracts De-
B, incoming pure solvent; B, outgoing solvent rich in solute (S); S, rived by Supercritical Extraction," Food Processing 50, 50-54
solute originally in food. (1989).
GEORGE PIGOTT
The amount of solvent remaining in the food stream is Sea Resources Engineering, Inc.
dependent on the partial miscibility of the two liquids. Of- Kirkland, Washington
ten the solute is recovered from the solvent as a viable
product, or economics and environmental factors dictate
that the solvent must be recycled. These goals are accom- EXTRUSION
plished by steam stripping, evaporation, distillation, ad-
sorption or chemical means, depending on the require-
ments and the materials. DEFINITION AND HISTORY OF USAGE
Vent port
stuffer
Extruder Extruder
drive feed
Vents Barrel
section
Heaters Screw
shafts
Cooling
BIBLIOGRAPHY
APPLICATIONS AND DESCRIPTION FOR EXTRUSION conditions used. The extruded cereals are then sugar-
COOKING OF DIFFERENT CATEGORIES OF PRODUCTS coated, if desired, and then dried or toasted in an oven as
with the other three types of extruded cereals.
Breakfast Cereals
Snacks
There are four types of breakfast cereals that can be pro-
duced by HTST extrusion cooking process: (7) extrusion Many advances have been made over the years since corn
flaked cereals, (2) extrusion gun-puffed cereals, (3) extru- collet was commercially developed in the 1940s. For ex-
sion shredded cereals, and (4) extrusion expanded cereals ample, extruded snacks now come in many different
(13). Traditional flaked cereals are produced by flaking shapes other than the common collets or curls and in many
cooked grits. Extruded flaked cereals are different from different flavors other than basic cheese/oil such as prod-
traditional flaked cereals in that the grit for flaking is ucts from potato, wheat, rice flour, or brans along with
formed by extruding the mixed ingredients with a feed starches or modified starches (2).
moisture of 25 to 35%. After exiting from the die holes, the Collet snacks can be divided into two types, baked or
product is cut off at the desired size and forms pellets. The fried, depending on the moisture of the collets (14). Baked
pellets are then dried slightly and tempered before flaking. corn collets are extruded using a collet extruder at low
This process allows additional flexibility in the ingredi- moisture (<15%) to produce highly expanded products
ents, such as multigrains or brans, used for the manufac- from degerminated corn grits. After extrusion, the collets
ture of flaked breakfast cereals. are dried (baked) in an oven and coated with flavor and oil.
Similar to extrusion flaked cereals, the first step of Fried collets are extruded from corn meal that is moistened
manufacturing extrusion gun-puffed and extrusion shred- to a higher moisture (20-30%). Product expansion takes
ded cereals is to form pellets with the HTST cooking ex- place during the deep fat frying step instead of during ex-
truders. The pellets are dried and tempered before gun- trusion. The latter partially cooks and forms the product
puffing or tempered only before shredding. Thus, the pellet shape.
moisture content for flaked and gun-puffed cereals is usu- In addition to corn meal or corn grits, potato and other
ally lower than that for shredded cereals. After flaking, grain-based extruded snacks have been developed. Some
gun-puffing, or shredding, cereals may be sugarcoated if examples are French fried potato stick, flatbread, rice
desired and then dried or toasted in an oven to impart ce- cake, and multigrain snacks. Similar to collet snacks, they
reals with a desirable toasted color and crisp or crunchy can be divided into either baked or fried types. Although
texture. the collet extruder can be used in some cases, other snacks,
Extrusion expanded cereals differ from the other three such as crispbread, may require more sophisticated extru-
types of extruded cereals in that the cereals are expanded ders such as the HTST single-screw or twin-screw cooking
into a porous matrix during the HTST extrusion cooking extruders.
process. A typical moisture content in feed is about 15 to Extruded half-products are another type of snack prod-
25%, depending on the type of extruder and the extrusion ucts. Potato and other starches or modified starches are
extruded to form very dense and thin pellets that are dried a homogeneous mass. A very accurate control of semolina
at a low temperature and controlled humidity environment flour and water are needed. Traditional pasta product
for storage stability. The half-products need to be expanded uses low-temperature extrusion (<50C). If the tempera-
by deep fat frying or baking and then enrobed with flavor- ture of the dough exceeds 6O0C, the cooking quality of the
ings before consumption. finished product will be damaged (2,18). Thus, excessive
The latest development in the extruded snacks involves heat generated from mechanical energy input must be re-
dual or coextrusion of two different components to form a moved by circulating cooling water around the extruder
single piece of snack using a specially designed die. Two barrel.
extruders may be needed although, occasionally, one of the
extruders may be substituted by a high-pressure gear
pump if the second component is pumpable. This allows BIBLIOGRAPHY
the development of many new snacks, for example, dual-
textured snack products. The flow rates of the two extru- 1. E. W. Schuler, "Twin-Screw Extrusion Cooking Systems for
ders and the viscosity of the two components must be well Food Processing," Cereal Foods World 31, 413 (1986).
regulated.
2. J. M. Harper, Extrusion of Foods, Vol. I and II, CRC Press,
Boca Raton, FIa., 1981.
Texturized Protein Meatlike Products 3. Q. Lu et al., "Model and Strategies for Computer Control of a
Twin-Screw Extruder," Food Control 4, 25 (1993).
According to Harper (2), two types of texturized meatlike
products are derived from extrusion processes. The first is 4. F. Hsieh, I. C. Peng, and H. E. Huff, "Effects of Salt, Sugar
and Screw Speed on Processing and Product Variables of Corn
the meat extender, which can be produced by a single Meal Extruded With a Twin-Screw Extruder," J. Food ScL 55,
HTST extrusion cooking step using defatted soy flours or 224 (1990).
soy grits mixed with a variety of additives. The resulting
5. F Hsieh et al., "Twin-Screw Extrusion of Rice Flour With Salt
product is highly expanded and shows distinct fiber for- and Sugar," Cereal Chem. 70, 493 (1993).
mation. Once hydrated, the products can be used to extend
6. B. W Garber, F. Hsieh, and H. E. Huff, "Influence of Particle
ground meat or meat products. This product has found ex- Size on the Twin-Screw Extrusion of Corn Meal," Cereal
tensive applications in pizza toppings, meat sauces, and Chem. 74, 656 (1997).
fabricated food formulations.
7. M. K. Kulshreshtha and C. A. Zaror, "An Unsteady State
The second type of texturized meatlike product is a Model for Twin Screw Extruders," Trans. I. ChemE., Part C,
meat analog that can be used to replace meat. The finished Food and Byproducts Proc. 69, 189 (1992).
product must be dense and have a layered fiber formation
8. G. Delia Valle, J. Tayeb, and J. P. Melcion, "Relationship of
similar to that found in real meat. Additional require- Extrusion Variables With Pressure and Temperature During
ments include maintaining a meatlike character after ex- Twin-Screw Extrusion Cooking of Starch," J. Food Eng. 6,423
tensive cooking or retorting and giving the appearance and (1987).
taste of real meat. The manufacture of meat analogs usu- 9. F. Martelli, Twin-Screw Extruders, Van Nostrand Reinhold,
ally requires multiple extrusion processes or specially New York, 1983.
cooled dies (15). 10. M. Liang et al., "Barrel-Valve Assembly Affects Twin-Screw
Extrusion Cooking of Corn Meal," J. Food ScL 59, 890 (1994).
Breadings and Croutons 11. D. W. Stanley, "Protein Reactions During Extrusion Process-
ing," in C. Mercier, P. Linko, and J. M. Harper, eds., Extrusion
The manufacture of breadings by either single-screw or co- Cooking, American Association of Cereal Chemists, St. Paul,
rotating twin-screw extruders has been described (16,17). Minn., 1989, pp. 321-341.
The starting materials are corn flour, wheat flour, or the 12. "Extruder Directory," Feed Tech 2, 32 (1998).
second clears of wheat flour. Leavening agents, dry skim
13. R. B. Fast, "Manufacturing Technology of Ready-to-Eat Ce-
milk, salt, emulsifier, and other food additives may be reals," in R. B. Fast and E. F. Caldwell, eds., Breakfast Cereals
added. Processing conditions during extrusion can be var- and How They Are Made, American Association of Cereal
ied to obtain breadings that are functionally similar to tra- Chemists, St. Paul, Minn., 1990, pp. 15-42.
ditional breadings. The extrudate is wet milled and sized 14. S. A. Matz, "Extruding Equipment," in S. A. Matz, ed., Snack
prior to drying. Croutons are made in a similar manner. Food Technology, AVI, Westport, Conn., 1984, pp. 203-230.
The small cubes are sized at the die of the extruder using
15. A. Noguchi, "Extrusion Cooking of High-Moisture Protein
a variable speed knife. Thus, the wet milling stage for the Foods," in C. Mercier, P. Linko, and J. M. Harper, eds., Extru-
extrudate is not needed. sion Cooking, American Association of Cereal Chemists, St.
Paul, Minn., 1989, pp. 343-370.
Pasta 16. O. B. Smith, "Extrusion Cooking of Corn Flours and Starches
as Snacks, Breadings, Croutons, Breakfast Cereals, Pastas,
The raw materials used in pasta products is semolina, the Food Thickeners, and Additives," in G. E. Inglett, ed., Maize:
purified middlings of durum wheat, or durum flour, water, Recent Progress in Chemistry and Technology, Academic
eggs and other ingredients (18). Commercially, pasta Press, New York, 1982, pp. 193-219.
products are formed by the extruder or continuous press 17. P. L. Noakes and W A. Yacu, "Extrusion Cooking of Wheat
with a deep flighted screw. The screw not only forces the Flour to Process Breadings," Cereal Foods World 33, 687
dough through the die, but it also kneads the dough into (1988).
18. O. J. Banasik, "Pasta Processing," Cereal Foods World 26,166 a few min), the cooking process is often referred to as high-
(1981). temperature, short-time (HTST) extrusion. The forming
extruder is used to produce special shapes from precooked
FU-HUNG HSIEH material. Typically, the operating temperature of forming
University of Missouri extruders are lower than that of cooking extruders.
Columbia, Missouri Two major types of extruders are used in the food in-
dustry: single-screw and twin-screw extruders. The twin-
screw extruders can be further classified according to the
See also EXTRUSION PROCESSING: TEXTURE AND type of screws, ie, nonintermeshing or intermeshing and
RHEOLOGY. the type of rotation, ie, corotating or counter-rotating. Use
of single-serew extruders began in the early years of the
industry and they are still used today, though the twin-
EXTRUSION PROCESSING: screw machines are becoming increasingly popular. Twin-
TEXTURE AND RHEOLOGY screw extruders are comparatively more expensive than
single-screw machines of the same production capacity.
In recent years extruders have been widely used in the The flow of material in single-screw extruders depends on
human food and animal feed industry to manufacture the friction between the barrel wall and the material.
products such as textured proteins, snack foods breakfast Hence the type of material that can be used is limited by
cereals, pasta, confectioneries, and pet foods. A list of prod- its properties; proper conditioning of the material is
ucts presently produced using the extrusion process is necessary to reduce or eliminate process instability. The
given in Table 1. The history of food extrusion has been corotating, intermeshing twin-screw extruder uses the
reviewed in Ref. 2. positive pumping characteristics created by the two inter-
The two major functions of a food extruder are cooking meshing screws to convey the material forward. This type
and forming. In the cooking process, the product is heated of mechanism reduces the need to precondition material.
through the transfer of heat energy, which is applied by Other potential advantages of the corotating twin-screw
steam injection or heaters and/or by the dissipation of extruder over the single-screw extruder include (1) narrow
viscous energy through shearing action between the rotat- residence time distribution, leading to uniform processing,
ing screw and the material. As a result of the cooking pro- (2) better mixing capabilities, and (3) wide formulations of
cess, starches are gelatinized, proteins are denatured, un- product, particularly low bulk density and high fat mate-
desirable enzymes are inactivated, and antinutritional rial that cannot be processed using a single-screw ma-
substances (eg, trypsin inhibitors in soybeans) are de- chine. The twin-screw extruder provides better control of
stroyed. Because the temperature reached during the pro- the process and more uniform product characteristics than
cess can be quite high (ca 20O0C) and the material takes a does the single-screw extruder. These advantages of the
relatively short time to travel through the extruder (5 s to twin-screw machine compensates to some extent for the
types of products (9). The first are meat analogues that are
sold in place of meat. Such products have found acceptance
in some countries, such as Japan (10). The second type of
textured plant proteins (TPP) is as a meat extender. Sev-
eral reviews on protein texturization using extruders can
be found (9,11-15). During the extrusion process in the
presence of water, globular proteins and aluerone granules
unravel and align themselves in the presence of the shear
field that exists in the extruder (14). Thermal denaturation
(loss of native structure) is also expected to occur and is
thought to be necessary for texturization (9), although
some investigators contend that denaturation is not a nec- Temperature (0C)
essary step in the texturization process (16).
The mechanism of texturization has been the subject of Figure 1. Effect of process temperature on product density.
intense research. It is generally agreed that intermolecu- Source: Adapted with permission from Ref. 25.
variable, three-level fractional factorial design to measure
the effect of extrusion of defatted soy flakes on residual
trypsin inhibition activity (TIA), Warner Bratzler shear
Figure 5. Flow pattern in an extruder barrel and die system. Shear Viscosity
Source: Adapted with permission from Ref. 66.
The rheological property that has received the most atten-
tion by scientists is shear viscosity. Some of the published
6. The free stream region, where the extrudate expan- viscosity studies are summarized in Table 3. A die or a
sion reaches an equilibrium value. viscometer (capillary or slit cross section with multiple
pressure transducers located along the wall) attached to
These flow situations of viscoelastic fluids necessitates the the extruder is often used to measure the viscosity. Alter-
measurement of rheological parameters such as steady natively, a single pressure transducer mounted near the
shear viscosity, primary and secondary normal stress dif- exit of the barrel, along with capillary dies of different
ferences, and elongational viscosity. lengths but having the same radius and entry geometry,
Two types of flows occur during extrusion cooking. The can be used to obtain the shear viscosity (77).
first is the shear flow that occurs owing to the presence of The first investigators to evaluate the viscosity of
the walls, as in the screw channel and the die. The second doughs during extrusion found that doughs exhibited
is the extensional flow that is present farther away from shear thinning behavior (68). The viscosity decreased ex-
the wall where the stream lines converge or diverge, such ponentially with temperature and was found to follow Ar-
as at the entrance and exit to the die. The stress (er) com- rhenius kinetics. Moisture was found to act as a plasticizer.
ponents in shear flow, are given by: Increased moisture content (M) decreased the dough vis-
cosity. An empirical model of the form below was proposed:
=
<?12 = W, <723 GTlS = O, ffll - ^22 = N1, 1
rjB(y, T, M) = rj*^' exp(4E/RT) exp(KM) (3)
022 - ^33 = N2 (1)
where 1 is the direction in which the fluid flows, 2 is the This model is one of the simplest and the most popular.
direction of the velocity gradient, and 3 is the remaining The following model was proposed for constant moisture
neutral direction. The shear viscosity (rjs) and the normal dough (69):
stress differences (N1, N2) are functions of shear rate. For
Newtonian fluids the shear viscosity is a constant and un- TJs(T, y, t) = rfyn-^ Qxp(AE/RT)
der simple shear flow N1 and N2 = O. exp I" k exp(AEk/RT(t))dt (4)
For extensional flows, extensional viscosity is defined
by:
In equation 4 it is assumed that the temperature is a func-
ffll - ^22
=
tfe* tion of time is known. Reactions such as gelatinization and
denaturation can lead to network formation and affect vis-
Extensional viscosity is constant for a newtonian fluid, but cosity (parameters k and AEk control the reactions). A log
it may be a function of extensional rate for non-Newtonian polynomial model was used to express viscosity as a func-
fluids. tion of moisture content, shear rate, and temperature (71).
Table 3. Summary of Viscosity Studies Conducted During Extrusionlike Processes
Product Method Moisture (% w.b.) Temperature (0C) Reference
Cooked cereal dough CDV 25-30 67-100 68
Defatted soy flour CR 32 35-60 69
Pregelatinized corn flour dough CD 22-35 90-150 70
Soy fluff CD 25.5-35.5 100-160 71
Soy flour CR 25-60 25-120 72
Corn grits SDV 20-32 100-140 73
Potato grits SDV 18-42 80-140 73
Cornstarch CDV 20-40 100-170 74
Corn grits CDV 15-30 130-180 75
Corn grits SDV 25-45 150-180 76
Note: CD, capillary die attached to the extruder; CR, capillary rheometer; CDV, capillary die viscometer is capillary die with multiple transducers along its
length; SDV, slit die viscometer is slit die with multiple transducers along its length.
To account for the shear history in the extruder, an equa- viscoelastic fluids, inelastic models are inadequate. Evi-
tion was suggested of the form (73). dence has been presented that the pressure drop experi-
enced at the entrance of the die is much greater than that
i7s(y, T9M9N) = rj*yn~l exp(4E/RT) exp(KM)N~a (5) predicted by shear viscosity alone, indicating that elastic-
ity is important (79). As will be discussed later, elasticity
The flow curves obtained using a capillary rheometer is important in the manufacture of products at tempera-
(9) and slit-die viscometer were significantly different for tures below 10O0C.
food doughs (corn grits and potato flour), whereas for low- Extruded starches are used as thickening agents or as
density polyethylene the flow curves were the same ingredients in instant foods. The viscosity of powdered ex-
whether obtained using a capillary rheometer or slit-die trudate in solvent (water) has also received attention. Typ-
viscometer. The flow behavior index was found to be af- ically, shear thinning behavior is observed in all cases. In-
fected by screw speed and temperature. This would indi- creasing the concentration of wheat starch from 5 to 9% in
cate that shear history is varying, due to different screw solution resulted in the shifting of flow behavior from al-
speeds. Hence, the Bagley procedure for obtaining the vis- most Newtonian to shear thinning (83). For plastic poly-
cosity during extrusion cooking is invalid because the fluid mers it is known that when the molecular weight is greater
entering the die is rheologically not the same for each con- than a certain critical molecular weight, non-Newtonian
dition. A model has been developed that accounts for the flow behavior is observed (81). Extruded cornstarch in so-
thermal and mechanical energy imparted to the product lution exhibited a constant viscosity at high and low shear
(shear history) before the viscosity is measured (78). rates (Fig. 6) (84). Increasing barrel temperature de-
In addition to these viscosity models, two recent models creased the values of the constant viscosities, whereas in-
are worth mentioning. They present almost identical ex- creasing moisture content was found to increase the values
pression for starch and protein doughs based on reaction of constant viscosity, ie, depended on the severity of the
kinetics (79,80). The models are cumbersome because of extrusion environment.
the large number of constants (10 or more). One notable The effect of emulsifiers on dough viscosity has also
feature of these models is the inclusion of yield stress. An- been studied (70). The presence of sodium stearoyl-2-
other study indicated that soy doughs exhibited yield lactylate (SSL) was found to affect the viscosity, whereas
stress (72). The magnitude of yield stress was found to be diacetyltartaric acid ester of monoglyceride did not affect
a function of temperature. the viscosity. Fat did not affect the viscosity when SSL was
There are several drawbacks to the existing viscosity present, but it was found to increase the viscosity in the
models. The model of Harper and co-workers (68) assumes absence of additives.
that the decrease in viscosity is due to shear thinning only.
Most plastic polymers are modeled by a network of mac- Normal Stress Difference
romolecular entanglements. Shear thinning flow is asso- It is seen from equation 1 that when N1 and N2 are not
ciated with the decrease of the entanglement density un- equal to zero the normal stresses are unequal. The pres-
der the influence of deformation of the polymer (81). For ence of unequal normal stresses can create some interest-
food doughs the decrease in viscosity is due to the sum of ing phenomena (85). The reason for nonzero values of N1
shear thinning process history (screw configuration, resi- and N2 can be attributed to the anisotropy of fluid micro-
dence time), and molecular degradation. A complete model structure in the flow field and is observed in elastic fluids
that quantifies the effect of parameters other than product (86). The ratio of primary normal stress difference to the
moisture and temperature on shear viscosity is still lack- wall shear stress is an indirect measure of the elasticity of
ing. These effects are discussed in Ref. 82, though no at- the fluid, ie, the higher the ratio, the more elastic is the
tempt has been made to quantify them. Another drawback fluid.
of these models are that the fluid is assumed to be inelastic, Measurement of normal stress differences on-line has
ie, normal stress effects are neglected. Because doughs are been a subject of intense research among polymer engi-
The exit pressure technique has been used to calculate
Raw corn the normal stress differences (87,88). As it is difficult to
measure the pressure at the die exit directly, exit pressure
is usually obtained by linear extrapolation of the pressure
profile from the region of fully developed flow in the die.
The expressions for the normal stress differences for a slit
die are (89):
1
"- - "4 + ^=]
Viscosity (Pa-s)
Extensional Viscosity
When a fluid flows from a larger to a smaller diameter tube
Exit pressure (106 [Pa])
N1 = 2PHE d}* (PHE) (Transverse slot) (7a) These equations have been derived assuming a power
a In (TW) law behavior in both shear and extensional flow. Expres-
sions for sudden contraction in cylindrical and rectangular
N2 = -PHE d^ (f "f (Parallel slot) (Tb) flow can also be found in Cogswell's paper. Several other
a In (TW)
expressions have been suggested using differing assump-
tions (118,119). There is no significant difference from the
N1 - N2 = 3PHE d^ (fHf (Circular hole) (7c)
a In (TW) values of strain rate obtained from these expression for low
die angles (<30). A spherical coordinates system was as-
where PHE signifies the elastic contribution to the hole sumed to arrive at a slightly modified expressions for equa-
pressure. Despite violations of some assumptions, reason- tions 8 and 9 (120). An alternative analysis for determining
ably good comparisons of N1 obtained from standard ge- the extensional viscosity in planar and uniaxial extension
ometries and slit die were obtained (90,96,111). However, has been proposed from entrance pressure-drop data (121-
recent numerical studies have shown the HPBL equations 123).
to be valid (113,114). Studies on extensional viscosity of food doughs are
This method is presently under evaluation in the au- scarce. A stretch-thinning behavior for corn grits using a
thors' laboratory and has yielded promising results. A po- capillary rheometer has been reported (124). Similar be-
havior for corn grits has been noted during extrusion cook- where the extrudates were cooled to below 10O0C (as in the
ing (76). Using Gibson's analysis, these authors found that forming or half-product process) before exiting the die were
the extensional viscosity decreased with increasing mois- reported (100). Extrudate swells (diameter of extrudate to
ture content. The shear component of the entrance pres- that of the die) of 1.5, 2.27, and 3.00 were obtained for
sure was less than 5%. The Trouton ratio for the doughs wheat flour, wheat starch, and manioc starch, respectively.
ranged from 80-100. Not all materials exhibit shear thin- When temperatures are below 10O0C, no water vapor is
ning and stretch-thinning behavior. Several polymeric liq- released. In such instances the expansion is due to the
uids exhibit stretch-thickening behavior while displaying elasticity of the material. A Newtonian fluid flowing out of
shear thinning behavior in shear flows. a tube would expand at low Reynolds numbers (<16) but
The entrance pressure-drop method for obtaining ex- shrink at higher Reynolds numbers (85).
tensional viscosity has not been universally accepted. The An approach commonly used to explain the extrudate
shear viscosity parameters (B and n in eq. 8) are assumed swell is the elastic recoil mechanism. When an elastic fluid
to be known a priori. These parameters can be calculated is flowing through the tube, it is subjected to extra tension
from the pressure profile and flow-rate data in the die. At along the stream lines. Once the fluid exits, the walls are
large die entrance angles, poor data fit is observed. The no longer present to constrain the flow, which causes the
assumption used in the calculation of the shear component fluid to contract along the stream lines, resulting in radial
of the entrance pressure drop can lead to error. However, expansion. The magnitude of this tension is represented
the magnitude of this error is expected to be small because by the primary normal stress difference. Expressions for
extensional flow dominates. Also, only average quantities obtaining the extrudate swell have been derived (129).
are computed, whereas in reality the stress and the rate Other factors affecting extrudate swell include surface ten-
of strain will change with position. It should be noted that sion, gravity, inertia, wall slip, temperature effects, flow
this method gives only qualitative comparisons and not de- behavior index, and extensional viscosity. In general, the
finitive data. Hence it is important that a comparison be effect of inertia, surface tension, gravity, and wall slip re-
made between the magnitude of the extensional viscosity duce the extrudate swelling, whereas temperature effects,
obtained from entrance pressure calculations with those flow behavior index, elastic recovery, and extensional vis-
obtained by other methods. Such a comparison has been cosity increase extrudate swell.
made for polymers, and the values obtained were reported The rheological phenomena involved during extrusion
to be of the same order of magnitude (125,126). cooking of foods have received some attention. The first
attempt to incorporate the effect of elasticity on extrudate
Dynamic Oscillatory Flow expansion qualitatively used pore volume as an indication
of elasticity, ie, if the pore volume was small, elastic
The dynamic properties of rice dough have been studied
effects was responsible for the expansion (58). Product
using an on-line rheometer (127). Storage and loss moduli
morphology was used to estimate dough elasticity (130).
increased with increasing frequency and decreasing mois-
These studies, along with that of Alvarez-Martinez and co-
ture content. However, these authors reported significant
workers (131), have speculated that dough elasticity is an
problems with the equipment and recommended several
important parameter that contributes to the magnitude of
modifications.
the radial expansion, although no quantification has been
attempted.
TEXTURE AND RHEOLOGY At temperatures above 10O0C the extrudate expansion
contains contributions from both the elasticity and the
The relationship between product structure and its texture moisture flash. A two-stage expansion occurs under these
is well recognized (9). The structure achieved is dependent conditions. This phenomenon has been observed and pho-
on the product composition, processing condition, and mo- tographed (132). The first stage happens immediately after
lecular configuration. Rheological properties are sensitive the extrudate emerges from the die and is due to the elastic
to changes in product composition, processing condition, effect. A few seconds after the first effect and further down-
and molecular configuration. Thus, rheological properties stream, bubble formation due to moisture vapor trying to
present themselves as a measure of product structure and escape can be observed. For high forces due to moisture
hence its texture. effects, the moisture vapor quickly finds its way out. At
One of the most important characteristics of an extru- these conditions the swelling occurs almost instantane-
date is the expansion ratio. To some extent, extrudate ex- ously. Depending on the process conditions, elastic or mois-
pansion is indirectly related to other textural properties ture effects may dominate.
such as breaking strength, bulk density, and WAI. The ex- Several investigators (58,131,133) have speculated that
pansion phenomena can be characterized in part from radial expansion alone is an insufficient parameter to
rheological parameters. Two recent articles discuss the ex- quantify extrudate expansion. It was proposed that expan-
pansion of extrudate from a rheological point of view sion occurs both radially and longitudinally and that a neg-
(100,128). ative correlation exists between the two (58). Longitudinal
During HTST (>100C) extrusion, the moisture that is expansion was defined as the mean length of unit mass of
unable to escape due to the high pressures in the die is free extrudate, or as the ratio of extrudate velocity to that of
to vaporize at or near the die exit and is assumed to be the velocity of fluid inside the die (58,131). Both these re-
responsible for the expansion of the extrudate. Expansion searchers report that longitudinal expansion is inversely
ratios as high as 15 have been obtained. Experiments proportional to the shear viscosity. However, these authors
do not give a reason why shear viscosity should be impor- rheological equation of state (one that will predict both the
tant in longitudinal expansion. viscous and elastic properties). Such equations of state
Consider the flow inside the die, where the melt adheres would be useful in numerical modeling of the food extru-
to the die but flows at a maximum velocity at the center sion process and help in developing a better understanding
(parabolic profile for a Newtonian fluid). Downstream of of the flow patterns in the extruder and aid in process con-
the die exit the velocity profile approaches that of a plug trol and product development.
flow, with all points having a uniform velocity. This means
that the surface layer must be accelerated from rest, and
NOMENCLATURE
it has been shown that conservation of mass and momen-
tum demands that this acceleration cause an extensional
A, B Constants in equations 8 and 9
flow in the surface layer while the center is decelerated and
compressed (134). This could be a possible reason for the b Slot width
longitudinal expansion. Owing to the extensional nature d Slot height
of the flow, this effects to account for extrudate swelling AE Activation energy of flow
are necessary (135). Another reason for longitudinal ex- AE^ Activation energy for cooking reaction
pansion may be the moisture vapor formed in the extru- H Slit height
date. As the vapor tries to escape from the extrudate, it
k Specific reaction velocity constant
stretches the dough. The magnitude of the expansion due
to moisture loss would depend on the extensional viscosity K Coefficient for moisture in equations 3 and 5
(biaxial extension) of the fluid. This phenomenon is similar M Moisture content
to the rise of bread during baking. The vapor pressure of in Power law index in extensional flow
the water will stretch the filament of dough that is cooling N1 Primary normal stress difference
in the ambient temperature. If the vapor pressure is suf- N2 Secondary normal stress difference
ficient to rupture the extrudate, open structures on the ex-
n Power law index in shear flow
trudate surface are produced. On cooling, the material
dries and solidifies to its final shape. P6x Pressure drop in the exit
One must caution against the use of shear viscosity to zfPshear Pressure drop due to viscous effects
explain the expansion phenomenon. It has been speculated ^Ext Pressure drop due to elongational flow
that lower shear viscosity is favorable for greater expan- zfPtot Total pressure drop
sion (41,136). Data contrary to the findings of these re-
APeni Entrance pressure drop
searchers have been presented (132). An increase in dough
moisture causes a decrease in shear viscosity, but also z/Pdie Pressure drop across the die
causes a reduction in extrudate expansion. Shear viscosity PHE Elastic hole pressure
is the least sensitive to molecular weight changes. From a Q Volume flow rate
rheological point of view, primary normal stress difference r0 Radius of the barrel
and elongational viscosity are probably far more impor- T1 Radius at the die
tant. These parameters may be able to better explain some
T Temperature
of the conflicting results that exist in the literature and
provide an insight as to why lipids, salts, and sugars be- t Time
have the way they do. Moreover, both primary normal a Half-cone angle of the die
stress difference and extensional viscosity are significantly 6 Elongational strain rate
more sensitive to average molecular weight and molecular y Shear rate
weight distribution (and hence to the structure of the ma-
T/S Shear viscosity
terial) than shear viscosity and could serve as an effective
tool in process control. rje Elongational viscosity
77* Reference viscosity
Cr1J Total stress
CONCLUSION T1J Extra stress components
Hexoses
Sphingosine
Sterol
Sterols esters
Cerebrosides
Fatty
acids
Glyceryl
Phosphatidyl Waxes Ether esters ether
esters
Fatty
alcohols
Phosphoric acid
Plasmalogens amino alcohols
Fatty
aldehydes
fatty acids starting from the carboxyl end; however, for bio- The vegetable oils and fats can be divided into three
logical activity it is interesting to number from the methyl groups on the basis of their fatty acid composition. The first
carbon, which is done by using the symbol CD. Three differ- group comprises oils containing mainly 16- and 18-carbon
ent types of fatty acids can be distinguished, the oleic type fatty acids and includes most of the seed oilscottonseed
with one double bond removed nine carbons from the oil, peanut oil, sunflower oil, corn oil, sesame oilas well
methyl end (18:lo>3). Three different types of unsaturated as palm oil. The second group comprises seed oils contain-
fatty acids can be distinguished: the oleic type with one ing erucic acid (docos-13-enoic), and includes rapeseed and
double bond removed nine carbon atoms from their methyl mustard oil. The third group is that of the vegetable fats,
end (18:lo>9 or oleic acid type); the linoleic type with two comprising coconut oil and palm kernel oil, which are
double bonds removed six carbon atoms from the methyl highly saturated and also known as lauric fats, as well as
end (18:2ctf6 or linoleic acid type); and the linoleic type with cocoa butter. The component fatty acids of some of the com-
three double bonds removed three carbon atoms from the mon vegetable oils and fats are listed in Table 5. Palmitic
methyl end (18:3co3 or linoleic acid type). The end struc- is the most common saturated fatty acid. Oils containing
ture is usually retained even if additional double bonds are high levels of linolenic acid are susceptible to rapid oxi-
introduced or if additional carbon atoms are added. Thus, dative deterioration.
linoleic acid (18:2^6) may be changed into arachidonic acid The Crucifera seed oils, including rapeseed and mus-
(20:4co6) while retaining the o>6 structure which confers tard oil, are characterized by high levels of erucic acid
essential fatty acid character to the molecule. The latter (docos-13-enoic) and smaller amounts of eicos-11-enoic
two types are now often referred to as n-6 and n-3 fatty acid. Plant breeders have succeeded in replacing virtually
acids. The high content of polyenoic fatty acids makes fish all of these fatty acids by oleic acid, resulting in what is
oils highly susceptible to autoxidation. The component now known as canola oil (8).
fatty acids of some marine and freshwater fish oils are Cocoa butter is unusual in that it contains only three
listed in Table 4 (5). major fatty acids, palmitic, stearic, and oleic, in approxi-
Considerable interest has developed recently in the mately equal proportions.
health effect of certain n-3 fatty acids, especially eicosa-
pentaenoic acid (EPA) (20:5o>3) and docosahexaenoic acid COMPONENT GLYCERIDES
(DHA) (22:6co3). These fatty acids can be produced slowly
from linoleic acid by herbivore animals, but not by hu- When a fat or oil is characterized by the determination of
mans. EPA and DHA occur in major amounts in fish from its component fatty acids, there still remains the question
cold deep waters, such as cod, mackerel, tuna, swordfish, of how these acids are distributed among and within the
sardines, and herring (6,7). Arachidonic acid is the precur- glycerides. The stereospecific numbering (sn) of glycerol for
sor in the human system of prostanoids and leukotrienes. a triacid glyceride is as follows:
Table 4. Major Component Fatty Acids of Some Marine and Freshwater Fish Oils
14:0 16:0 18:0 16:1 18:1 20:1 22:1 18:2a>6 I8:3co3 I8:4co3 20:4co6 20:5w3 22:5^3 22:6co3
Herring 6.4 12.7 0.9 8.8 12.7 14.1 20.8 1.1 0.6 1.7 0.3 8.4 0.8 4.9
Turbot 6.5 12.0 0.9 15.4 17.4 18.6 17.8 0.5 0.2 0.8 0.1 3.0 0.6 1.9
Sablefish 6.7 11.1 1.9 6.6 29.0 18.1 14.8 0.7 0.2 0.3 0.3 1.4 0.5 1.0
Cod 1.4 19.6 3.8 3.5 13.8 3.0 1.0 0.7 0.1 0.4 2.5 17.0 1.3 29.8
Sole 4.3 16.5 2.4 14.4 12.2 3.9 Tr 0.3 2.0 1.6 4.0 11.9 10.6 7.0
Halibut 0.8 9.6 9.0 2.5 12.3 4.0 5.0 Tr Tr 1.4 13.0 2.5 37.6
Carp 3.1 16.8 4.3 17.1 28.3 3.9 13.2 2.3 2.5 3.2
Trout 2.7 20.9 8.3 3.9 18.4 7.3 1.6 3.2 1.7 5.8 Tr 7.0
Catfish 1.0 15.2 3.9 2.9 29.7 0.9 10.0 0.5 0.4 0.8 0.2 0.2 0.6
Source: Ref. 5.
Note: Values are percentage of total: Tr = trace.
Table 5. Component Fatty Acids of Some Vegetable Oils
Fatty acid
Oil 14:0 16:0 18:0 20:0 22:0 16:1 18:1 18:2 18:3 Total C18
Cottonseed 1 29 4 Tr 2 24 40 68
Peanut Tr 6 5 2 3 Tr 61 22 88
Sunflower 4 3 3 4 5 9 9 6
Corn 13 4 Tr Tr 29 54 87
Sesame 10 5 40 45 90
Olive Tr 14 2 Tr 2 64 16 82
Palm 1 48 4 35 9 51
Soybean Tr 11 4 Tr Tr 25 51 9 89
Safflower Tr 8 3 Tr 13 75 1 92
Source: Ref. 10
Note: Values are weight %. Tr = trace.
CH2O2CR1 (1) bean oil are used as emulsifiers in foods. Soybean phos-
I pholipids, also known as soy lecithin, contain about 35%
R2CO2CH (2) lecithin and 65% cephalin. The acyl groups in phospholip-
I ids are usually more unsaturated than those of the tri-
CH2O2CR3 (3) glycerides in which they are present. Saturated fatty acids
are found mostly in position 1 and unsaturated fatty acids
The molecule is shown in the Fisher projection with the in position 2.
secondary hydroxyl pointing to the left. The location of
fatty acids in the various positions on the glycerol molecule UNSAPONIFIABLE COMPONENTS
can be determined by stereospecific analysis (9). Several
theories of glyceride composition have been proposed, such The unsaponifiable portion of fats consists of sterols, ter-
as even distribution, random distribution, and restricted penic alcohols, squalene, and hydrocarbons. In most fats
random distribution. The distribution of fatty acids in the the major unsaponifiable component is sterols. Animal fats
glycerides is of utmost importance for the physical prop- contain cholesterol, and in some cases, minor amounts of
erties of a fat. This is illustrated by pig fat and cocoa butter, the other sterols, such as lanosterol. Plant fats and oils
which have similar fatty acid composition. In pig fat most contain phytosterols, usually at least three and sometimes
of the unsaturation is located in the 1- and 3-positions, in four (10). The predominant phytosterol is /?-sitosterol; oth-
cocoa butter it is in the 2-position (Table 6). ers are campesterol and stigmasterol. The sterols are sol-
ids with high melting points; part of the sterols in natural
fats are present as esters of fatty acids, part in free form.
PHOSPHOLIPIDS
Cholesterol makes up 99% of the sterols offish. The sterol
content of some fats and oils is given in Table 7.
All fats and oils and fat-containing foods contain a number
of phospholipids. The lowest amounts are present in ani-
mal fats such as lard and beef tallow. In some crude vege- PROCESSING
table oils, such as cottonseed, corn, and soybean oils, phos-
pholipids may be present at levels of 2 to 3%. Phospholipids In the commercial production of fats and oils, processing
are surface active, because they contain a lipophilic and a is used to separate, purify, and modify the oils and fats to
hydrophilic portion. Since they can be easily hydrated, make them suitable for the various functions they fulfill in
they can be removed from fats and oils during the refining the food system. A large portion of the seed oils produced
process. The structure of the most important phospholipids in the temperate regions of the world are used in the form
is given in Figure 2. The phospholipids removed from soy- of solid fats: margarine, shortening, and frying and baking
Table 6. Positional Distribution of Fatty Acids in Pig Fat and Cocoa Butter
Fatty acid, mole %
Fat Position 14:0 16:0 16:1 18:0 18:1 18:2
Pig fat 1 0.9 9.5 2.4 29.5 51.3 6.4
2 4.1 72.3 4.8 2.1 13.4 3.3
3 O 0.4 1.5 7.4 72.7 18.2
Cocoa butter 1 34.0 0.6 50.4 12.3 1.3
2 1.7 0.2 2.1 87.4 8.6
3 36.5 0.3 52.8 8.6 0.4
Phosphatidylcholine
(lecithin)
Phosphatidylethanolamine
(cephalin)
Phosphatidylserine
Phosphoinositides
fats. Hydrogenation is most often used to change oils into oils are treated with bleaching earth or activated carbon.
fats. Another use for hydrogenation is to improve the oxi- The yellow-red color of most vegetable oils, mostly carot-
dative stability by partial hydrogenation to remove most enoids, is easily removed by bleaching earth. The green
of the linolenic acid. and brown pigments are more difficult to remove.
The separation of oils and fats from animal tissues is After refining and bleaching, vegetable oils are further
done by rendering, either dry rendering or steam render- processed into margarines, shortenings, and frying and
ing. The separation of oils from oilseeds usually involves a baking fats. Two-thirds of all liquid oils produced in North
pretreatment, crushing or flaking of the seeds, followed by America are used in the form of fats. Hydrogenation is
pressing (11). This is usually followed by solvent extraction used to change oils into fats, and involves the reaction of
to remove the remainder of the oil and yield a residue with gaseous hydrogen, liquid oil, and solid catalyst under pres-
less than 1% residual oil (12). sure and at high temperature (15). The catalyst used for
The crude oils obtained by rendering, pressing, and/or edible oil hydrogenation is invariably of the activated
extraction are purified by a series of operations designed nickel metal type (16). The hydrogenation reaction can be
to remove impurities that may detract from the quality of represented by the following scheme, in which the reacting
the oil. Removal of phospholipids is achieved by degum- species are the olefinic substrate (S), the metal catalyst
ming (13). The crude oils are treated with steam, which (M), and hydrogen:
hydrates the phospholipids and makes them settle out. De-
gumming can also be achieved by using solutions of phos-
phoric or organic acids. The soybean "gums" are purified
and used as food emulsifiers, known as soy lecithin.
Free fatty acids in crude oils are removed by alkali re-
fining (13). Solutions of caustic soda are used to reduce the
level of free fatty acid to 0.01 to 0.03%. Care is required to
prevent saponification of neutral oil. Removal of free fatty
acids can also be achieved by physical refining. This in-
volves treatment of the oils under vacuum with steam. The The intermediates 1, 2, and 3 are organometallic species
advantage of physical refining is that the process is similar and are labile and short-lived and cannot usually be iso-
to deodorization and these processes can be combined. A lated. In heterogeneous catalysis the metal surface per-
possible disadvantage of physical refining relates to the forms the catalytic function. In theory, the finer the par-
high temperatures (up to 27O0C) employed in this process. ticle size, the more active the catalyst will be. In practice,
This may cause randomization of the glyceride structure, however, particle size has to be balanced against filtera-
formation of dimers and conjugated fatty acids (positional bility, since removal of the catalyst at the end of the process
isomerization) and cistrans isomerization (14). should not be too difficult.
Bleaching is used to remove colored impurities, such as When hydrogen is added to double bonds in natural fats
carotenoids and chlorophyll. In the bleaching process the and the reaction is not carried to completion, a complex
Table 7. Sterol Content of Fats and Oils linoleate -^^^
Fat Sterol, % 1 ^Jr isooleate - stearate
Lard 0.12 conjugated dienes ^^
Beef tallow 0.08
Milk fat 0.3 Hydrogenation of linolenate is more complex and is greatly
Herring 0.2-0.6 dependent on reaction conditions. The possible reactions
Cottonseed 1.4 can be summarized as follows:
Soybean 0.7
Corn 1.0
Rapeseed 0.4 ^r isolinoleate^^___^
Coconut 0.08 linolenate * linoleate *- isooleate ^ stearate
Cocoa butter 0.2
^conjugated dienes-^^ I
oleate ^^^^
Fatty acid (wt %)
1 ^^^ stearate
isooleate ^^^
Although free-radical autoxidation is the primary mecha- THERMAL OXIDATION OF FATS AND OILS
nism for the formation of volatile flavor compounds from
fats and oils, photosensitized oxidation initiated by sensi- Although autoxidation is the principal mechanism for the
tizers such as chlorophyll in the presence of light should development of off-flavors in fats and oils, foods can retain
be included as oxidation mechanisms that contribute to the desirable flavors from fats and oils during deep-fat frying
formation of off-flavor volatile compounds (2,5). The reac- (10). Thermal oxidative decomposition of fats and oils oc-
curs as foods are continuously heated in oil at about 1850C
tion of fatty acids with oxygen to produce hydroperoxides
in the presence of air. The lipid decomposition mechanism
requires a change in their electron spin states because the
involved is virtually the same as in autoxidative processes,
unsaturated fatty acid and hydroperoxide are in singlet- where a hydrogen atom is abstracted from fatty acids to
states, whereas oxygen is in a triplet-state. The reaction form a fatty acid free radical, after which molecular oxygen
between singlet-state fatty acids and triplet-state oxygen reacts with the fatty acid free radical to form first the per-
to form singlet-state hydroperoxides can only occur if oxy radical, and then the hydroperoxide. The hydroperox-
enough energy is present to overcome the spin barrier. ide eventually decomposes to form volatile flavor com-
Electrophilic singlet-state oxygen can directly react with pounds. Flavor compounds formed at deep-fat frying
the electron-rich, singlet-state unsaturated fatty acids to temperatures are different from those produced at room
form singlet-state hydroperoxides. Naturally occurring temperature, where each particular pathway offlavorcom-
pigments such as chlorophyll in vegetable oils can absorb pound formation has its own activation energy. When the
ultraviolet and visible light and act as photosensitizers reaction rate (In K) versus temperature (1 /T) is plotted for
(sens) (6). The sensitizer transfers energy to triplet-state specific flavor compounds, one compound might be pro-
oxygen to form singlet-state oxygen, which reacts with un- duced at a higher rate at deep-fat frying temperatures, but
saturated fatty acids to form singlet-state hydroperoxides: when the temperature is decreased to room temperature,
another flavor compound might be produced at a higher
rate. Therefore, the formation of flavor compounds from
sens -> 1SCnS* -> 3sens* fats and oils is strongly dependent on the processing tem-
perature (11). Different fats and oils produce different vol-
3
sens* + 3O2 - 1O2 + 1SCnS atile compounds during deep-fat frying due to differences
in fatty acid composition. Corn and soybean oils produce
1
O2 + RH -> ROOH relatively large quantities of decadienals and unsaturated
aldehydes, whereas coconut oil produces more saturated
aldehydes, methyl ketones, and y and S lactones during
Singlet-state oxygen reacts directly with singlet-state deep-fat frying (12). Coconut oil, which contains 90 to 94%
double bonds of unsaturated fatty acids by an "ene" reac- saturated fatty acids, has extremely high thermal oxida-
tion to form hydroperoxides: tive stability. It has been reported that y lactones with un-
saturation at the 2 or 3 position are of particular signifi- position, a structure that is only present in fatty acids con-
cance in deep-fat-fried flavors (13). taining at least two nonconjugated double bonds. There-
fore, the higher the polyunsaturated fatty acid content in
FACTORS AFFECTING OXIDATION a vegetable oil, the more susceptible the oil is to enzymatic
oxidation and degradation.
Vegetable oils may also contain the enzyme hydro-
The rate of autoxidation in vegetable oils is affected by
peroxide lyase, which is responsible for catalyzing the for-
many factors including degree of unsaturation of fatty ac-
ids, metals, and antioxidants. For example, linoleic acid, mation of aldehydes directly from the fatty acid hydro-
peroxides formed by lipoxygenase (17). The "grassy" or
which contains two double bonds, is oxidized at a faster
"beany" flavors often attributed to fatty acid autoxidation
rate than oleic acid, which contains only one double bond.
in vegetable oils may also originate from the formation of
The relative rates of autoxidation of oleic to linoleic to lin-
olenic (3 double bonds) acid has been reported as 1:40- such volatile compounds as ds-3-hexenal and hexanal
50:100 on the basis of oxygen uptake (14). Reasons for dif- through the cleavage of hydroperoxides by hydroperoxide
ferences in autoxidative susceptibility include the fact that lyase.
the bond strength of linoleic acid (52 kcal/mole) is much
lower than oleic acid (77 kcal/mole), and linoleic acid has FLAVOR PROPERTIES OF FATS AND OILS
a higher reactivity with oxygen than oleic acid. Metals
such as copper and iron that exist in two different valence The types of volatile compounds produced from the oxida-
states play an important catalytic role in the oxidation of tion of fats and oils are strongly influenced by the compo-
fats and oils. Metals differ in their ability to catalyze the sition of the hydroperoxides formed as well as the extent
autoxidation of fats and oils depending on the concentra- of oxidative cleavage of double bonds contained in the fatty
tion, reaction temperature, and polarity of the reaction me- acids (18-20). Due to an abundance of possible reaction
dium. The addition of chelating agents such as ethylene- pathways, a variety of volatile compounds such as hydro-
diaminetetraacetic acid (EDTA), phospholipids, and/or carbons, alcohols, furans, aldehydes, ketones, and acids
free fatty acids to oils can improve their oxidative flavor are formed during oxidation. Most of the compounds re-
stability by sequestering the potentially catalytic metal at- sponsible for oxidized flavors, however, are the aliphatic
oms (15). carbonyl compounds (21). The flavor characteristics and
Natural and synthetic compounds that directly reduce corresponding threshold values of aldehydes vary as
the oxidation of fats and oils in one of three ways: (1) by shown in Table 1.
becoming oxidized themselves, (2) by donating hydrogen to
fatty acid free radicals to terminate free-radical chemical
chain reactions, or (3) by forming a complex between the CONTRIBUTION OF SPECIFIC OILS TO FLAVOR
lipid radical and the antioxidant radical. Examples of each
type of reaction can be seen here: Soybean oil, the most abundant vegetable oil in the United
States, contains approximately 7% linolenic acid. The rela-
Antioxidant (A) + O 2 -" Oxidized Antioxidant (1) tively unsaturated hydrocarbon of linolenic acid results
R- + AH -> RH + A- (2) in it being highly susceptible to oxidation and often
R- + A- - RA (3)
Antioxidants such as butylated hydroxyanisole (BHA), bu- Table 1. Flavor Characteristics and Threshold Values of
Aldehydes
tylated hydroxytoluene (BHT), tocopherols, and propyl gal-
late are commonly used in the food industry to minimize Threshold value in
the oxidation of fats and oils. The presence of light, oxygen, oil (ppm)
and high storage temperatures should be controlled to help Aldehyde Description Odor Taste
antioxidants most effectively minimize oxidative deterio- 3:0 Sharp-irritating 3.60 1.00
ration in fats and oils. 5:0 Sharp-bitter 0.24 0.15
6:0 Green 0.32 0.08
FLAVOR FORMATION BY ENZYMATIC REACTIONS 7:0 Oily-putty 3.20 0.05
8:0 Fatty-soapy 0.32 0.04
9:0 Tallowy-soapy 13.50 0.20
Flavors associated with fats and oils sometimes originate 10:0 Orange peels 6.70 0.70
through the activity of enzymes that first create fatty acid 5:1 Sharp-paint-green 2.30 1.00
hydroperoxides and then volatile secondary products (16). 6:1 Green 10.00 0.60
The release of free fatty acids through lipolytic processes 7:1 Putty-fatty 14.00 0.20
usually occurs before lipoxygenase, a major lipolytic en- 8:1 Woodbugs-fatty 7.00 0.15
zyme, can catalyze the oxidation of the polyunsaturated 9:1 Tallowy-cucumber 3.50 0.04
fatty acids linoleic and linolenic acid to hydroperoxides. 10:1 Tallowy-orange 33.80 0.15
Lipoxygenase is limited to reactions with polyunsaturated 7:2 Frying odor 4.00 0.04
fatty acids because of its substrate specificity for a cis,cis 9:2 Fatty-oily 2.50 0.46
penta-l,4-diene unit with a methylene group at the co-8 10:2 Deep-fried 2.15 0.10
responsible for the oxidation of oil to produce off-flavor ually or in combination to produce unique tastes and aro-
compounds. Soybean oil also contains photosensitizers mas. Any modification of the chemical composition of these
such as chlorophyll that produce singlet oxygen in the pres- compounds could drastically change the flavor character-
ence of light (22). Singlet oxygen can directly react with istics of food. Solid phase microextraction (SPME) is a rela-
fatty acid double bonds and oxidize the fatty acids at a rate tively new technology that holds great promise for aiding
1,500 times that of autoxidation (23,24). Analysis of head- in the evaluation of flavors by gas chromatography (30).
space has shown that 2,4-decadienals, 2-heptenal, 2,4- SPME is rapidly gaining popularity as the technique of
heptadienal, pentane, and hexanal are the principal vola- choice in the isolation and identification of volatile com-
tile compounds formed from oxidized soybean oil (25). The pounds because of its ability to integrate sampling, extrac-
flavor characteristics of oxidized soybean oil have been de- tion, concentration, and sample introduction in a single
scribed as grassy or fishy, but a single volatile flavor com- step. Both the cost and time involved with sample analysis
pound that gives unique grassy or fishy flavor in oxidized is reduced, while at the same time efficiency and selectivity
soybean oil has not been identified (26). However, trans-2- are increased (31).
hexenal and 2,6-nonadienal have been reported to give Threshold values are significantly different among fla-
general grassy flavors, whereas deca-trans-2,cis-4,trans-7- vor compounds, thus the presence of a small quantity of a
trienol and oct-l-en-3-one have been linked to fishy flavors compound with a low threshold value could have a more
(13). significant influence on the overall flavor than the presence
Vegetable oils such as corn, cottonseed, peanut, coconut, of a large quantity of a particular compound with a high
safflower, and olive oil, as well as animal fats such as lard threshold value (Table 2). Hydrocarbons, for example, have
and beef tallow provide unique flavor characteristics to a threshold value of 90 to 2,150 ppm; alkanals, 0.04 to 1.0
foods. Oil processing, which involves the three steps of re- ppm; and vinyl ketones, 0.00002 to 0.007 ppm (2). This
fining, bleaching, and deodorization, removes impurities wide range of threshold values for flavor compounds illus-
that contribute to the development of undesirable flavors. trates how one specific flavor compound could have a sig-
Olive oil, which contains 50 to 83% oleic acid, is popular in nificant influence on the overall flavor regardless of the
the United States as a result of the positive nutritional concentration. Several volatile compounds have been
implications of monounsaturated fats. The flavor com- proven to be responsible for specific described flavors in
pounds of olive oil have been separated and identified by oxidized fats, as shown in Table 3 (13).
gas chromatography-mass spectrometry. Hexanal, trans-
2-hexenal, 1-hexanol, and 3-methylbutan-l-ol, which are
SENSORY EVALUATION
formed by autoxidation, are the principal volatile com-
pounds of olive oil. Its flavor can be influenced by many
Sensory evaluation is considered the most important test
factors such as climatic and soil conditions, the maturation
to determine the flavor quality and stability of oils and is
process of the olive, and storage conditions (27). Although
therefore used to evaluate the effects of processing condi-
many volatile compounds have been identified, specific
tions, storage time and periods, and packaging environ-
chemical compounds that are responsible for olive oil's fla-
ments on the flavor of fats and oils. The most common sen-
vor have not been determined. Safflower oil, which con-
sory evaluation method involving fats and oils is a hedonic
tains 78% linoleic acid, possesses the highest content of
scale of 1 to 10; with 1 indicating a "repulsive" flavor and
polyunsaturated fatty acid of all the commercial oils. The
10 a "completely bland" flavor, as shown in Table 4 (32).
high content of linoleic acid increases the susceptibility of
Sensory evaluation can be expensive, subjective, diffi-
the oil to oxidation, resulting in the formation of off-flavor
cult to reproduce, time-consuming, and not readily avail-
compounds (28). Cottonseed oil, which contains 18% oleic
able. As a result, chemical and physical methods such
acid and 53% linoleic acid, is mainly used in restaurants
as peroxide value, thiobarbituric acid (TBA), conjugated
for frying potato chips, seafood, and snacks. The bland fla-
diene determination, fluorescence, Schaal oven test, and
vor of cottonseed oil reportedly does not mask the flavor of
active oxygen methods have been developed to more effi-
the product nor does it revert during deep-fat frying (29).
ciently evaluate the flavor quality and stability of fats and
oils. The identification of volatile compounds that are re-
DETERMINATION OF FLAVOR COMPOUNDS sponsible for specific flavors such as fishy or grassy has
been made possible by correlating sensory evaluations
with instrumental analysis such as gas chromatography.
The isolation, separation, and identification of volatile fla-
vor compounds is important to determine the chemical
mechanisms of flavor compound formation from fats and FLAVOR EVALUATION BY GAS CHROMATOGRAPHY
oils during storage, to identify chemical compounds that
are responsible for specific desirable and undesirable fla- With recent advancements in isolation techniques for fla-
vors, and to develop optimum processing and storage vor compounds, gas chromatography, and statistical anal-
methods that can minimize the undesirable oxidation of yses, several evaluations of oil flavor quality by gas chro-
fats and oils. Analysis of the flavor compounds present in matographic methods have been published (3236). These
fats and oils is difficult because of their volatility, presence papers have reported excellent correlation coefficients of
in low concentrations, and likelihood of undergoing chem- better than 0.9 between sensory scores and predicted sen-
ical alteration during isolation. Food flavors are extremely sory scores by gas chromatography of corn oil, soybean oil,
complex mixtures of volatile compounds that act individ- sunflower oil, and hydrogenated soybean oil. When com-
Table 2. Effect of Threshold Values on Flavor Significance of Soybean Oil Volatiles
Major volatiles Relative % Threshold value" (ppm) Weighted % (l-octen-3-ol) Relative order
t, t-2 ,4-decadienal 33.7 0.10 2.5 2
,c-2, 4-decadienal 17.9 0.02 6.7 1
t, c-2 ,4-heptadienal 11.1 0.04 2.1 3
2-heptenal 5.6 0.2 0.21 8
t, t-2 ,4-heptadienal 4.5 0.1 0.34 7
n-hexanal 4.5 0.08 0.42 6
ra-pentane 3.1 340 6.8 X ICT5 16
rc-butanal 1.5 0.025 0.45 5
2-pentenal 1.2 1.0 0.009 13
l-octen-3-ol 0.9 0.0075 0.9 4
2-pentyl furan 0.8 2.0 0.9 14
ft-pentanal 0.7 0.07 0.075 10
2-hexenal 0.7 0.6 0.009 13
rc-nonanal 0.7 0.2 0.026 11
tt-heptanal 0.6 0.055 0.082 9
l-penten-3-ol 0.5 4.2 8.9 X 1(T4 15
2-octenal 0.5 0.15 0.025 12
Source: Ref. 23.
a
Ref. 19.
Table 3. Compounds Responsible for Specific Flavors in isothiocyanate, the major flavor constituent of mustard,
Oxidized Fats and acetic acid and ethyl acetate, the flavor compounds in
Flavor Source compound(s) vinegar, did not change during the six-month storage pe-
riod. There was a correlation coefficient of greater than 0.9
Cardboard Non-ra7is-2,-r<ms-6-dienal between actual sensory scores of mayonnaise and pre-
Oily Aldehydes
Pent-2-enal, aldehydes
dicted sensory scores by gas chromatography. Therefore,
Painty
Fishy Deca-mAis-2,cis-4,rcms-7,trienol, oct-l-en-3-one the shelf life of mayonnaise can be accurately predicted by
Grassy Thms-hex-2-enal, nona-2,6-dienal analyzing specific compounds associated with off-flavors
Deep-fried Deca-trans-2,trans-4-dienal such as pentane and 2,4-decadienal during storage pe-
riods.
Gas chromatography can also be used to study the ef-
fects of storage conditions and processing methods on the
Table 4. Sensory Evaluation of Oil oxidation of fats and oils. Soybean and corn oils were ex-
Flavor posed to different periods of light to produce a wide range
score Description of flavor of flavor quality (38). As the period of light storage in-
creased, the amount of 2,4-decadienal (as measured by gas
10 Completely bland
9 (good) Trace of flavor, but not recognizable chromatography) increased and the sensory scores de-
8 Nutty, sweet, bacony, buttery creased. The correlation of sensory evaluation and instru-
7 (fair) Beany, hydrogenated mental analysis using gas chromatography was greater
6 Raw, oxidized, musty, weedy, burnt, grassy than 0.95.
5 (poor) Reverted, rubbery, butter
4 Rancid, painty BIBLIOGRAPHY
3 (very poor) Fishy, buggy
2 Intensive flavor and objectionable 1. M. Supran, Lipids as a Source of Flavor, American Chemical
1 (repulsive) Society, Washington, B.C., 1978.
2. E. N. Frankel, "Chemistry of Autoxidation: Mechanism, Prod-
ucts and Flavor Significance," in D. B. Min and T. H. Smouse,
eds., Flavor Chemistry of Fats and Oils, American Oil Chem-
pared with sensory evaluation, gas chromatography has ists' Society, Champaign, 111., 1985, pp. 1-37.
many advantages including rapid analysis time, conven-
3. H. W.-S. Chan, "The Mechanism of Autoxidation," in H. W.-S.
ience, low cost, and high reproducibility. A preliminary gas Chan, ed., Autoxidation of Unsaturated Lipids, Academic
chromatographic analysis of flavor compounds of mayon- Press, Orlando, FIa., 1987, pp. 1-16.
naise has been done to predict the sensory quality of may- 4. H. W. Chan and G. Levett, "Autoxidation of Methyl Linoleate.
onnaise during storage (37). Various flavor compounds Separation and Analysis of Isomeric Mixtures of Methyl Lin-
have been identified in mayonnaise including allyl isothio- oleate Hydroperoxides and Methyl Hydroxylinoleates/'LjpiWs
cyanate, acetic acid, ethyl acetate, pentane, and isomers of 12, 99-104 (1977).
2,4-decadienal. As storage time increased, levels of pen- 5. I. Lee et al., "Quantitation of Flavor Volatiles in Oxidized Soy-
tane and 2,4-decadienal increased, whereas other volatile bean Oil by Dynamic Headspace Analysis," J. Am. Oil Chem.
concentrations stayed the same. The flavor compound allyl Soc. 72, 539-546 (1995).
6. M. Y. Jung and D. B. Min, "Effects of Quenching Mechanisms 26. T. Mounts, "Processing of Soybean Oil for Food Uses," Cereal
of Carotenoids on the Photosensitized Oxidation of Soybean Foods World 34, 268 (1989).
Oil," J. Am. Oil Chem. Soc. 68, 653-658 (1991). 27. G. Montedoro, M. Bertuccioli, and G. Anichini, "Flavor of
7. H. W.-S. Chan and D. T. Coxon, "Lipid Hydroperoxides," in H. Foods and Beverages," Academic Press, Orlando, FIa., 1972.
W.-S. Chan, ed., Autoxidation of Unsaturated Lipids, Aca- 28. T. J. Weiss, Food Oils and Their Use, AVI Publishing, West-
demic Press, Orlando, FIa., 1987, pp. 17-50. port, Conn., 1970.
8. S. Kaiser et al., "Physical and Chemical Scavenging of Singlet 29. J. D. Dziezak, "Fats, Oils, and Fat Substitutes," Food Technol.
Molecular Oxygen by Tocopherols," Arch. Biochem. Biophys. 7, 65-74 (1989).
277, 101-108 (1990).
30. C. L. Arthur and J. Pawliszyn, "Solid Phase Microextraction
9. H. Sies and W. Stahl, "Vitamins E and C, ^-carotene, and other with Thermal Desorption using Fused Silica Optical Fibers,"
Carotenoids as Antioxidants," Am. J. Clin. Nutr. 62, 1315S- Anal. Chem. 62, 2145-2148(1990).
1321S (1995). 31. Z. Zhang, M. J. Yang, and J. Pawliszyn, "Solid Phase Microex-
10. W. W. Nawar, "Chemistry of Thermal Oxidation of Lipids," in traction," Anal. Chem. 66, 844A-853A(1994).
D. B. Min and T. H. Smouse, eds., Flavor Chemistry of Fats 32. D. B. Min, "Analyses of Flavor Qualities of Vegetable Oils by
and Oils, Champaign, 111., 1985, pp. 39-60. Gas Chromatography," J. Am. Oil Chem. Soc. 60, 544-545
11. S. S. Chang, R. J. Peterson, and C.-T. Ho, "Chemistry of Deep (1983).
Fried Flavor," in M. K. Supran, ed., Lipids as a Source of Fla- 33. H. P. Dupuy, S. P. Fore, and L. A. Goldblatt, "Direct Gas Chro-
vor, ACS Symposium Series 75, American Chemical Society, matographic Examination of Volatiles in Salad Oils and
Washington, D.C., 1978, p. 18-22. Shortenings," J. Am. Oil Chem. Soc. 54, 340-342 (1973).
12. M. W. Formo et al., "Composition and Characteristics of In- 34. J. L. Williams and T. H. Applewhite, "Correlation of the Flavor
dividual Fats and Oils," in D. Swern, ed., Bailey's Industrial Scores of Vegetable Oils with Volatile Profile Data," J. Am. Oil
Oil and Fat Products, Vol. 1, John Wiley & Sons, New York, Chem. Soc. 54, 461-463 (1977).
1979, p. 289-478.
35. K. Warner, E. N. Frankel, and K. J. Moulton, "Flavor Evalu-
13. W. Grosch, "Lipid Degradation Products and Flavour," in I. D. ation of Crude Oil to Predict the Quality of Soybean Oil," J.
Morton and A. J. Macleod, eds., Food Flavours, Part A, Intro- Am. Oil Chem. Soc. 65, 386-391 (1988).
duction, Elsevier, Amsterdam, The Netherlands, 1982, pp. 36. K. Robards et al., "Headspace Gas Analysis as a Measure of
325-398. Rancidity in Corn Chips," J. Am. Oil Chem. Soc. 65, 1621-
14. R. T. Holman and O. C. Elmer, "The Rates of Oxidation of 1626 (1988).
Unsaturated Fatty Acids and Esters," J. Am. Oil Chem. Soc. 37. D. B. Min and D. B. Tickner, "Preliminary Gas Chromato-
24, 127-129 (1947). graphic Analysis of Flavor Compounds on Mayonnaise," J.
15. J. Pokorny, "Major Factors Affecting the Autoxidation of Lip- Am. Oil Chem. Soc. 59, 226-228 (1982).
ids," in H. W.-S. Chan, ed., Autoxidation of Unsaturated Lip- 38. D. B. Min, "Correlation of Sensory Evaluation and Instru-
ids, Academic Press, Orlando, FIa., 1987, pp. 141-206. mental Gas Chromatographic Analysis of Edible Oils," J.
16. H. Brockerhoff and R. G. Jensen, Lipolytic Enzymes, Aca- Food Sd. 46, 1453-1456 (1981).
demic Press, New York, 1974.
17. R. Tressl and F. Drawert, "Biogenesis of Banana Volatiles," J.
Agric. Food Chem. 21, 560-565 (1973). DAVID B. MIN
DONALD F. STEENSON
18. E. Selke, W. K. Rohwedder, and H. J. Dutton, "Volatile Com-
The Ohio State University
ponents from Triolein Heated in Air," J. Am. Oil Chem. Soc.
Columbus, Ohio
54, 62-67 (1977).
19. E. N. Frankel, J. Nowakowska, and C. D. Evans, "Formation
of Methyl Azelaaldehydrate on Autoxidation of Lipids,"J. Am.
Oil Chem. Soc. 38, 161-162 (1961). FATS AND OILS: PROPERTIES, PROCESSING
20. A. C. Noble and W. W. Nawar, "Identification of Decomposi- TECHNOLOGY, AND COMMERCIAL
tion Products from Autoxidation of Methyl 4,7,10,13,16,19- SHORTENINGS
Docosahexaenoate," J. Am. Oil Chem. Soc. 52, 92-95 (1975).
21. D. A. Forss, "Odor and Flavor Compounds from Lipids," Prog. Fats and oils are key functional ingredients in a large va-
Chem. Fats and Other Lipids 13, 177-258 (1972). riety of food products. Common product applications are
22. Y. A. Tan, C. L. Chong, and K. S. Low, "Crude Palm Oil Char- baked goods, snacks, icings, confections, fried food, and im-
acteristics and Chlorophyll Content," J. Sd. Food Agric. 75, itation dairy products. Fats and oils are also key parts of
281-288 (1997). the human diet providing concentrated sources of energy
23. E. N. Frankel, "Soybean Oil Flavor Stability," in D. R. Erick- and essential nutrients. This article briefly covers the
son, et al., eds., Handbook of Soy Oil Processing and Utiliza- chemistry, processing, physical characteristics, formula-
tion, American Soybean Association, St. Louis, Mo., and tion, nutrition, and consumption of fats and oils in food
American Oil Chemists' Society, Champaign, 111., 1980, pp. applications.
229-244.
24. H. R. Rawls, and P. J. Van Santen, "A Possible Role for Singlet
Oxygen in the Initiation of Fatty Acid Autoxidation," J. Am. CHEMISTRY AND STRUCTURE
Oil Ch. Soc. 47, 121-125 (1970).
25. E. N. Frankel et al., "Comparison of Gas Chromatographic Fats and oils are predominately mixtures of triglycerides.
Methods for Volatile Lipid Oxidation Compounds in Soybean Triglycerides are the triesters of fatty acids and glycerol
Oil," J. Am. Oil Chem. Soc. 62, 620 (1985). formed as a condensation product.
6. M. Y. Jung and D. B. Min, "Effects of Quenching Mechanisms 26. T. Mounts, "Processing of Soybean Oil for Food Uses," Cereal
of Carotenoids on the Photosensitized Oxidation of Soybean Foods World 34, 268 (1989).
Oil," J. Am. Oil Chem. Soc. 68, 653-658 (1991). 27. G. Montedoro, M. Bertuccioli, and G. Anichini, "Flavor of
7. H. W.-S. Chan and D. T. Coxon, "Lipid Hydroperoxides," in H. Foods and Beverages," Academic Press, Orlando, FIa., 1972.
W.-S. Chan, ed., Autoxidation of Unsaturated Lipids, Aca- 28. T. J. Weiss, Food Oils and Their Use, AVI Publishing, West-
demic Press, Orlando, FIa., 1987, pp. 17-50. port, Conn., 1970.
8. S. Kaiser et al., "Physical and Chemical Scavenging of Singlet 29. J. D. Dziezak, "Fats, Oils, and Fat Substitutes," Food Technol.
Molecular Oxygen by Tocopherols," Arch. Biochem. Biophys. 7, 65-74 (1989).
277, 101-108 (1990).
30. C. L. Arthur and J. Pawliszyn, "Solid Phase Microextraction
9. H. Sies and W. Stahl, "Vitamins E and C, ^-carotene, and other with Thermal Desorption using Fused Silica Optical Fibers,"
Carotenoids as Antioxidants," Am. J. Clin. Nutr. 62, 1315S- Anal. Chem. 62, 2145-2148(1990).
1321S (1995). 31. Z. Zhang, M. J. Yang, and J. Pawliszyn, "Solid Phase Microex-
10. W. W. Nawar, "Chemistry of Thermal Oxidation of Lipids," in traction," Anal. Chem. 66, 844A-853A(1994).
D. B. Min and T. H. Smouse, eds., Flavor Chemistry of Fats 32. D. B. Min, "Analyses of Flavor Qualities of Vegetable Oils by
and Oils, Champaign, 111., 1985, pp. 39-60. Gas Chromatography," J. Am. Oil Chem. Soc. 60, 544-545
11. S. S. Chang, R. J. Peterson, and C.-T. Ho, "Chemistry of Deep (1983).
Fried Flavor," in M. K. Supran, ed., Lipids as a Source of Fla- 33. H. P. Dupuy, S. P. Fore, and L. A. Goldblatt, "Direct Gas Chro-
vor, ACS Symposium Series 75, American Chemical Society, matographic Examination of Volatiles in Salad Oils and
Washington, D.C., 1978, p. 18-22. Shortenings," J. Am. Oil Chem. Soc. 54, 340-342 (1973).
12. M. W. Formo et al., "Composition and Characteristics of In- 34. J. L. Williams and T. H. Applewhite, "Correlation of the Flavor
dividual Fats and Oils," in D. Swern, ed., Bailey's Industrial Scores of Vegetable Oils with Volatile Profile Data," J. Am. Oil
Oil and Fat Products, Vol. 1, John Wiley & Sons, New York, Chem. Soc. 54, 461-463 (1977).
1979, p. 289-478.
35. K. Warner, E. N. Frankel, and K. J. Moulton, "Flavor Evalu-
13. W. Grosch, "Lipid Degradation Products and Flavour," in I. D. ation of Crude Oil to Predict the Quality of Soybean Oil," J.
Morton and A. J. Macleod, eds., Food Flavours, Part A, Intro- Am. Oil Chem. Soc. 65, 386-391 (1988).
duction, Elsevier, Amsterdam, The Netherlands, 1982, pp. 36. K. Robards et al., "Headspace Gas Analysis as a Measure of
325-398. Rancidity in Corn Chips," J. Am. Oil Chem. Soc. 65, 1621-
14. R. T. Holman and O. C. Elmer, "The Rates of Oxidation of 1626 (1988).
Unsaturated Fatty Acids and Esters," J. Am. Oil Chem. Soc. 37. D. B. Min and D. B. Tickner, "Preliminary Gas Chromato-
24, 127-129 (1947). graphic Analysis of Flavor Compounds on Mayonnaise," J.
15. J. Pokorny, "Major Factors Affecting the Autoxidation of Lip- Am. Oil Chem. Soc. 59, 226-228 (1982).
ids," in H. W.-S. Chan, ed., Autoxidation of Unsaturated Lip- 38. D. B. Min, "Correlation of Sensory Evaluation and Instru-
ids, Academic Press, Orlando, FIa., 1987, pp. 141-206. mental Gas Chromatographic Analysis of Edible Oils," J.
16. H. Brockerhoff and R. G. Jensen, Lipolytic Enzymes, Aca- Food Sd. 46, 1453-1456 (1981).
demic Press, New York, 1974.
17. R. Tressl and F. Drawert, "Biogenesis of Banana Volatiles," J.
Agric. Food Chem. 21, 560-565 (1973). DAVID B. MIN
DONALD F. STEENSON
18. E. Selke, W. K. Rohwedder, and H. J. Dutton, "Volatile Com-
The Ohio State University
ponents from Triolein Heated in Air," J. Am. Oil Chem. Soc.
Columbus, Ohio
54, 62-67 (1977).
19. E. N. Frankel, J. Nowakowska, and C. D. Evans, "Formation
of Methyl Azelaaldehydrate on Autoxidation of Lipids,"J. Am.
Oil Chem. Soc. 38, 161-162 (1961). FATS AND OILS: PROPERTIES, PROCESSING
20. A. C. Noble and W. W. Nawar, "Identification of Decomposi- TECHNOLOGY, AND COMMERCIAL
tion Products from Autoxidation of Methyl 4,7,10,13,16,19- SHORTENINGS
Docosahexaenoate," J. Am. Oil Chem. Soc. 52, 92-95 (1975).
21. D. A. Forss, "Odor and Flavor Compounds from Lipids," Prog. Fats and oils are key functional ingredients in a large va-
Chem. Fats and Other Lipids 13, 177-258 (1972). riety of food products. Common product applications are
22. Y. A. Tan, C. L. Chong, and K. S. Low, "Crude Palm Oil Char- baked goods, snacks, icings, confections, fried food, and im-
acteristics and Chlorophyll Content," J. Sd. Food Agric. 75, itation dairy products. Fats and oils are also key parts of
281-288 (1997). the human diet providing concentrated sources of energy
23. E. N. Frankel, "Soybean Oil Flavor Stability," in D. R. Erick- and essential nutrients. This article briefly covers the
son, et al., eds., Handbook of Soy Oil Processing and Utiliza- chemistry, processing, physical characteristics, formula-
tion, American Soybean Association, St. Louis, Mo., and tion, nutrition, and consumption of fats and oils in food
American Oil Chemists' Society, Champaign, 111., 1980, pp. applications.
229-244.
24. H. R. Rawls, and P. J. Van Santen, "A Possible Role for Singlet
Oxygen in the Initiation of Fatty Acid Autoxidation," J. Am. CHEMISTRY AND STRUCTURE
Oil Ch. Soc. 47, 121-125 (1970).
25. E. N. Frankel et al., "Comparison of Gas Chromatographic Fats and oils are predominately mixtures of triglycerides.
Methods for Volatile Lipid Oxidation Compounds in Soybean Triglycerides are the triesters of fatty acids and glycerol
Oil," J. Am. Oil Chem. Soc. 62, 620 (1985). formed as a condensation product.
Fats and oils may contain a number of other minor con-
stituents such as waxes, gums, hydrocarbons, and fatty
alcohols. These materials are generally of little importance
and are typically handled during processing.
Fatty Acids
Fatty acid Glycerol Triglyceride
The key to understanding the chemical and physical char-
acteristics of a fat is understanding the component fatty
Triglycerides may range from solid to liquid consistency at acids that comprise the triglyceride. These can vary in
room temperature depending on the fatty acid esters they chain length (number of carbon atoms), type of carbon-
contain. Solid triglycerides are commonly called fats, and carbon bonding (saturated or unsaturated with hydrogen),
liquid triglycerides, oils. If all three fatty acids that com- and stereochemistry both within the fatty acid and its po-
prise the triglyceride are the same, it is called a single tri- sition in the triglyceride. The most common edible fatty
glyceride; conversely, if the fatty acids differ, the triglyc- acids are aliphatic, straight chain, saturated and unsatu-
eride is mixed. rated, containing an even number of carbon atoms and
Triglycerides typically comprise about 95% of fat or ending in a carboxyl group.
oil. The other components include free fatty acids, mono-
glycerides, diglycerides, phosphatides, sterols, vitamins,
natural antioxidants, color-causing pigments, minerals, O
Ii
flavor-odor compounds, and other substances. Free fatty H^C (CH^)n COH
acids are the uncombined or unesterified fatty acids pres-
ent in a fat or oil. Crude oils may contain several percent Saturated Carboxyl
fatty acids, which result from hydrolysis. The formation of aliphatic group
free fatty acids via hydrolysis leaves the partial glycerides carbon chain
(mono- and diglycerides) behind. Monoglycerides and di-
glycerides are frequently used in foods as emulsifiers. They Small amounts of odd-numbered, straight-chain acids,
are often found in functional cake and icing shortenings. branched chains, and cyclical acids are also present in ed-
They are produced commercially by the alcoholysis reac- ible vegetable oils (9,14).
tion of triglycerides or fatty acids with glycerol or by es- The length of the chain can vary in edible fatty acids
terification of glycerol with fatty acids (1). from as few as 4 carbons to as many as 24. Most fats pre-
Phosphatides are found in fat and oil from plant and dominately contain fatty acids that are 16 or 18 carbons
animal sources. These materials consist of a polyhydric al- long, although there are some exceptions like coconut oil,
cohol (usually glycerol) that is esterified with fatty acids, palm kernel oil, and butterfat, which contain high per-
phosphoric acid, and a nitrogen-containing compound. The centages of shorter (8-14 carbons) chain fatty acids.
most common phosphatide is a family of compounds found The fatty acids are classified by structure:
in soybean oil referred to as lecithin, which includes chem-
ical lecithin (phosphatidyl choline), cephalin (phosphatidyl
ethanolamine), lipositols (phosphatidyl inositol) (2). Sphin-
gomyelins are a group of phosphatides that contain no
glycerol (3). Lecithin is typically used as a food additive for
its emulsification properties. Phosphatides are essentially
removed in the refining process. Saturated
Colored materials occur naturally in fats and oils and
generally are a result of two classes of pigments. Carote-
noids and chlorophylls are the yellow-red and green colors,
respectively, found in fats. Level and type of pigment vary
greatly with the source, from the orange color of crude
palm oil due to its carotene content to the dark green color
of canola (or rapeseed) oil due to its high chlorophyll con-
tent. Vegetable oils also contain tocopherols that serve as Monounsaturated
natural antioxidants, retarding oxidation, and as a source
of the essential nutrient vitamin E. Other antioxidants
may be added to processed fats to preserve freshness (4,5).
In contrast, meat fats contain negligible levels of toco-
pherols.
Sterols are common minor components of all natural
fats and oils. Cholesterol, the infamous sterol associated
with heart disease, is the principal sterol found in animal Polyunsaturated
fats. Vegetable oils only contain trace quantities of choles-
terol. Vegetable oils contain other sterols that vary in type The more unsaturated the fatty acid, the more chemi-
and quantity with the vegetable oil source (6-13). cally reactive a fatty acid will be. Saturated fatty acids
have a higher melting point than the corresponding un-
saturated fatty acids of the same chain length. The more
unsaturated, the lower the melting point. Fatty acids with
double bonds may differ in geometric form. Orientation of
the hydrogen atoms around a double bond determines Nonconjugated Conjugated
whether the fatty acid is cis or trans. (cis-cis) (cis-trans)
Table 3. Fatty Acid Ester Melting Points, 0F cal parameters are reaction time, temperature, pressure,
Fatty acid Monoglyceride Diglyceride 0
Triglyceride catalyst type and amount, and gas purity. Vessel design to
provide effective mass and heat transfer is also critical.
C12:0 Laurie 145 136 116 Less commonly, the oil may be bleached again after hydro-
C14:0 Myristic 159 152 135 genation.
C16:0 Palmitic 171 169 146
C18:OStearic 179 175 164
Hydrogenation raises the melting point of the triglyc-
C18:lOleic 95 71 42 eride mixture, thus altering physical properties. It also
C18:lElaidic 137 131 108 improves oxidative and thermal stability by reducing
C18:2 Linoleic 54 27 8 the number of labile, polyunsaturated reaction sites in the
C18:3 Linolenic 60 10 -12 fatty acids of the triglyceride. Hydrogenation allows the
0
1,3 diglyceride
processor to differentiate products for their various appli-
cations. A processor may make a full range of products,
from salad oils to solid frying shortenings, margarines to
bakery shortenings, by hydrogenating and blending vari-
meat fats are chemically refined, but for some vegetable ous oils.
oils, notably coconut and palm, physical refining is more Deodorization typically follows hydrogenation or
economical. The choice is generally determined by the con- bleaching if natural liquid oil is desired. The process is a
venience and economics of the process. high-temperature, vacuum, steam distillation that re-
Chemical, or caustic refining, is intended to remove moves residual fatty acids as well as undesirable flavor
most of the free fatty acids present in the crude oils. The and odor compounds. This step will also remove a small
process consists of treating the crude with an alkali solu- portion of the natural antioxidants. The high-temperature
tion, which converts the free fatty acids to soap. These exposure also reduces the color due to transformation of
soaps are removed by centrifugation and water washing. the red and yellow pigments into nonchromophores. Key
Phospholipid, mucilagenous, and proteinaceous materials elements are temperature, vacuum, steam rate, and ex-
are also removed in this step. Caustic strength, tempera- posure time. Again, vessel design is critical to provide ef-
ture, mixing, contact time, and removal are critical process fective and efficient heat and mass transfer.
parameters. Liquid oils may be packaged directly after deodoriza-
The residual moisture is removed by vacuum drying tion, but fluid or plastic shortenings are usually votated,
prior to bleaching. The natural pigments, carotenes and or crystallized, after deodorization. The blended, melted
chlorophylls, are removed by physical absorption on acid- product is fed under pressure to a scraped-surface heat
activated clay or bleaching earth. Other absorbent mate- exchanger at slightly above its melting point. The product
rials such as activated carbon may also be used in specific is chilled creating crystal nuclei, which are allowed to grow
situations. The critical variables are absorbent level, con- slowly for a controlled time in a mildly agitated vessel,
tact time, temperature, and removal of the spent absorb- commonly referred to as a B unit. Nitrogen may be added
ent. Typically, hydrogenation follows bleaching. Hydrogen to gasify a solid shortening, providing a whiter, more plas-
is added to unsaturated fatty acids in this heterogeneous tic product. Proper crystal conversion may require tem-
reaction with gaseous hydrogen and catalyst, usually pering. Liquid products may be tempered in process,
nickel although other precious metals may be used. Criti- whereas solids are typically stored for 24 to 48 h at their
tempering temperature. Key parameters are flow rate, Table 4. Additives Used in Fats and Oils
temperature, and tempering conditions. Control of crystal Additive Effect
structure is essential for functional bakery shortenings.
Antioxidants
Other Processes Tocopherols Retard oxidation
There are other specialized processing steps. The most no- Butylated hydroxyanisole
(BHA)
table are winterization, fractionation, transesterification, Butylated hydroxytoluene
interesterification, and directed interesterification. Win- (BHT)
terization and fractionation separate melting fractions by fer-Butylhydroquinone
cooling the shortening and separating the solids that crys- (TBHQ)
tallize. Processors use winterization to provide stable Propyl gallate
salad oils. Fractionation consists of cooling the oil and
separating the solids a number of times to obtain various Colors
melting fractions. These are used to create hard butters ^-carotene Provides yellow color to
(cocoa butter substitutes) for coating applications and high Tumeric and annatto finished product.
stability oils. These processes may employ a solvent (hex-
ane or acetone) to improve the separation, which is com- Flavors
monly referred to as solvent winterization or solvent frac- Various acids, aldehydes, and Provide flavor and odor to the
tionation (24). ketones finished product
Transesterification, a type of interesterification, is a Phosphoric acid Metal chelators, process
process that rearranges or redistributes the fatty acids on Citric acid hydrating agents,
the glycerine backbone of the triglyceride. Processors may Dimethylpolysiloxane (methyl neutralizing agents.
select conditions to distribute the fatty acids more ran- silicone) Antifoaming agent, high-
domly, thus modifying the physical properties of the short- Polyglycerol esters temperature antioxidant
ening. This process does not create a significant level of Oxystearin Crystal inhibitors, crystal
fatty acid isomers (trans) like hydrogenation. Hydrogena- modification
tion may be combined before or after the process to allow Emulsifiers
further modification of the shortening.
Interesterification involves two or more oil sources, ran- Monoglycerides, diglycerides Emulsification, aeration,
domizing the fatty acids of the source triglycerides. By cool- Lecithin dough conditioning, wetting,
ing and removing the higher-melting triglycerides the re- Polyglycerol esters antispattering, antisticking,
Calcium/sodium steroyl separation and viscosity
action can continue with the remaining components lactylate control
redirecting the interesterification. This process, used to Lactylated monoglycerides
provide relatively pure triglycerides, is called directed in- and diglycerides
teresterification (25-27). If excess glycerol is present, Sorbitan esters
monoglycerides and diglycerides are formed. The relative Propylene glycol esters
amounts of each at equilibrium are a function of the ratio
of fatty acids available to glycerol (28). This is commonly
called glycerolysis.
Fat is multifunctional in most applications. Frying and
cooking fats provide lubricity, a heat-transfer medium, and
PROCESSING AIDS AND ADDITIVES
a flavor medium in some applications. Fats provide lubric-
A number of food-approved materials may be added at low ity and aeration in cakes and additionally structure in ic-
levels to improve processing or to protect the oil quality ings, cream fillers, and the like.
during processing (Table 4). These materials are removed
or reduced to minimal levels in the final product. Other SALAD AND COOKING OILS
additives may also be used to provide a functional effect in
the final product. These uses must comply with Food and Salad and cooking oils are usually prepared from refined,
Drug Administration (FDA) regulations covering addition bleached, and deodorized vegetable oils, or they are lightly
levels, methods of addition, permissible residual levels, hydrogenated and winterized for stability. The oil may be
and labeling. used for flavor (eg, peanut and olive oils), nutrition (eg,
corn and canola oils), and stability. Antioxidants and crys-
FATS AND OILS FUNCTIONALITY tal inhibitors may be added to salad oil (29,30). Oils may
be blended for flavor and stability, if they are intended for
Fats and oils provide several functional characteristics in heating and reuse, and dimethylpolysiloxane may also be
a variety of food products. Shortening products can provide added. Oils used in salad dressings typically have light
lubricity, structure, a heat-transfer medium, a moisture color and bland flavor and must resist clouding. Salad
barrier, and aeration. Fat systems can also act as a carrier dressing must contain a minimum of 30% oil by federal
for flavor, color, and vitamins. Oils themselves provide vi- regulation (31). Mayonnaise is an emulsified, semisolid
tal nutrition. dressing that must contain 65% vegetable oil and whole
eggs or egg yolks (32). Reduced-calorie dressings must con- GRIDDLE AND PAN FRYING SHORTENINGS
tain at least one-third fewer calories than the conventional
product. This is usually accomplished by reducing the fat Specialty colored and flavored shortenings are designed to
content and stabilizing the increased water content with replace butter or margarine in grilling, pan frying, and
gums and thickeners to provide emulsion stability. other applications (soups, sauces, gravies, basting, and
bun wash). These may be liquid or solid, resist darkening,
FRYING SHORTENINGS reduce waste (no water), and eliminate scorching (no milk
solids). Other ingredients may be added. These include salt
Frying fats must maintain stability under abusive condi- (flavor enhancement), flavorings (garlic), and even small
tions that include high temperature, extractable materials amounts of butter itself (33-36). Coconut oil may be added
from the fried food, and oxygen from the air. Stability of for abusive, high-temperature applications (37).
fried products (snack foods) is also important. The short-
ening imparts textural and flavor effects to the fried food. BAKERY SHORTENINGS
The key is the type of oil used and its chemical and physical
properties. There are now new varieties of common vege-
A variety of general and specialized shortenings are avail-
table oils with modified fatty acid compositions through able for baking applications (24,38). The principal products
breeding and genetic modification to expand the variety of
are bread, rolls, biscuits, cakes, icings, cookies, pastry,
properties available.
doughnuts, and pies. All-purpose shortening is intended to
Frying shortenings are available as meat fats, meat fat-
function adequately in a broad variety of applications from
vegetable blends, and solid or liquid vegetable shortenings. baking to frying. It is formulated to have stability, a wide
Meat fat and solid vegetable products provide excellent
plastic range for proper mixing, and some structure for ap-
stability, particularly under abusive conditions. But these
plications like icings.
products have poor nutritional attributes (cholesterol in
Cake and icing shortening is designed to meet the dual
meat fat, saturated fat, and trans fatty acids). Pourable,
needs of cake and icing applications. The shortening must
vegetable, liquid shortenings offer convenient handling
entrap and disperse air as an emulsion that is a cake batter
with good frying stability. There is some compromise on
or icing. In a cake, the fineness and amount of the air bub-
oxidative stability, but fry stability is acceptable for most
bles determine the finished height and cell structure. The
applications. Liquid products have lower saturated and shortening also lubricates the batter components and ten-
trans fatty acid levels than solid products.
derizes the cake. In icings, the shortening must provide the
Fry life is a function of the chemical and physical char-
structural properties (body and firmness) as well as its
acteristics of the frying shortening. These depend on the
creaming or aerating ability. Monoglyceride and diglycer-
source oil(s) and processing. Fry life is also a function of
ide emulsifiers are typically added to cake and icing short-
many operational factors such as the type and amount of
ening to improve the emulsifying properties. Table 6 shows
food fried, the size of the fryers, the time and temperature
the typical analytical data for all-purpose and cake and
of frying, frequency of filtration, and cleaning procedures.
icing shortenings.
Analytical characteristics vary with the product (Table 5).
The development of emulsifier technology has allowed
the formulation of specialized cake or icing shortenings
and the development of prepared mixes. Their formulation
Table 5. Typical Fly Shortening Analysis
is a function of their application: continuous versus batch
Solid Liquid
Meat fat- Partially Partially
vegetable hydrogenated hydrogenated Table 6. Typical Shortening Analyses
Analysis blend soybean soybean
Analysis All-purpose Cake and icing
Iodine value 52 69 101 (soy base) (soy base)
Mettler dropping
point, 0F 117 103 95 Iodine value 74.00 74.00
Solid fat Index Mettler dropping point, 0F 120.00 120.00
at 50 F 40 50 5 Solid fat index
at 70 F 27 36 4 at 50 F 24.00 24.00
at 80 F 23 30 3 at 70 F 20.00 20.00
at 92 F 17 14 2 at 80 F 19.00 19.00
at 104 F 12 2 2 at 92 F 16.00 16.00
Fatty acid at 104 F 10.00 10.00
composition, % Lovibond color, red,
C16 24 11 11 maximum 1.00 2.00
CIS 18 11 7 Free fatty acid, wt%,
C18:l 41 70 46 maximum 0.05 0.15
C18:2 8 2 28 Peroxide value, meq/kg,
C18:3 1 trace 3 maximum 1.00 1.00
a-monoglyceride, wt%,
Lovibond color (1.5 red maximum), free fatty acid (0.05 wt% maximum) and
maximum 3.50
peroxide value (1.0 meq/kg maximum) are identical for all products.
mixed, rich or lean formulation, liquid content, and sugar timately, which reduces flakiness, increases toughness,
content. The shortening base is formulated and processed and increases shrinkage. The shortening system contains
to obtain optimum emulsifier performance. Emulsifiers a loosely bound oil fraction to provide lubricity and ten-
generally permit a richer, moister cake due to their capa- derness to the crust.
bility to incorporate high levels of moisture in the batter Lard is the classic choice for pie shortening due to its
(Table 7). The specialized mix shortenings contain even solids content, plasticity at cool temperatures, and crystal
higher levels of emulsification and are used for consumer structure. Vegetable shortenings have been formulated to
cake mixes, leaner snack-type cake applications, or cake provide similar functional properties with an improved nu-
products where long shelf life is required (39-41). tritional (cholesterol and saturates) profile.
Similarly, emulsifier technology has allowed incorpo-
ration of high levels of moisture and air into the icing. The Puff Pastry and Danish Shortening
shortening must provide structure to allow the icing to
hold this moisture and air as well as retain its shape. Pro- Puff pastry and Danish shortenings are referred to as roll-
cessing of the shortening, particularly formulation and vo- in products because they are formed from a laminated
tation, is critical to provide this structure. Generally, cooler dough sheet, consisting of alternating layers of dough and
votation conditions improve the icing's ability to aerate, as shortening, that is traditionally formed by rolling the
measured by specific gravity, and resistance to separation coated dough sheet and folding it to form layers.
and slumping. Danish has a higher fat content than puff pastry, and
Different levels and types of emulsification are required softer-consistency products are used to achieve lubricity.
for formulations with increased moisture and aeration re- Long refrigerated retarding (dough-relaxing) steps are
quirements (Table 8). Flat or thick fudge icings require lit- used between folds to minimize toughness and maximize
tle, if any, aeration. However, butter cream and some dec- lubricity while maintaining structural integrity of the fat
orator icings require some emulsification ability, usually film. Puff pastry shortening contains higher solids for flak-
accomplished with monoglycerides and diglycerides or low iness due to the lower fat content used. This shortening
levels of polysorbates. Specialty icing products are formu- must be carefully formulated and processed so it remains
lated to produce fluffier and higher moisture-type icings. workable, not stiff, to properly apply to the dough sheet.
Polyglycerol esters or combinations of monoglyceride and Dough and shortening temperature are critical. Puff pas-
diglyceride, poylsorbate emulsifier systems are used. As try has larger expansion because of the number of layers
the level of emulsification increases, the structure pro- and the water vapor sealed by the shortening between the
vided by the shortening becomes more critical to icing per- dough layers.
formance. Butter was originally used for these applications. Puff
pastry and Danish are formulated to have similar compo-
Breads and Rolls sition (fat, moisture, and salt) and functionality and may
be butter flavored as well.
Shortening is added at relatively low levels to breads for
lubricity, softening, and shelf life. Structure is primarily
obtained from starch and protein complexes. Emulsifiers OTHER APPLICATIONS
are employed as dough conditioners to resist staling (dry-
ing) (Table 9). These may be added either as part of the
There are a number of other specialized shortening appli-
shortening or hydrated first by heating in water until a
cations. Confectionery fats are primarily intended to be
liquid crystalline phase (mesophase) is formed and main-
substitutes or extensions for cocoa butter in confections
tained by cooling the mixture. Biscuit shortenings are for-
and coatings. These consist of lauric-based products (co-
mulated to blend as small, discrete chunks into the cold
conut and palm kernel oils), which may be hydrogenated,
dough, yet still provide sufficient solids for a flaky, tender
fractionated, or interesterified to better match the solids
texture.
profile and melting point of cocoa butter. Domestic substi-
tutes may be hydrogenated or fractionated as well (18-42-
Pie Crust Shortening
45). These do not generally have the same crystal type as
Pie shortenings are also mixed loosely into the cold dough cocoa butter, and they do not require tempering. Eating
to maintain separate fat layers for a flaky crust. Overmix- quality, snap, mouth melt, and glossy appearance are key
ing, or mixing too warm, incorporates the shortening in- performance factors. Coatings provide a moisture barrier
Fat replacers may be used for multiple purposes. One moti- Table 2. Why People Used Reduced-Fat Products
vation is to facilitate a reduction in total and saturated fat
consumption by maintaining the appeal of foods reduced in fat Percentage of
content. The goal of fat reduction is to decrease the incidence adult Americans
of obesity and chronic diseases. A second purpose may be to Reason citing
reduce total energy consumption to improve health and en- To stay in better overall health 77
hance physical appearance and self-concept. A third option en- To eat or drink healthier food and beverages 71
tails using fat replacers to increase the volume of palatable To reduce fat 68
foods that may be consumed without increasing fat or energy To reduce cholesterol 61
intake. (5) To maintain current weight 57
To reduce calories 56
To maintain an attractive physical appearance 52
To reduce weight 43
According to Calorie Control Council research, the pri- For refreshment or taste 39
mary reason people use reduced-fat foods is to stay in bet- To help with a medical condition 31
ter overall health (see Table 2). Not surprisingly, a food's
fat content is the first item shoppers look for when reading Source: Calorie Control Council 1998 National Survey.
a nutrition label (6). Yet even though consumers seem in-
creasingly committed to lowering their dietary fat intake, year before. By 1995 the number of fat-modified products
they continue to rank taste as their top consideration when had risen to 8500 (9,10).
selecting food (see Table 3). And few nutrients affect the
taste and overall sensory experience of food more than fat.
Fat not only adds aroma and flavor to food, but also COMPOSITION OF FAT REPLACERS
influences palatability, flakiness, creaminess, and crisp-
ness. And to most people, the textureor mouth-feelof Focus groups conducted by the International Food Infor-
food ranks alongside taste as an important selection cri- mation Council suggest that there is a lack of knowledge
terion. From the creaminess of ice cream, to the moist ten- concerning fat replacers among consumers as well as
derness of cake, to the crispness of potato chips, fat is a among health professionals. For example, very few con-
critical component. Thus, removing fat from a food can af- sumers realized that the fat removed from low- and
fect far more than taste. Research has shown that most reduced-fat foods is replaced with another ingredient. And
consumers, when given a food from which the fat has been although health professionals understood that product re-
removed and no replacement added, find the food unac- formulation replaced the taste and texture of fat, they typ-
ceptable (7). The delicate balance between fat and a pleas- ically had very little specific information (11).
ant sensory experience can be seen in the home-cooking Usually a fat replacer is not itself a fat. Some fat re-
arena as well. Home bakers can replace some of the fat or placers, however, are lipids, but because of their structure,
oil in muffins and cakes with applesauce or pureed prunes. they may be undigestible or only partially digestible. Most
But removing all the fat will result in unacceptable ap- fat replacers are limited in their use. Some are good thick-
pearance, texture, and taste. ening agents; others provide creaminess; still others make
Responding to a market that is ripe for low- and food moist. Having a variety of fat replacement options
reduced-fat foods (see Table 4 and 5), manufacturers have available allows manufacturers to use a "systems ap-
made fat modification an increasingly important aspect of proach" to formulating low-fat and fat-free foods with the
their research and development. Their objective is three- functional and sensory characteristics of their full-fat
fold: to create food products that qualify for nutrient counterparts. The combination of fat replacers used in a
content/health claim status (see Table 6); to capture the product depends on which properties of that product are
sensory attributes and functionality of fat; and to achieve being duplicated. Combinations may include proteins,
all of this cost effectively. In 1990 Healthy People 2000 starches, dextrins, maltodextrin, fiber, emulsifiers, and fla-
called on the food industry to create 5000 reduced-fat foods voring agents. Some fat replacers are themselves blends of
over the next decade. By 1992 manufacturers had exceeded various ingredients (see Table 7).
that goal by 600 (8). In 1990 alone, the food industry rolled
Types
out more than 1400 products bearing a reduced- or low-fat
label claimup 70% from the number of such products the Fat replacers fall into three functional categories (5,7,12):
Table 3. Importance of Various Factors in Food Selection: 1994-1998
Percentage of consumers saying "very important"
Factor 1994 (%) 1995 (%) 1996 (%) 1997 (%) 1998 (%)
Taste 90 90 88 87 89
Nutrition 76 74 78 77 76
Product safety 69 69 75 73 75
Price 70 69 66 66 64
Source: Ref. 1.
Table 4. Percentage of Consumers Who Eat Various loric; those based on starch and protein provide 4
Reduced-Fat Foods kcal/g.
Among shopper segment 2. Low-calorie fats include products such as caprenin
% Total % Healthy % Nutritionally and salatrim, both of which provide 5 kcal/g. They
Food who eat eaters apathetic are metabolized more like carbohydrate and are rap-
idly used as energy rather than stored as fat.
Salad dressing 68 78 49
Mayonnaise 55 60 39 3. Fat replacers, substitutes, or analogs are similar to
Crackers 53 61 35 fats and oils in function and in sensory properties.
Icecream 52 60 35 Theoretically, they can replace fat on a one-to-one
Chips 51 57 40 weight basis. Generally, they are heat stable and
Cookies 51 54 40 can be used for frying. Fat replacers provide O to 3
Source: Ref. 6. kcal/g. Olestra is a zero-calorie fat replacer.
Derivations
Table 5. Most Popular Reduced-Fat Products Fat replacers are also classified according to the sub-
Percentage of stances from which they are derived (see Table 8). Carbo-
adult Americans hydrate- and protein-based fat replacers are fat mime tics;
Product who consume fat-based fat replacers are low-calorie fats or fat replacers
(5,7,13):
Skim or low-fat milk 62
Salad dressings/sauces/mayonnaise 56
Margarine 44 Carbohydrate-based. Carbohydrates such as
Chips/snack foods 40 starches, fibers, cellulose, and gums are commonly
Meat products 39 used in low-fat and fat-free foods as texturing agents,
Ice cream/frozen desserts 36 bulking agents, moisturizers, and stabilizers. Car-
Cakes/baked goods 32 bohydrate-based ingredients provide O to 4 calories
Dinner entrees 30 per gram.
Candy 18
Protein-based. Milk, egg, or whey protein is heated
Source: Calorie Control Council 1998 National Survey. and blended at high speed to produce tiny particles
that feel creamy to the tongue. This process is called
microparticulation. Protein-based ingredients also
Table 6. Food Label Nutrient Content Claims help to stabilize emulsions in sauces, spreads, and
salad dressings. These ingredients are fully absorbed
Claim0 Criterion by the body and range in calories from 1 to 4 kcal/g,
Fat free Less than 0.5 fat depending on degree of hydration.
Low fat 3 g or less of fat Fat-based. Some fat-reduction ingredients are actual
Reduced or less fat At least 25% less fat6 fats designed to contribute fewer calories and less fat
Light One-third fewer calories or 50% less fat6 to foods. Others, such as olestra, are structurally
"The Food and Drug Administration and the U.S. Department of Agricul- modified to be calorie-free.
ture have established specific regulation concerning allowable nutrient con-
tent claims. The following claims are defined for one serving.
6
As compared with a standard serving size of the traditional food. NUTRITIONAL IMPACT OF FAT REPLACERS
ories expended. Fat-modified foods are but one tool that fat is needed simply to prevent weight gain, even if fat in-
can be used to create this energy balance. take is moderate. But increased fat consumption coupled
The theory is that people may be cutting down on fat with stagnant-to-falling exercise rates is the magic for-
consumption, but by overindulging in fat-modified foods, mula for positive energy balance and weight gain.
they are consuming extra calories and dramatically tip- Another often overlooked fallacy in the theory that fat-
ping the energy balance toward obesity. But the fact is that modified foods have led to obesity concerns timing. Re-
despite the proliferation of low-fat and fat-free foods, cently released population figures on obesity were com-
Americans are actually eating more fat than in the past. piled as of 1990when 33% of the American public was
Although between the 1970s and the 1990s, Americans de- identified as overweight. The market influx of fat-modified
creased their intake of fat from approximately 37% of cal- foods, however, didn't peak until 1995 (14). In addition,
ories to approximately 34% of calories, this drop in percent first-generation fat-modified foods of the 1980s were far
of calories from fat represents neither a decrease in calories less palatable than today's low-fat and fat-free products. A
nor a decrease in fat grams. Over the same 20-year time proliferation of good-tasting fat-modified foods in the
span, the average adult's daily calorie intake increased 1990s can't be blamed for obesity statistics based on 1980s
by 300, and total fat gram consumption increased from data.
about 81 g/day to 83 g/day (13). At 9 calories per gram, this
2-g/day increase in consumption adds up to about 540 ex- Satiety
tra calories per month, or almost 6500 extra fat calories
per year. Bell and colleagues have demonstrated that people eat to
In addition, the 1996 National Institutes of Health Con- a certain volume, rather than to a calorie count (15). Diets
sensus Conference Statement on Physical Activity and high in fat are calorically dense and highly palatable, but
Cardiovascular Health identified physical inactivity as a they are generally less satiating than diets high in carbo-
major U.S. public health crisis. Inactivity reduces muscle hydrates. Although once in the intestine, fat seems to cre-
mass, which translates into fewer calories burned, even at ate strong signals of satiety, the "I'm full" feeling is delayed
rest. When physical activity is low, a reduction in dietary because of the time it takes time for fat to reach the intes-
Table 8. Example Fat Replacers: Ingredients and Applications
Type Brand name(s) Ingredients Applications
Protein-based fat replacers
Microparticulated Simplesse Milk and/or egg/white proteins, Imparts fatlike creaminess and richness but
protein K-Blazer sugar, pectin, citric acid no fat flavor; not heat stable; 1-2 kcal/g;
digested as protein; used in ice cream,
butter, sour cream, cheese, yogurt
Modified whey Dairy-Lo Whey or milk protein concentrate Improves texture, flavor, stability of low-fat
protein foods; 4 kcal/g; used in frozen dairy
desserts, hard and processed cheese, sour
cream, dips, yogurt, sauces, baked goods
Isolated soy protein Supro Used in foods for 35 years; added
ProPlus to meat to reduce fat
Supro Plus
tinal tract. Large amounts of energy-dense fat can be in- weight, fat replacers may be a useful tool for helping man-
gested before satiety signals kick in. Thus, eating high-fat age both fat and calorie intake (23-25).
foods leads to what researchers call "passive consumption" When research participants did know that a fat replacer
or high-fat hyperphagiathat is, a tendency to consume had been added to their food, compensation behavior re-
excess energy (16). mained negligible. In a 10-day study of 96 habitual potato-
Because of the weak effect it has on satiety, removing chip eaters, some individuals who knew they were eating
some fat or substituting for it does not substantially de- fat-free potato chips ate a few more chips. Most partici-
crease the satiating effect of a food, but it can result in pants however, ate the same amount of chips regardless of
fewer calories being eaten. Consequently, lower-fat diets whether or not they knew they were eating full-fat chips
including use of fat-modified foods, rather than contribut- or chips made with a fat replacer. It is important to note
ing to obesity, actually have the ability to reduce the pas- that all participants eating chips made with a fat replacer
sive consumption of excess calories. CSFII data from 1995 benefited from both a fat and a calorie reduction (26).
show that adults who used more fat-modified foods also In another study examining the behavioral aspects of
consumed less energy overall (17). In addition, research by compliance with a low-fat diet, two groups totaling 44
Arsenault and colleagues and by Sigman-Grant demon- women attempted to maintain a diet having less than 30%
strates that individuals who consume fat- and calorie- of calories from fat. Women who were allowed to use prod-
reduced foods have a more nutrient-dense diet than those ucts with fat replacers reported feeling less deprived be-
who do not (18-20). cause they had a wider range of foods from which to choose
(27). A six-month study conducted by Westerterp and col-
Compensating Behaviors leagues tracked 217 free-living, nonobese men and women
who received either reduced-fat or full-fat products. At the
Probably the most common argument used to support the end of the intervention, study participants in the reduced-
notion that overindulging in fat-modified foods is respon- fat group had consumed fewer calories and had not gained
sible for obesity is the compensation theorythat people weight. The control group, however, showed both an in-
equate "fat-free" with "low-calorie" and therefore eat more. crease in calorie intake and weight (28). Similarly, in a
Most of the research on dietary compensation and fat re- recent three-month trial, conducted by Kelly and col-
placers has been done on olestra, available under the leagues, study participants consuming a full-fat diet
brand name Clean. gained weight, whereas those consuming foods made with
Among individuals who did not know a fat replacer had a fat replacer did not (29).
been added to their diet, researchers have observed two
behaviors, depending on participants' ability to regulate
calories. The research has shown that children and young REGULATING FAT REPLACERS
adult males, who generally regulate calories well, did com-
pensate for the energy deficit created by fat replacement The 1958 Food Additives Amendment to the Federal Food,
(21,22). In both groups, however, compensation was not Drug and Cosmetic Act requires that the Food and Drug
100% nor was it fat-specific. Consequently, although these Administration (FDA) approve all food additives prior to
children and lean young men did compensate for calories, their use. Manufacturers must submit a food additive pe-
they nevertheless consumed a diet that was lower in fat. tition (FAP) to FDA, detailing the additive's production, its
Researchers also studied a group of 105 individuals who expected consumption level (average as well as 90th per-
do not regulate calories well. Among these participants, centile); exposure by age group; and its safety profile, in-
they observed both a decrease in the percentage of calories cluding for potentially sensitive subpopulations. When
from fat and in total calories consumed. These preliminary Congress enacted this legislation, it exempted (with some
findings indicate that for people who need to control body qualifications) two groups of substances:
"Prior-sanctioned substances" are those which the seeking GRAS status for a food component and filing a pe-
FDA or the USDA had determined prior to 1958 as tition for approval of a food additive, however, is that the
safe for use in foodfor example, sodium nitrate and safety information about a GRAS substance is available in
potassium nitrate used to preserve luncheon meats. the scientific literature and readily accessible to the man-
GRAS substances are substances in use before 1958 ufacturer, whereas safety information for the food additive
that are "generally recognized as safe" by scientific may not yet be published. Acting independently from the
experts based on the substances' history of use in food FDA, manufacturers can convene a panel of experts to re-
or on scientific procedures. If a substance was not in view the scientific information and determine whether or
use in foods before 1958, its safety must be deter- not a substance should be considered GRAS for a specific
mined based on scientific procedures. Common GRAS use.
substancesamong the several hundred used in The majority of fat replacers have garnered approval
foodare sugar, baking soda, and vitamins. through the GRAS procedure (eg, various carbohydrate
polymers, gums, gels and starches; microparticulated pro-
Establishing GRAS status and filing a FAP require teins; whey proteins; and fat emulsifiers). Procter & Gam-
similar scientific support. One key difference between ble's caprenin offers a good example of an independent
ANALYSIS
FIBER, DIETARY
The different chemical properties of the various compo-
Dietary fiber is a general term for plant polysacharides and nents of dietary fiber make it quite challenging to deter-
lignin that are not broken down by the digestive enzymes mine the fiber content of various plants and foods. Early
of human beings. Dietary fiber is found in plant cell walls, methods for isolating dietary fiber commonly destroyed
mucilages, gums, and algal polysaccharides. Synthetic many of the water-soluble components of the fiber matrix.
polysaccharides used in the food industry are also consid- The term crude fiber is used to describe fiber content de-
ered dietary fiber. Resistant starch, starch that is not di- termined by an acid and alkali extraction. A rapid, reliable
gested in the small intestine, is chemically and physically method of determining total dietary fiber content (water
similar to other nondigestable polysaccharides and also soluble and insoluble) has been recommended by the As-
may be included in the definition of fiber. Many compounds sociation of Official Analytical Chemists (AOAC). This
with a wide range of physical and chemical properties are methodology combines gravimetric and enzymatic pro-
referred to as dietary fiber. In a single plant, the fiber com- cesses and is appropriate for measuring dietary fiber con-
position of the stem or leaves is very different from the tent of foods for labeling purposes. Analysis of the individ-
fiber in the fruit or seeds. Dietary fiber is not a uniform ual components of dietary fiber is much more complex. The
substance and every plant has a unique dietary fiber best known procedure, developed by Southgate (1), re-
makeup. Because dietary fiber includes many compounds moves the individual fractions of dietary fiber through a
with very different physicochemical properties, it is diffi- series of extractions. The addition of gas liquid or liquid
cult to characterize. Division of fibers by their solubility in chromatography allows for the identification of individual
water is the most common method of classification, and is sugars present in each fraction.
convenient because many of the physiological properties of
fiber seem to be based on this physical property. As a rule,
water-soluble fibers form viscous solutions and are used in PHYSICOCHEMICAL PROPERTIES
the food industry as emulsifiers, food thickeners, and gel-
ling agents. In the body, soluble fibers are associated with Every fiber source has unique physicochemical properties
lipid and carbohydrate metabolism. Insoluble dietary fi- that elicit variable physiological responses in the body and
bers, such as those found in wheat bran, tend to contribute allows for a wide range of uses in the food industry. These
to fecal bulk and decreased intestinal transit time. properties are variable and are influenced by factors such
as particle size (coarsely ground wheat bran versus finely
ground bran), cooking or freezing, and breakdown of the
COMPONENTS matrix during digestion. Properties such as water-holding
capacity or the hydration of dietary fibers to form a gel
Complex polysaccharides from plants are divided into sev- matrix influence the viscosity of the gastrointestinal con-
eral distinct groups based on chemical structure. The most tents and can increase fecal bulk and stool softness. Ad-
common structural component of the cell wall is cellulose. sorption and binding of organic molecules is also an im-
Cellulose is composed of long linear chains of glucose mol- portant trait of dietary fibers. Polysaccharides with an
ecules (approx. 10,000) with beta 1-4 links, which cannot electrical charge, such as pectin and lignin, are known to
be broken down by digestive enzymes. The hemicelluloses sequester or bind bile acids and increase their excretion.
24. J. O. Hill et al., "Effects of 14 Days of Covert Substitution of found in plants are a heterogeneous group of compounds
Olestra on Spontaneous Food Intake," Am. J. Clin. Nutr. 67, that contain a variety of different sugars arranged in a
1178-1185(1998).
primary chain or backbone, with numerous side chains.
25. C. deGraff et al., "Nonabsorbable Fat (Sucrose Polyester) and The specific names of the hemicelluloses are based on their
the Regulation of Energy Intake and Body Weight," Am. J.
Physiol 270, R1386-R1393 (1996).
sugar content, such as xyloglucans (xylose and glucose),
glucomannans (glucose and mannose), and arabinoxylans
26. D. L. Miller et al., "Effect of Fat-Free Potato Chips With and
Without Nutrition Labels on Fat and Energy Intakes," Am. J.
(arabinose and xylose). Solubility in water is dependent on
of Clin. Nutr. 68, 282-290 (1998). the sugar components and the physical structure of the
27. M. P. Bolton, P. W. Pace, and R. S. Reeves, "Use of Olestra
individual hemicellulose, but most compounds in this
Products in a Nutrition Education Program," Journal of Nu- group are soluble in dilute alkali. Pectin from plants refers
trition in Recipes and Menu Development 2, 33-42 (1996). to a complex mixture of substances that is composed of a
28. K. R. Westerterp et al., "Dietary Fat and Body Fat: An Inter- galacturonic acid core esterfied with methyl groups on the
vention Study," International Journal of Obesity 20, 1022- uronic acid residues. Rhamnose is also found in the back-
1026 (1996). bone of pectins. Pectin is water soluble and used to produce
29. S. M. Kelly et al., "A 3-Month, Double-Blind, Controlled Trial highly viscous gels, whereas protopectins are insoluble.
of Feeding With Sucrose Polyester in Human Volunteers,"^ The only nonpolysaccharide included in the definition of
J. Med. 30, 41-49 (1998). dietary fiber is lignin. The lignins consist of chains of
phenyl propane residues that cement and anchor the cell
wall matrix and stiffen the plant tissue. As plants grow
SUZETTE MIDDLETON and age they undergo a process of lignification, and the
Procter & Gamble Co.
Cincinnati, Ohio dietary fiber makeup changes over time.
ANALYSIS
FIBER, DIETARY
The different chemical properties of the various compo-
Dietary fiber is a general term for plant polysacharides and nents of dietary fiber make it quite challenging to deter-
lignin that are not broken down by the digestive enzymes mine the fiber content of various plants and foods. Early
of human beings. Dietary fiber is found in plant cell walls, methods for isolating dietary fiber commonly destroyed
mucilages, gums, and algal polysaccharides. Synthetic many of the water-soluble components of the fiber matrix.
polysaccharides used in the food industry are also consid- The term crude fiber is used to describe fiber content de-
ered dietary fiber. Resistant starch, starch that is not di- termined by an acid and alkali extraction. A rapid, reliable
gested in the small intestine, is chemically and physically method of determining total dietary fiber content (water
similar to other nondigestable polysaccharides and also soluble and insoluble) has been recommended by the As-
may be included in the definition of fiber. Many compounds sociation of Official Analytical Chemists (AOAC). This
with a wide range of physical and chemical properties are methodology combines gravimetric and enzymatic pro-
referred to as dietary fiber. In a single plant, the fiber com- cesses and is appropriate for measuring dietary fiber con-
position of the stem or leaves is very different from the tent of foods for labeling purposes. Analysis of the individ-
fiber in the fruit or seeds. Dietary fiber is not a uniform ual components of dietary fiber is much more complex. The
substance and every plant has a unique dietary fiber best known procedure, developed by Southgate (1), re-
makeup. Because dietary fiber includes many compounds moves the individual fractions of dietary fiber through a
with very different physicochemical properties, it is diffi- series of extractions. The addition of gas liquid or liquid
cult to characterize. Division of fibers by their solubility in chromatography allows for the identification of individual
water is the most common method of classification, and is sugars present in each fraction.
convenient because many of the physiological properties of
fiber seem to be based on this physical property. As a rule,
water-soluble fibers form viscous solutions and are used in PHYSICOCHEMICAL PROPERTIES
the food industry as emulsifiers, food thickeners, and gel-
ling agents. In the body, soluble fibers are associated with Every fiber source has unique physicochemical properties
lipid and carbohydrate metabolism. Insoluble dietary fi- that elicit variable physiological responses in the body and
bers, such as those found in wheat bran, tend to contribute allows for a wide range of uses in the food industry. These
to fecal bulk and decreased intestinal transit time. properties are variable and are influenced by factors such
as particle size (coarsely ground wheat bran versus finely
ground bran), cooking or freezing, and breakdown of the
COMPONENTS matrix during digestion. Properties such as water-holding
capacity or the hydration of dietary fibers to form a gel
Complex polysaccharides from plants are divided into sev- matrix influence the viscosity of the gastrointestinal con-
eral distinct groups based on chemical structure. The most tents and can increase fecal bulk and stool softness. Ad-
common structural component of the cell wall is cellulose. sorption and binding of organic molecules is also an im-
Cellulose is composed of long linear chains of glucose mol- portant trait of dietary fibers. Polysaccharides with an
ecules (approx. 10,000) with beta 1-4 links, which cannot electrical charge, such as pectin and lignin, are known to
be broken down by digestive enzymes. The hemicelluloses sequester or bind bile acids and increase their excretion.
It is hypothesized that in the intestine dietary fiber is re- levels. In the colon, most soluble fibers are degraded by the
sponsible for binding or adsorbing toxic and mutagenic microflora and produce short chain fatty acids (SCFA). It
substances, thus enhancing their removal from the body. has been hypothesized that SCFA absorbed from the colon
Dietary fiber also has the capacity to act as a cation ex- may directly inhibit cholesterol synthesis in the liver.
changer in the intestine. Minerals and electrolytes can High-fiber diets also alter the structure of the intestine. In
bind to fiber, potentially decreasing their absorption in the experimental animals, intestinal length is increased and
digestive tract. An additional characteristic of fiber is the there is a marked increase in mucosal and muscle mass
ability to undergo degradation or fermentation by micro- following fiber consumption (4). It is assumed that mor-
flora of the large intestine. Water-soluble fiber sources phological changes in the intestine alter absorption pat-
such as pectin or gums may be totally degraded in the terns thus influencing metabolic processes in the body.
colon, whereas cellulose, being a tightly packed linear in- Many varieties of soluble fibers influence the rate of car-
soluble polysaccharide, is almost totally resistant to fer- bohydrate digestion and absorption. It has been shown
mentation by the human colonic flora. In plant tissues a that when certain fibers are added to test meals, postpran-
mixture of polysaccharides and lignin is produced making dial glucose and insulin levels are decreased (5). In addi-
it difficult to accurately predict their physicochemical tion, intake of high-fiber foods tends to modulate glucose
properties and their potential physiological effects in the excursions following meal consumption. This helps to
body. This explains why the effects of oat bran are so dif- maintain glucose homeostasis and is of particular impor-
ferent than those of wheat bran and why the overall char- tance to individuals with impaired glucose tolerance or di-
acteristics of a fiber source may not be related to the phys- abetes.
icochemical properties of the individual polysaccharides it Prevention of cancer is also considered a health benefit
contains. of high-fiber diets. Epidemiological studies indicate that
dietary fiber, and in particular a diet rich in cereals and
PHYSIOLOGIC AND METABOLIC EFFECTS vegetables, helps to prevent colon cancer (6). It is thought
that the insoluble fibers that promote laxation and de-
Burkitt and Trowell (2) were the first to report the physi- crease intestinal transit times are responsible for this ef-
ological importance of dietary fiber consumption. Based on fect. If toxins and mutagens in foods are moved rapidly
epidemiological studies, they showed associations between through the intestine, exposure of the mucosa to these
low-fiber diets and chronic disorders such as constipation, harmful materials is minimized. Although it is thought
diverticulosis, colon cancer, diabetes, and cardiovascular that dietary fiber may have a role in preventing numerous
disease. Since the 1970s research has been carried out cancers including mammary and prostate, this hypothesis
that, for the most part, confirms the role of dietary fiber in has yet to be proven.
disease prevention. Normal laxation is an important
health benefit of dietary fiber consumption. Certain vari-
eties of dietary fiber have been shown to increase stool RECOMMENDATIONS
weight and frequency, soften feces, increase fecal bulk, and
reduce gastrointestinal transit times. This is particularly The numerous types of dietary fiber and their many com-
true of insoluble dietary fibers such as cellulose, found in ponents have led to difficulties in establishing recom-
large quantities in wheat bran, and of soluble but nonfer- mended daily allowances. However, several professional
mentable fibers such as psyllium gum. Constipation may groups have issued guidelines for levels of dietary fiber in-
be prevented, or successfully treated, by increasing dietary take that should promote good health and have little or no
fiber intake. Various hypotheses have been suggested as to negative side effects. The United States Department of
how dietary fiber affects the composition of fecal material Agriculture (USDA) has suggested a guideline of 11.5 g
and the frequency of defecation. A likely explanation is the dietary fiber per 1,000 calories consumed ranging from ap-
sponge theory. Dietary fiber in the gastrointestinal tract proximately 20 to 35 g/day for adults (7). Recent recom-
acts as a "water-laden sponge" (3). The sponge entraps or mendations of the American Health Foundation suggest a
adsorbs water, ions, and nutrients, altering intestinal con- goal of minimal intake of dietary fiber for children and
tents and changing the rate of peristalsis. The presence of young adults 3 to 20 years of age be the equal to age plus
fiber also affects the microfloral activity of the colon, the 5 g of dietary fiber per day (age plus 5). This recommen-
end result being decreased intestinal transit time with in- dation suggests that 3-year-old children consume no less
creased fecal bulk and water. Stools tend to be softer and than 8 g/day of dietary fiber and a 20-year-old consume 25
larger accompanied by increased frequency of defecation. g/day (8).
Consumption of soluble dietary fibers has been shown
to lower blood cholesterol levels in both laboratory animals
and humans. Fibers such as oat bran, guar gum, and pectin NUTRITIONAL VALUE
all have a hypocholesterolemic effect. Several mechanisms
of action appear to be responsible for this physiological re- Dietary fiber has been called a nonnutritive bulking agent.
sponse. Soluble fibers increase the viscosity of intestinal This is not an accurate description because dietary fiber
contents, which alters the mixing and diffusion of nutri- does indeed contribute energy to the body. In cases where
ents in the intestine and changes rates of nutrient absorp- the fiber undergoes fermentation by the intestinal micro-
tion. Impaired bile acid and/or cholesterol absorption from flora, the SCFAs that are formed and absorbed into the
the intestine is thought to lead to lowered blood cholesterol blood contribute kilocalories to the body. Not all fibers
are degraded by bacteria, so an average caloric value of 2 other fibers are used in industry to improve food quality
kcal/g fiber has been suggested by the British Nutrition and produce new products.
Foundation Task Force. Actual values for different fiber
sources range from O to 4 kcal/g.
DANGERS OF HIGH-FIBER DIETS
USES IN THE FOOD INDUSTRY A major concern regarding the safety of high-fiber diets is
the effect of dietary fiber on the bioavailability of vitamins
The physicochemical properties of individual fiber sources and minerals. This remains one of the few possible adverse
determine their usefulness in the food industry. Many syn- effects of increasing dietary fiber consumption. Dietary fi-
thetic or modified fibers are used as thickening agents, tex- ber can bind or adsorb ions and act as a physical barrier,
turizers, or stabilizers. Gums, also called hydrocolloids, are potentially interfering with absorption of important micro-
considered food additives. To achieve desired properties in nutrients from the intestine into the bloodstream. In young
food systems, they are used at levels of less than 2%. Some children and the elderly, where only small quantities of
examples of gums include seaweed extracts such as algin- foods are consumed and variety may be limited, dietary
ates, agar, and carrageenan. Gums are also isolated from fiber consumption should conform to the recommended
seeds (locust bean, guar) or dried resins that are expelled daily intakes. Despite studies that suggest that high-fiber
from trees (gum arabic, gum ghatti, gum karaya, gum tra- diets may have deleterious effects, many researchers
gancanth). firmly believe that there is no convincing scientific evi-
Derivatives of cellulose are also used in the food indus- dence that dietary fiber, even when consumed in large
try. Chemical modification of cellulose produces water- amounts, has any adverse effects on nutrition in humans.
soluble fibers such as carboxymethylcellulose, methyl- Deficiencies have not developed in long-term vegetarian
cellulose, and hydroxypropylme thy!cellulose. These adults who consumed more than 50 g of dietary fiber per
compounds have a wide variety of uses such as incorpo- day (9).
ration into baked goods to increase shelf life and to improve
crumb texture. Pectin, which is commercially derived from
citrus peels and apple pomace, is used as a thickener, gel- BIBLIOGRAPHY
ling agent, and suspending agent. The degree of methyla-
tion of the main polygalacuronic acid backbone determines
the gel strength and gelling time of the pectin. Numerous 1. D. A. T. Southgate, "The Chemistry of Dietary Fibre," in G. A.
Spiller and R. J. Amen, eds., Fiber in Human Nutrition, Ple-
num Press, New York, 1976; pp. 31-72.
2. D. P. Burkitt and H. C. Trowell, Refined Carbohydrate Foods
Table 1. Dietary Fiber Content of Commonly Eaten Foods and Disease. Some Implications of Dietary Fibre, Academic
Press, London, 1975.
Product Dietary fiber (g/100 g) 3. M. A. Eastwood and E. R. Morris, "Physical Properties of
Fruits Dietary Fiber that Influence Physiological Function: A Model
for Polymers Along the Gastrointestinal Tract," Am. J. Clin.
Apple (fresh) 1.9 Nutr. 55, 436-442 (1992).
Banana 2.4
Orange 2.4 4. A. Stark, A. Nyska, and Z. Madar, "Metabolic and Morpho-
Grapes 1.0 metric Changes in Small and Large Intestine in Rats Fed a
Peach 2.0 High Fiber Diet," Toxicol Path. 24, 166-171 (1996).
Watermelon 0.5 5. A. Stark and Z. Madar, "Dietary Fiber," in I. Goldberg, ed.,
Functional Foods: Designer Foods, Pharmafoods, Nutraceuti-
Vegetables cals, Chapman & Hall, New York, 1994, pp. 183-201.
Broccoli 3.0 6. M. J. Hill, "Cereals, Dietary Fibre and Cancer," Nutr. Res.
Cucumber 0.7 (N. Y.) 18, 653-659(1998).
Corn 2.7 7. U.S. Department of Agriculture. Food Guide Pyramid: A Guide
Lettuce 1.4 to Daily Food Choices. U.S. Department of Agriculture, Wash-
Tomato 1.1 ington, D.C., 1992.
Potato 1.6 8. C. L. Williams, M. Bollella, and W. L. Wynder, "A New Rec-
Peas 2.3 ommendation for Dietary Fiber in Childhood," Pediatrics 96,
985-988 (1995).
Grains and legumes
9. J. Rattan et al., "A High Fiber Diet Does Not Cause Mineral
Wheat flour (white) 2.7 and Nutrient Deficiencies," J. CZm. GastroenteroL 8, 390-393
Wheat bran 42.8 (1981).
White bread 2.3
Whole wheat bread 6.9
All Bran (Kellogg's) 32.3
Lentils (cooked) 7.9
ALIZA STARK
Hebrew University of Jerusalem
Source: USDA Nutrient Data Base. Rehovot, Israel
FILTH AND EXTRANEOUS MATTER IN FOOD filth in the product is removed. Reconditioning processes
are often approved by FDA (12-14).
THE FEDERAL FOOD LAWS
"Too Small to See" Defense
Soon after the new century began in 1900, the efforts of Another landmark case involved some tomato paste that
that great champion of food purity, Dr. Harvey Wiley, be- contained bits and pieces of larval corn earworms (HeIi-
gan to pay off. The U.S. Congress passed the Pure Food coverpa zed). The owner of the tomato paste claimed that
Law in June of 1906 (1-3). A stronger and more detailed the insect fragments could not be considered filthand the
law emerged from Congress in 1938 (4). Since then the food consumer would not so perceive thembecause the frag-
law has been amended and expanded on several occasions. ments were too small to see. The court rejected that ar-
Today, the Federal Food, Drug, and Cosmetic Act (FD&C gument (15).
Act) stands as a major achievement in the protection of
consumer health (5). Actions Against Persons: The Park-Acme Case
As great as that achievement was, however, it should A series of inspections (1970-1972) of Acme Markets ware-
be noted that protection of consumer health was not the houses in Philadelphia and Baltimore resulted in charges
only objective of the Pure Food Law. The courts have con- against both the company and its president (Mr. Park) for
sistently ruled that it was the intention of Congress to keep violations of Section 402(a)(4) of the FD&C Act. The pres-
filth, whether harmful or not, out of food. Congress wanted ident claimed to be innocent on the grounds that the vio-
food held to the highest standards of hygiene and aesthet- lative acts were committed by subordinates to whom he
ics (6,7). The hygienic standard has, however, received the had delegated authority and that he had no knowledge of
greater amount of attention by the Food and Drug Admin- or responsibility for the violations. When the Supreme
istration (FDA) in its mission to protect the public's Court decided the case, it vitiated the excuse of "delega-
health (8). tion" and determined that top executive officers do indeed
bear complete responsibility for violations that occur in
Two Sections on Filth their organizations (7,13,16-18).
The FD&C Act (9) contains two paragraphs that are es-
pecially pertinent to the topic of filth. The first, 402(a)(3), Filth: "Too Little to Matter"
states that a food shall be deemed to be adulterated if it The bold statements in the two principal filth sections of
consists in whole or in part of any filthy, putrid, or decom- the FD&C Act would seem to totally preclude the presence
posed substance or if it is otherwise unfit for food. The sec- of any filth in or around food. The courts, however, have
ond, 402(a)(4), states that a food shall be deemed to be never held to the letter of the law; in other words, there is
adulterated if it has been prepared, packed, or held under such a thing as de minimis filthtoo little to matter
insanitary conditions whereby it may have been contami- (12,13,15). Some judges have been remarkably lenient in
nated with filth, or whereby it may have been rendered their interpretations of what constitutes significant filth in
injurious to health. There have been numerous challenges or around foods, whereas other judges have been less for-
to FDAs interpretation of the "filth sections" of the Act. giving. In any case, it must be admitted that, without the
unconscionable waste of raw food materials, it is impossi-
ENFORCEMENT OF THE ACT ble to produce foods that are 100% free of filth. The Act, on
the other hand, prohibits filth.
Enforcement actions fall roughly into two categories: ac-
tions against products and actions against persons (10). Food Defect Action Levels
To bridge the gap between this practical reality and the
The Butter Oil Case absolute ban on filthy food called for in the Act, the FDA
In a precedent-setting case, the "butter oil case," decided has established a regulatory tool not mentioned in the
in 1947, federal agents seized a large quantity of butter FD&C Act, namely, the food defect action levels (DALs)
because the cream from which it had been made was con- (19,20). The DALs, which apply to about 90 categories of
taminated with insect and rodent filth. The owner of the foods, mainly refer to field infestations and other unavoid-
butter wished to recoup his losses by making strained but- able contamination. Infestations of stored foods and re-
ter oil out of the butter. FDA objected to this procedure on lated insanitary conditions get no relief from the DALs.
the grounds that the resulting butter oil would still contain The food DALs are administrative guidelines that are
soluble insect and rodent filth. The court upheld this ob- set on the basis of no hazard to human health (21). Any
jection, thus making soluble (invisible) filth just as much products that might be harmful to consumers are acted
an adulterant as particulate (visible) filth (11). against on the basis of their hazard to health, whether or
not they exceed the action levels. DALs are resorted to be-
Reconditioning cause it never has been possible to grow, harvest, and pro-
cess foods that are totally free of natural defects. Insani-
What the owner of the butter had proposed is a process tary manufacturing practices will prompt regulatory
called reconditioning; by this procedure a substandard action whether or not the resulting product is above or be-
product may be brought into compliance if the offending low the pertinent DAL.
Recalls food DALs permit very low levels of natural hard objects
(usually pit or shell fragments) in a few kinds of foods (21).
To maintain their good reputations, many food firms are
When hard foreign objects occur in foods for which there is
willing to act promptly to initiate a recall to protect both
no applicable DAL, each alleged violation is treated on a
themselves and the public. Even though recalls are not
case-by-case basis.
mentioned in the FD&C Act and in spite of the fact that
recalls pertaining to food are technically voluntary on the
part of industry (10), the FDA can still be instrumental in MODES OF CONTAMINATION
prompting a recall when circumstances warrant it (7,22-
24). On the Farm
Extraneous Matter The circumstances by which foods may become adulterated
by filth and extraneous matter are legion. The place where
The courts have always denned filth in its ordinary sense
the food is grown may be the first source of filth. All field-
(ie, the dictionary definition) rather than giving the term
grown crops are to some degree infested with or affected
a technical meaning (19). The same can be said for extra-
by insects, mites, rodents, birds, and molds (45). The pro-
neous matter, that is, things that do not belong in food such
cess of harvesting or gathering the food from the field may
as filth or any foreign matter that comes to be in food as a
inadvertently involve also bringing along live or dead ani-
result of objectional conditions or practices in production,
mals, molds, weed seeds, pebbles, and particles of soil. The
storage, or distribution of food. Included within the mean-
feces of animals or humans that live in or frequent the field
ing of extraneous matter are filth (any objectionable mat-
may also be accidentally collected.
ter contributed by animal contamination such as rodent,
This kind of contamination is becoming increasingly im-
insect, or bird matter), decomposed material (decayed tis-
portant in crops such as lettuce, strawberries, and rasp-
sues due to parasitic or nonparasitic causes), and miscel-
berries that are marketed with minimal after-harvest
laneous matter such as sand, soil, glass, rust, or other for-
cleaning (4648). Foods grown and harvested from aquatic
eign substances (but not bacteria) (25).
habitats may also be subject to adulteration by a wide ar-
The more common kinds of filth encountered during
ray of contaminants (49,50). Foodborne disease outbreaks
food inspections and analyses are whole and fragmented
associated with cross-contamination at retail outlets or in
insects and mites, mammalian hairs and feces (mostly of
the home are at least as common, or perhaps more com-
rodent origin), feather barbules, urea (from mammalian
mon, than outbreaks linked to contamination that occurs
urine), and uric acid (from avian excretions). Other kinds
where the food is harvested.
of filth and extraneous matter include molds and other
fungi and weed seeds (26,27).
In Storage
Light Filth If the crop is temporarily stored on the farm or placed in
Since the 1930s the principal method for separating light longer-term storage off the farm, it may be attacked by
filth such as rat hairs, feather barbules, and bits of insect insects, mites, molds, rodents, or birds (51,52). These adul-
exoskeleton from food has been by flotation. When mineral terating entities produce mostly surface contamination,
oil is added to a sample of food mixed in water, the oleo- but some insects and molds are capable of penetrating food
philic particles (ie, the light filth) float to the surface while materials and living inside the seeds of beans, corn, wheat,
the hydrophilic particles (ie, most foods) settle to the bot- and other crops.
tom. When the oily portion is passed through filter paper, Many kinds of manufactured foods that are stored in
the filth elements remain on the surface of the paper; the warehouses are very susceptible to molds and pests (in-
particles of filth are then identified and enumerated by a sects, mites, rodents, birds). Food items stored in metal,
food analyst (28). Analysts often use reference manuals to glass, or plastic containers are generally safe from the pen-
assist them in identifying filth elements (26,2935). etrating sorts of infestations or contaminations (eg, urine),
Although flotation methods are still the mainstay of but these containers and all other kinds of packaging are
food analysts, other kinds of analytical techniques have susceptible to surface contamination by the urine and feces
been and continue to be developed. These newer methods of rodents and birds. Rats and mice have little difficulty
use biochemical analyses to search out contaminants or chewing their way into most kinds of plastic, paper, foil, or
indicators of contamination that cannot be detected by di- cloth packaging; some insects also have great penetrating
rect visual inspection (36-42). capabilities (53).
MICROBIOLOGY AND QUALITY Canned Fish. Most canned fish are fully processed prod-
ucts such as canned tuna, salmon, sardines, mackerel, fish
Fish Products balls, and other fish. These canned fish are commercially
sterile with 12D process to destroy all pathogenic and
Fish carries a variety of organisms and should be handled
other organisms, allowing a satisfactory shelf life at room
adequately and processed as soon as possible. Refrigera-
temperature. However, some problems may arise due to
tion, freezing, canning, pasteurization, salting, drying, fer-
the presence of heat-resistant spore formers in the under-
mentation, curing, and a combination of these methods are
processed products or can leakage from improper seam clo-
commonly used to process seafood into relatively stable,
sure and cross-contamination through cooling water. In oil
marketable products. Other methods such as irradiation
pack, the oil may protect bacterial spores against heat re-
and modified atmospheric preservation (59) have been ex-
sulting in nonsterile canned products (67). Flat sour spoil-
tensively studied and proved to have potential application.
age may occur due to thermophiles, such as B. stearother-
mophilus, which survive processing and multiply during
Refrigerated and Frozen Fish. Refrigeration at 50C ceases
slow cooling and storage at high temperatures. Swollen
the growth of the mesophiles and as the temperature is
cans are occasionally encountered when clostria such as C.
further lowered, psychrophiles are eliminated. During re-
sporogenes survive inadequate processing.
frigeration storage a gradual killing off of the microorgan-
isms occurs. Gram-negative asporogenous pseudomonads
are cold sensitive, whereas gram-positives such as micro- Dried, Salted, and Smoked Fish. Dehydration is an old
cocci, lactobacilli, and streptococci are more resistant process that reduces the water activity (A1J of the fish
(60,61). products below that required for the growth of microorgan-
Cooling rate affects the survival of microorganisms. The isms. The process involves drying with or without other
maximum survival of E. coli is at a cooling rate of about preservatives to form dried, salted, or smoked fish.
Dried salted fish, fish bits (fried shredded fish), katsuo- X 105/g under poor plant sanitation (75). Cooked crabs
bushi (dried and smoked skipjack stick), dried shark fins, should be stored in refrigeration (<2C), separated from
and dried mullet roe are popular in Asia (68). Smoked the live crabs. Refrigerated cooked crabs before picking
salmon, herring, dogfish, and other fish are common fish- usually contain bacteria of <104/g while cooked sponge
ery products in Europe. Growth of halophilic bacteria or crabs (gravid females carrying an egg mass) taken from
molds may occur, resulting in the spoilage of salted fish. the picking table contain bacterial levels as high as 106/g
Aspergillus and Penicillium are major species associated of whole crabs (76,77). Cooked sponge crabs have consis-
with the color deterioration of salted round herring (68). tently been found to harbor greater numbers of bacteria
Halophilic bacteria such as Halobacterium andHalococcus than crabs without a sponge (77). Similarly, cooked green
commonly present in solar salts are most troublesome dur- crabs, blue crabs that have recently molted and contain a
ing the salting and drying process. These bacteria cause higher level of water than fat crabs, carry higher levels of
red and pink discoloration and induce softness in salted bacteria than normal crabs into the picking room. They
fish. contain higher moisture, which encourages bacterial
growth during overnight refrigerated storage (76).
Surimi-Based Products. Surimi is a mechanically de- The commercial machine Quik Pik, which mechanically
boned, water-washed frozen fish paste containing cryopro- removes the body meat of blue crabs was started on a trial
tectants. This high-protein, gel-forming material can be basis in 1978 and now operates successfully in Maryland
chopped and then mixed with salt, starch, and flavor com- under proper procedures (76,78). One quick Pik machine
pounds. The surimi mix is colored, textured, and cooked in can pick 150 Ib meat per hour, a rate equal to the work
two stages to set the gel to process into seafood analogues capacity of 30 hand pickers. The cooked crabs are placed
such as imitation crab, shrimp, lobster, or scallop. Freshly in a round, rotating slotted cage to remove legs, fins, and
processed crab leg and flaked crab leg analogues contain claws, which are dropped through the slots. The crabs then
only 102-103/g bacteria. During storage bacteria grow and pass through the debacking machine and cleaning device.
SPC reaches 2 X 108/g at 1O0C in 25 days and 104-106/g The cores are loaded on racks for steam heating and then
at 50C in six weeks (69). SPC in flaked crab leg increases placed in the quik Pik shaker, which vigorously vibrates at
rapidly to 109/g after two and four weeks at 5 and O0C, 70 oscillations/s for 4 s. All the meat from cores will fall on
respectively. Spoilage and quality deterioration of crab an- the collecting belt for further inspection for broken shells
alogues are indicated by number of bacteria (107/g), visible and packaging (76).
slime, odor, and appearance. Slime formation, softened Machine picking requires constant attention to clean-
texture, sour odor, and discoloration are consequences of liness and sanitation to produce a meat product with a
spoilage. Bacillus is predominant initially but Pseudo- satisfactory bacterial quality. The machine should be dis-
monas gradually grows and finally outnumbers other gen- assembled and thoroughly cleaned and sanitized at the
era at two weeks of storage at 0-50C. Bacillus, which is end of the day. Liquid on the machine during operation
possibly derived from the ingredient starch, is the major creates an aerosol that can greatly contaminate the meat
organism throughout the six-day storage at 150C (69). The (79). The meat conveyor belt needs continual washing with
spoilage of other fish cake products such as kamaboko can
a tap water spray and sanitation in a chlorine (>200 ppm)
be attributed to Streptococcus, Leuconostoc, and Micrococ-
bath. A comparison of the bacterial levels indicates that
cus (70,71).
both the SPC and coagulase positive S. aureus for
machine-picked meat are lower than for the hand product.
Shellfish Products However, a higher E. coli count is found in machine-picked
After being harvested, shellfish should be kept refrigerated meat than in hand-picked meat. This is not surprising be-
or at low temperature and processed as soon as possible. cause machine picking is processed under wet and warm
Shrimp should be beheaded, peeled, or left unshelled and environment whereas hand picking is operated in cool and
frozen. dry conditions.
The normal shelf life of fresh crabmeat is 7-10 days and
Crabmeat. Blue crabs rank first in U.S. crab landings, may last up to 14 days if meat with a low initial bacterial
and their major products are fresh and pasteurized meat. count (80) is stored under optimum refrigeration tempera-
Other crabs caught are king, Dungeness, and tanner-snow ture. To extend the shelf life of crabmeat, the pasteuriza-
crabs from which frozen section, claws and meat, and tion process of holding crabmeat for 1 min at 171-210F,
canned meat are commonly made (72,73). depending on the desired shelf life from 1 to 12 months,
To process blue crabmeat, live crabs are steam cooked was patented (81). A process of 1850F for 1 min in the cen-
at 1210C for 10 min. Cooked crabs are refrigerated over- ter of a 1-lb can (401 X 301) was found to sufficiently re-
night and the meat is removed by hand or machine. The duce an inoculated 108/100 g of C. botulinum type E spores
meat is packed in plastic cups for fresh crabmeat or sealed to <6/100 g and to keep the meat nontoxic for 6 months at
in tin cans to process for pasteurized crabmeat (74). Three 4O0F (82,83). A recommendation has been made to increase
kinds of meat are available: lump meat taken from the the time at 1850F to 3 min to provide for 12D cook based
back fins, claw meat extracted from claws, and regular on the thermal death time studies of type E C. botulinum
meat collected from main body (72). In good plant sanita- (84-86). Table 2 shows the thermal resistance character-
tion, fresh crabmeat usually has a geometric mean SPC of istics of C. botulinum type E. For a complete process, an
1.5 X 104-4.5 X 104/g, which increases to 1.4 X 105-3.2 F-value of 31 based on an F 16/185 value and a cooling
Table 2. Decimal Reduction Time (D10) for Heating C. botulinum Type E Spores
Strain Heating medium Temperature range (0C) D10-value minimum at 82.20C Z-value (0C) Reference
Beluga Blue crab meat 73.9-85.0 0.75 6.5 85
Beluga Crabmeat 73.9-85.0 0.84 6.5 85
Sarotoga Crabmeat 80.0-82.2 1.90 6.3 87
Alaska Whitefish chubs 73.9-85.0 2.21 7.6 88
Sarotoga Sardines in tomato sauce 76.7-82.2 2.9 6.3 87
Sarotoga Tuna in oil 72.2-82.2 6.6 6.1 87
Strain 202 Crabmeat 76.7-85.0 1.16 6.38 85
meat temperature of 550F within 180 min of heat process ejection of electrons from atoms or molecules. Only radia-
following storage at 350F have been recommended (87). tion with strong penetration, including gamma rays, x-
If storage temperature of pasteurized crabmeat rises rays, and electron beams, is useful in food preservation.
above 380F, surviving bacteria may grow and bacterial Gamma rays from radioactive isotopes such as Co-60 have
spores may germinate leading to spoilage. Any leakage due been the most acceptable radiation source due to its avail-
to can defects can introduce psychrotrophic bacteria from ability, price, and properties. One rad, a unit of irradiation
cooling water and result in spoilage during refrigerated dosage, is equal to 100 ergs of radiation energy absorbed
storage (89). Poor meat quality with a high level of initial per gram of substrate. A megarad (Mrad) is a million rads,
bacteria will increase the chance of survival of potential and a kilorad (krad) is a thousand rads.
spoilage bacteria. The spoiled pasteurized crabmeat usu- There are several advantages in using ionization radi-
ally contain both aerobic and anaerobic bacteria ranging ation for seafood preservation. The extension of shelf life
from 4.0 X 102 to 5.0 X 108/g. Spoiled crabmeat prepared of seafood by using low-dosage irradiation allows the ex-
from machine picking has more anaerobic organisms than pansion of markets farther inland where fresh seafood is
hand-picked crabmeat (79). otherwise unavailable. The long shelf life of irradiated sea-
food can adjust the seasonal production providing a year-
Bivalves. Heat shock has been attempted to facilitate round supply and unfluctuating prices. Irradiation of high-
oyster shucking by quickly passing the stocks through a quality catches produces top-quality seafood thus reducing
steam tunnel to slightly open the shells. Although this pro- the need to discard or process deteriorating fish to fish
cess increases the shucking rate, disadvantages are yield meal (94,95). Ionization radiation directly affects living
reduction and high risk of bacterial contamination (90). cells by causing breaks in DNA and indirectly affects other
Canning bivalves serves as a long-term preservation cell components. The presence of water increases the de-
method. When recommended processing times and tem- gree of the DNA damage. Complex cells are more sensitive
peratures are followed, few microbiological problems are to irradiation than simple ones. The death or injury of mi-
encountered (88). However, loss of texture and economical croorganisms is due to the direct hit on DNA and the in-
infeasibility are problems with this processing. direct effects from ionization and diffusion of free radicals
Pasteurization of oysters at 72-740C for 8 min in a flex- and peroxides produced around the cells.
ible pouch results in a relatively stable product with or- Food irradiation can be classified into three classes de-
ganoleptic properties similar to raw oysters. The products pending on the level of microorganisms to be destroyed
stored at 0.50C for three months have a low level of both (60). Radappertization or Radiation sterilization is the use
aerobic and anaerobic bacteria (91). Immediately after of high dose with 12D usually more than 2 Mrad for com-
pasteurization, all the surviving bacteria in the oysters are plete destruction of all or practically all of the organisms.
Bacillus sp. At storage of five months Bacillus continues Radurization or radiation pasteurization is using low dose
to dominate the aerobic bacteria while Clostridium, Cory- of radiation to destroy a sufficient number of organisms to
nebacterium, Listeria, Peptostreptococcus, and Staphylo- enhance the shelf life of foods. This process usually uses
coccus constitute the facultatively anaerobic bacteria (92). 100-1,000 krad to destroy 90-99% of the organisms. Rad-
Combining safe preservatives with the pasteurization can icidation is a low-level irradiation treatment that kills
provide a safe and longer shelf life of oysters. nonspore-forming pathogens to reduce or eliminate the
food-borne illness problem. This kind of irradiation treat-
ment normally uses 400-600 krad dose for destruction of
SEAFOOD IRRADIATION salmonellae from poultry and red meat or feed but not for
spores of C. botulisum or C. perfringens.
Irradiation is a process extending seafood shelf life by ex- In seafood irradiation, radiation resistance is expressed
posing seafood to a certain level of ionizing radiation. Stud- as the decimal reduction dose (D10), the dose (krad) re-
ies on the utilization of ionization radiation in food pro- quired for a 90% or 1-log reduction in bacterial count. The
cessing began in the early 1940s, and an extensive radiation resistance of microorganisms varies, depending
program implementing this process was launched in the on strains and species and the Z)10-values of various or-
early 1950s, in the United States (93,94). Ionization radi- ganisms are shown in Table 3. The resistance in descend-
ations are a group of corpuscular and electromagnetic ra- ing order is yeast, Micrococcus, Moraxella-Acinetobacter,
diations of extremely short wavelengths that can cause Flavobacterium, and Pseudomonas (60). The gram-positive
Table 3. Decimal Reduction Doses CD10-Values) for eration without altering the fresh-product characteristics
Irradiation of Some Microorganisms and Toxins (Table 4). Compared with the regular 10- to 14-day shelf
Suspending life of the unirradiated products, low-dose irradiated prod-
Organism or toxin medium D10 (krad) Ref. ucts have a shelf life two to three times longer (94,109). To
insure efficiency and successful processing, the seafood
Vibrio parahaemolyticus Crabmeat 5-12 96
Proteus vulgaris Oysters 20 95
should initially be of high quality and irradiated products
Crabmeat 10 95 should be maintained as near O0C as possible without
Aeromonas hydrophila Blue fish 14-22 96 freezing.
Escherichia coli Soft-shells clams 39-42 96 The safety of irradiated seafood must be evaluated
Mussel 41-48 96 based on the absence of microorganisms and microbial tox-
Oysters 35 95 ins harmful to man, the nutritional contribution of the
Crabmeat 14 95 product, and the absence of any significant amount of toxic
Salmonella typhimurium Soft-shell clams 60 96 compounds formed in the irradiated products (101). Low-
Mussel 58-63 96 dose irradiated seafood, particularly lean fish species, have
S. paratyphi A Oysters 75 95 been found to pose no potential health hazards (94,110).
Crabmeat 50 95
Shrimp 85 95
Despite the approval of over 35 countries irradiation in
S. paratyphi B Shrimp 61 97 foods and the USDA clearance of low-dose application for
Shigella flexneri Mussel 24-34 96 poultry irradiation, seafood irradiation has not been per-
S. sonnei Oysters 27 95 mitted. This process can become a successful technique for
Staphylococus aureus Oysters 150 95 seafood preservation once it is approved in the United
Crabmeat 80 95 States.
Shrimp 190 95
Adeno virus, echovirus Eagles medium 410-490 60
Toxins, botulinum type E SEAFOOD MICROORGANISMS OF PUBLIC HEALTH
Washed cells Buffer 1,700-2,100 60 SIGNIFICANCE
Purified Buffer 40 60
Staphylococcal Seafood, particularly shellfish, may contain a variety of
Enterotoxin B purified Buffer 2,700 60 pathogenic microorganisms that impose a threat to the
consumers' health. These potential pathogens include both
indigenous organisms and contaminating organisms.
bacteria are more resistant than gram-negative ones. Coc- Pathogens may contaminate the seafood after harvest or
coid forms are more radioresistant than rod-shaped cells. during processing. Some indigenous pathogens found are
Bacterial spores exhibit the most resistance to radiation Vibrio, Clostridium botulinum type E, Aeromonas, and poi-
with the exception of some gram-positive cocci. Compared sonous phytoplankton such as dinoflagellates (111,112).
to bacterial spores, viruses are more or equally resistant Extraneous pathogens include Salmonella, Shigella, Lis-
to irradiation. Although the amount of radiation needed to teria, Campylobacter, Staphylococcus aureus, E. coli, Ba-
inactivate microbial toxins is similar to that for bacterial cillus cereus, Hepatitis A, and Norwalk virus (64,112).
spores, the radiation level for inactivation of botulinum The consumption of bivalves is of greatest concern to
toxin is much higher than that needed to kill the bacterial the public due to several factors. Bivalves, especially oys-
cells (98) (Table 3). ters, are frequently consumed raw. The whole animal is
In general, D10-values for bacterial vegetable cells (ex- consumed rather than just the muscle tissue, as in the case
cluding cocci), bacterial spores, M. radiodurans, viruses,
and bacterial toxins are 20-100, 150-450, 200-600, 400-
800, and 200-2,000 krad, respectively (99-104). Table 4. Shelf Life at O0C of Selected Seafood after
Low-dose irradiation treatment of seafoods usually does Optimal Dose Irradiation Treatment
not induce detectable changes in flavor, texture, and ap-
Shelf life Optimal dose
pearance with the exception of a slight loss of flavor in a Seafood (weeks) (Mrad) Ref.
few products (105,106). The level of irradiation is one fac-
tor in determining the type of microorganisms remaining Haddock fillets 3-5 0.15-0.25 107
that cause spoilage of irradiated seafood. The spoilage mi- Cod fillets 4-7 0.10 108
croflora of irradiated fish after a low dose of < 100-150 Ocean perch fillets 4 0.15-0.25 107
Mackerel fillets 4-5 0.25 107
krad treatment consists mainly of pseudomonads. At dose English sole fillets 4-5 0.20-0.30 107
levels higher than 100 krad, Maraxella-Acinetobacter rep- Smoked chub 6 0.10 107
resented the dominant group of organisms in fish spoilage. Petrale sole fillets 2-3 0.20 107
Irradiation of packaged fish favors the growth of lactic acid Shrimp 4 0.15 107
bacteria that will be the major spoilers. In general, non- Lobster meat (cooked) 4 0.15 107
irradiated fish spoils at an aerobic plate count (APC) of King crab meat (cooked) 4-6 0.20 107
106/g whereas low-dose irradiated fish spoils at about Dungeness crab meat (cooked) 3-6 0.20 107
108/g(94). Oyster meat 3-4 0.20 107
Under the optimum dose of 100-300 krad, fish and Note: Fish or shellfish were packed aerobically in hermetically sealed cans
shellfish can be maintained three to seven weeks at refrig- or oxygen-impermeable plastic bags.
of other raw crustaceans and raw fish. Bivalves are filter V. cholerae causes a gastrointestinal illness in humans
feeders that can trap microorganisms from the growing called cholera (132). This species is usually divided into
water into their bodies. Because the animals grow in near- two groups, serotype Ol and non-01: both are found in
shore estuarine waters that may encounter sewage pollu- aquatic environment. The Ol serotype contains two bio-
tion, bivalves may become a vector for disease transmis- types: classical and El Tor. The classical biotype prevailed
sion. Based on past records of bivalve shellfish borne worldwide until the 1960s and the El Tor biotype presently
disease between 1900 and 1986, there were 12,376 cases predominates, including in the United States
of food-borne illnesses in the United States excluding cases (111,133,134). Cholera in the United States is relatively
of paralytic shellfish poisoning (112). This has been esti- rare but occasional outbreaks occur in southern states such
mated to be only 5-10% of the actual number of cases. as Texas, Louisiana, and Florida due to consumption of
These documented cases include 43% gastroenteritis, 26% raw or partially cooked molluscs, cooked crabs, and other
typhoid, 11% infectious hepatitis, 11% Norwalk virus, and shellfish (133,134). The infective dose is estimated to be
2% Vibrio. The specific etiologic agents have been identi- about 106 cells. Taking antiacids or medication to lower
fied as Salmonella typhi, Vibrio cholera 01, V. cholera gastric acidity will lower the infective dose (115). The in-
non-01, V vulnificus, V. parahaemolyticus, V. fluvialis, V. cubation time varies from 6 h to 5 days. Severe symptoms
mimicus, V. hollisae, V. furnissii, E. coli, Salmonella sp., include profuse watery diarrhea, dehydration, and death
Shigella sp. Bacillus cereus, Staphylococcus sp., Campy- in the absence of prompt treatment. In the beginning, the
lobacter sp., Aeromonas hydrophila. Pleisomonas shigello- stool is brown with fecal material and quickly acquires the
ides, hepatitis A, Norwalk virus, and other viral agents classic rice-water appearance. Enormous amounts of fluid
(112-115). leave the body resulting in dehydration and difficulties in
Food poisoning outbreaks reportedly have often been circulation. The stool is high in potassium and bicarbonate
due to the consumption of seafood. The most common (111,133). Besides severe diarrhea, victims suffer from
agent involved is V. parahaemolyticus (114,116). This spe- thirst, leg cramps, weakness, hoarse speech, and rapid
cies was first isolated in 1950 in Japan from seafood pulse (132,133). In emergency treatment, prompt replace-
(117,118). Since then it has been implicated in more than ment of fluid and electrolyte losses by intravenous injec-
1,000 outbreaks per year in Japan and accounts for over tion is often used. After an initial recovery, oral intake of
50% of that country's bacterial food poisoning. V. parahae- glucose and electrolytes can improve the condition. In gen-
molyticus strains require a low concentration of salt for eral, V. cholerae is sensitive to heat and cold, but it can
growth, but some cultures isolated from fresh water have survive at low temperatures for a certain time (135).
been reported (119-124). Raw seafood is the major vehicle Non-01 cholera is a group of nonagglutinable (NAG)
for the organism in Japan; cooked seafoods that have been cholerae, which exist naturally in estuarine and coastal
recontaminated are the source of implication in the United waters and also in rivers and brackish waters (128). Only
States (117). Kanagawa reaction is commonly used to dif- about 5% of this group from seafood and patients isolates
ferentiate between virulent and avirulent isolates by test- in the United States produce cholera toxin. However, the
ing whether a strain can produce a heat-stable hemolysin nontoxigenic strains cause gastrointestinal illness with
to lysis a blood agar containing 7% NaCl and mannitol. principal symptoms of abdominal cramps, fever, bloody
Cultures isolated from stools of patients are always Kan- stools, nausea, and vomiting (133). Some human isolates
agawa positive (99%). On the contrary only about 1% of of this group in the United States are from extraintestinal
isolates from waters or seafoods is Kanagawa positive sources including wound infection, ear infection, and pri-
(125,126). The mechanism for this discrepancy is still un- mary and secondary septicemia (133). Eating raw oysters
known. One of the hypotheses is that there may be a trans- has been found to be the major cause of most non-01 V.
formation of Kanagawa-positive strains on passage cholerae infection cases in the United States. Other sea-
through the intestines. There is a possible competitive ad- food, egg and asparagus salad, or potatoes can occasionally
vantage for Kanagawa positive strains to proliferate more be a vehicle for these organisms (134).
readily in the intestines. The current method of isolating V^ vulnificus is widely distributed in the environment
and identifying Kanagawa-positive strains in seafoods and and has been found in most U.S. estuarine and coastal wa-
waters may also leave some undetected (116,126). ters (136-138). This water and seafood organism is found
The infective dose of V. parahaemolyticus for humans most frequently at water temperatures >20C and low sa-
ranges from 105 to 107 viable cells, and a decrease in stom- linity of 0.51.6%. Environmental isolates are phenotypi-
ach acidity may lower the infective dose. The incubation cally identical to clinical isolates. Some strains show bio-
period for symptoms is 5-90 h and the duration of the ill- luminescence and may also be pathogenic (138). This
ness is normally 2-10 days. The frequencies of symptoms organism can cause illness and infection through the con-
are diarrhea, 98%; abdominal cramps, 82%; nausea, 71%; sumption of contaminated raw or undercooked seafood,
vomiting, 52%; headache and fever, 27%; and chills, 24% particularly mollusks such as oysters and clams. The in-
(116,126). The organism has three biologically active he- cubation period for this illness is 16-48 h after ingestion.
molysins, substances that can lyse the animal's blood cells: Symptoms include weakness, chills, fever, hypotension,
a heat-stable peptide with 45,000 mol. wt., a heat-labile and fatigue with occasional vomiting and diarrhea. Infec-
hemolysin, and a phospholipase (127,128). V parahaemo- tion occurs, progresses rapidly, and may cause death in 40-
lyticus are heat sensitive and most food-poisoning cases 60% of patients (128). Patients may have greater risk of
result from cross-contamination or poor sanitation (129- infection if they have skin cuts or suffer chronic liver dis-
131). ease, gastric disease, or hemochromatosis (111,128).
Other potential Vibrio pathogens such as V. hollisae, V. hepatitis in the United States (114). Outbreaks of Norwalk
mimicus and V^ furnissi have been implicated in seafood- virus gastroenteritis by shellfish ingestion must be docu-
borne illnesses (111). Vehicles for these organisms are mented in Australia and the United States (97).
shellfish including oysters, clams, shrimp, and crawfish. According to the Centers of Disease Control annual
Common symptoms are diarrhea, nausea, vomiting, and documentation, nearly 90% of all reported outbreaks of
abdominal cramps. Both toxigenic and nontoxigenic seafood-borne illness are associated with consumption of
strains of V. mimicus have been isolated but food-poisoning molluskan shellfish and a very few species of fish
cases have mostly occurred with nontoxogenic ones. Some (148,149). In geographic distribution, Hawaii has the most
strains of these organisms have been newly isolated in the cases accounting for 35% of all these seafood-borne ill-
last few years, and more information will be available after nesses. About half of all these seafood-borne illness cases
further studies (111). are found in four states and territories: Hawaii, Puerto
Clostridium botulinum type E is another intrinsic path- Rico, Virgin Islands, and Guam. Another third of these
ogen in seafood causing botulism type E intoxication. seafood-related illnesses occur in the continental states of
Based on the serological classification of the neurotoxin, C. New York, California, Washington, Connecticut, and Flor-
botulinum is composed of eight types: A, B, C1, C2, D, E, F, ida (149).
and G (139). These types are divided into four groups ac- Chemical intoxication resulting from the harmful me-
cording to proteolytic activity (140,141). Groups I and II tabolites of microorganisms are often implicated in sea-
are of particular importance for causing botulism in hu- food. An allergic food poisoning after eating deteriorated
mans. Group I includes type A and proteolytic strains of scombroid fish is caused by formation of histamine by mi-
types B and F. Group II contains all type E and nonpro- crobial enzyme histidine decarboxylase when fish have
teolytic strains of types B and F. Type E is distributed in been exposed to environments favorable to bacterial
sediments of marshes, lakes, and coastal ocean waters and growth. The organisms involved in histamine poisoning in-
is common in the intestines of fish and shellfish. The or- clude Pseudomonas putrefaciens, Aeromonas hydrophila,
ganism does not proliferate in living fish but it may mul- Proteus vulgaris, Clostridium perfringens, Enterobacter
tiply in bottom deposits and in aquatic vegetation when aerogenes, and Vibrio alginolyticus (150).
the growth of algae reduces the oxygen level of the water
to conditions suitable for C. botulinum. Type E can grow
and produce toxin at 40C and is heat sensitive (142,143). MICROBIOLOGICAL CRITERIA AND INSPECTION
It is inhibited by water activity of <0.975 (5% NaCl) and
pH <5.3 (144). Most outbreaks of botulism associated with Microbiological criteria are an important but controversial
fishery products have been with semipreserved products. issue in establishing a regulatory food-control program,
Smoked, salted, fermented, and canned products are eaten particularly for seafoods in the United States. The pur-
without further cooking and can involve the risk of botu- poses of microbiological criteria are to insure food safety,
lism due to inadequate processing (89,143). Satisfactory adhere to good manufacturing practice, and provide estab-
heat processing is critical in assuming quality safety of lished measure for food inspection and marketing. Accord-
pasteurized crabmeat described above. ing to the degree of compliance, microbiological criteria
Plesiomonas shigelloides is found in fresh surface water include three categories: standard, guideline, and specifi-
and possibly in seawater and is more often isolated in the cation (151). A standard is part of a law or ordinance and
summer months. This organism has been implicated in hu- is a mandatory criterion. A guideline is a criterion for as-
man gastroenteritis for 40 yr (145). Seafood that may carry sessing microbiological quality during processing, distri-
this organism are cuttlefish, raw oysters, salt mackerel, bution, and marketing of foods. A specification is used in
and undercooked oysters. Incubation time for symptoms is purchase agreements between buyers and vendors
one to two days after ingestion of the food. Symptoms in- (152,153).
clude diarrhea, abdominal pain, nausea, chills, fever, vom- As more countries are recognizing the need to assess the
iting, and headache (145). safety and quality of foods due to food-poisoning outbreaks
Enteric viruses are those animal viruses that are ex- and international trade disputes, several agencies have
creted in feces and discharged into domestic sewage. These formed organizations to formulate microbiological criteria.
viruses are more resistant than enteric bacteria to sewage The International Committee on Microbiological Specifi-
treatment process and various environmental stresses. cations for Foods (ICMSF) was established by the Inter-
Several human enteric viruses may be implicated in the national Association of Microbiological Society (IAMS) in
viral disease by seafood consumption, such as hepatitis, 1962 for this and related purposes (154). The committee
fever, diarrhea, paralysis, meningitis, and myocarditis. assists in establishing microbiological standards imple-
Shellfish may play a significant role as vectors in the trans- menting method of examination, promoting safe move-
missions of viral diseases. A study of cockles-borne disease ment of foods in international trade, and mediating dis-
indicated that about one-quarter of the hepatitis A cases putes caused by disparate criteria. The committee also
in the southeast UK could be caused by shellfish consump- publishes books of its reports and recommendations (153-
tion (146,147). In Frankfurt, Germany, about one-fifth of 155). Many of the ICMSF recommendations were incor-
infectious hepatitis was associated with the consumption porated into the work of Code Alimentarius Commission
of contaminated oysters (148). Molluskan shellfish is the to implement the Joint FAOAVHO Food Standard Pro-
major seafood involved in the outbreak of hepatitis A in- gram of the United Nations World Health Organization.
cidence (58) and also attributes to 12.5% of non-A, non-B The goal of the Joint Food Standard Program is to protect
the health of consumers, ensure fair practices in the food such as inadequate growth temperature and media com-
trade, guide the preparation of draft standards and codes position, often result in disputable results of seafood sam-
of practice, and promote the incorporation of all food stan- ple analysis. The large number of nonculturable viable
dards by different governments. The program has also cells in marine bacteria greatly limits the study of the role
published recommended international codes of practice for of these organisms in the natural aquatic ecosystem and
many common seafood products such as shrimps or prawns the relation to fish and shellfish.
and frozen fish (156,157). The fast growth of psychrophilic and psychrotrophic
To ensure consumer safety, inspection systems are en- bacteria cause fish and shellfish to spoil rapidly even in
forced by the regulatory agencies in most of the countries. refrigeration. In addition to spoilers the potential patho-
In the United States, the inspection program is carried out genic microorganisms present in seafood can proliferate
by different levels: local, state, and federal government. expeditiously and threaten consumer safety. Prompt sea-
The federal regulatory seafood control systems include the food handling and adequate processing are critical in the
Food and Drug Administration (FDA), U.S. Department of control of both spoilage and pathogenic organisms to pro-
Agriculture (USDA), U.S. Department of Commerce vide safe and stable products. Good quality control and in-
(USDC), U.S. Department of Defense (USDD), and the En- spection, particularly the HACCP program, can ensure a
vironmental Protection Agency (EPA). The FDA is in high quality of seafood products.
charge of imported seafood inspection, a mandatory sur- Application of modern basic microbiology, biochemistry,
veillance system. The National Marine Fisheries Service and biotechnology can advance fish and shellfish microbi-
of USDC operates the voluntary Fishery Product Inspec- ology. DNA probe, immunoassay, monoclonal antibody, and
tion Program mainly for domestic seafood industry on a other rapid-detection methods provide accurate and expe-
fee-for-service basis. The USDA and other federal agencies ditious procedures for determination of seafood pathogens.
are responsible for some inspection systems related to The study of bacterial cell envelope, a new field that has
their domain of authority. Much of the domestic seafood arisen in the last two decades, can provide information
products are inspected by the states and municipalities in about the functions and physiochemical properties of cell
their respective territories. In recent years, the public con- envelope components, which are important in understand-
cern in seafood safety and confusion among various in- ing bacterial survival and interaction with other organ-
spection systems have led to the proposal of a national sea- isms in the aquatic ecosystem. This field of knowledge will
food surveillance system. At the time of this writing the also be helpful in establishing new technology to control
USDA will likely be chosen to head this mandatory seafood bacterial growth during processing. Study of nonculturable
inspection program. viable or dormant cells may lead to a new field of study:
Microbiological criteria have been controversial and bacterial survival in the natural environment and its im-
confusing because of the variation in agency objectives, leg- pact on seafood. This can provide another avenue in ex-
islative authorities, unsatisfactory definitions, questions ploring the key factors behind many nondetectable food
in sampling procedures, methodology, quality require- pathogens. The progress in seafood microbiology will
ments, and uninsured consumer protection. In recent greatly benefit the seafood industry, providing safe, better
years a hazard analysis critical control point (HACCP) ap- quality seafoods.
proach has been regarded as an effective, practical, and
economic program in microbiological monitoring and
safety of the products (152,158). The industry should de- BIBLIOGRAPHY
velop the actual details of a HACCP program and insure
the implementation of the complete process. In conducting 1. R. E. Martin, W. H. Doyle, and J. R. Brooker, "Toward an
hazard analysis of the products each step of the processing Improved Seafood Nomenclature System," Mar. Fish. Rev.
operation should be defined to specify the hazards associ- 45, 1-20 (1983).
ated with each step. The preventative measures at each 2. D. C. Georgala, "The Bacterial Flora of the Skin of North Sea
processing step will be identified for elimination of the haz- Cod," Journal of General Microbiology 18, 84-91 (1958).
ards. The critical control points are thus defined, bringing 3. J. Listen, "Qualitative Variations in the Bacterial Flora of
the hazards under control. The theory behind the HACCP Flatfish," Journal of General Mic