Documenti di Didattica
Documenti di Professioni
Documenti di Cultura
to Deterioration of Foods
1.P. Labuza
Department of Food Science and Nutrition, University of Minnesota, St. Paul, MN 55108
A maior goal for the food scientist is the prediction of the microbe with time. Much literature data exist for the growth
change fn q"ality of a particular food a s a function of both time rate constants of microhes under certain conditions. In ad-
and environmental conditions. This has become the focus of dition, many food processes involve heating the foods to in-
many research and development projects because the infor-
mation ohtained is needed by those in the food industry so
.
activate both harmful and sooilaee - microoreanisms.
"
simple, as well as complex, kinetic mathematical models have
Verv
that they can been develoved to nredict the amount of kill a eiven nrocess
will achieve,'thus enabling one to predict the i n i t 2 loa4 before
1) evaluate the effectof the addition of new ingredients or additives the food is stored. It is important to recognize that, in general,
on shelf life, the processing of food is intended, first, to reduce the micro-
2) set an open date for the food on the package (e.g., a "use by" or
"hest if used
~-~~~ ~.
hv" date) so that consumers are better informed
in handling the product,
bial load as much as possible and, second, to minimize mi-
crobial growth in the packaged or stored product.
3) insure that the food meets the compliance standards if nutri-
tional labeling is used (i.e., it does not fall below label value).
In order to make useful predictions about shelf life, the Senescence
research scientist needs information regarding
Once a plant is harvested or an animal slaughtered the
1) the potential major modes for loss of quality of the product, tissues are deprived of any external source of carbon or ni-
2) the factors which control the initial quality or nutritional value trogen, and thus utilize their internal carbohydrate, protein,
during manufacture, or fat as a source of energy. They do this by continuing their
3) the environmental conditions the food will be exposed to in- normal enzymatic reactions in an aging process usually termed
cluding temperature, relative humidity and light, senescence. Eventually the energy sources run out, or end
4) whether it is packaged in a semi-permeable container, and, if
so, the permeability of that film to oxygen, water vapor, and nroducts accumulate to render the food unacceotahle. A fa-
light, and kiliar illustration of th/? process is the loss of sweetness in corn
5) the kinetics of the reactions leading to loss of quality or nutri- on the cob durine storaee. The studv of the rates of these
tional value as a function of the reaction phase conditionsin the senescence reactions is imponant to the processor who wishes
food and the external environment. to insure hich uualitv" inrredients in orocessrd food. It is also
important for ihe fresh produce supplier. Once the food has
Since foods are very complex systems (food science is been ~rocessed.however. the enzvmes are usuallv denatured
sometimes referred to as the study of "messy" chemistry), it or t h i internal environment is chinged so thar other reactions
is not always possible to isolate clear-cut chemical reaction Ieadinr to loss of aualitv vrcdominate. It should he noted that,
mechanisms which lead to the observed changes in quality or as se&scence pr&ceeds;many fresh products become more
to have elegant mathematical models that can describe the susceptible to invasion by surface microorganisms which then
reaction rate under a variety of conditions. Thus compromises become the apparent agent of deterioratkn.
must be made. In addition, in the industrial research and
development environment, it is not always possible to do ex-
tended studies to isolate the mechanisms and develop the
data, so abuse conditions are chosen to get quick results. From Enzymatic Chemical Deterioration
the data ohtained under these abuse conditions it is hoped to When a food is processed in some way (heated, salted, dried,
project what would happen under normal, long-term storage. frozen. etc.) its internal structures are disrunted so that
This article will briefly review the possible major modes of membranes are damaged. Thus, the neatly compartmental-
deterioration that should he evaluated, then a general review
of the application of simple kinetic methods will be made, and can nbw come into contact and react. ~ h e s reactions
e
" .
ized svstem is destroved. and chemicals normallv senarated
then
finally some mathematical examples will he given. For a more become the maior modes for loss in aualitv. The number of
extensive review of shelf-life deterioration see Labuza ( I ) . different hnds of reactions possible is knorkous, hut most can
be classified in thc several areas outlined below.
General Modes of Food Deterloratlon
toxicoloeical urooerties. Lahuza (6)has thorouehlv reviewed which is not treatable hy most simple kinet', models. An r x -
the kinetics df the lipid oxidation mechanism. it probably is ample of the first is the sudden loss of crispuess of dry snark
the maior form of deterioration of most d m foods as well as or rereal foods when they gain moisture and reach a certain
some frozen foods. water activitv (10). Thc second tvne is re~resentedbv lcssof
quality in some frozen fwds due toconcentration acceieration
Vitamin Loss and membrane damage (11) as temperature decreases and by
the physical staling of bread, which becomes tougher faster
The loss of vitamins in a food leads to its decrease in nu- when i t is stored refrigerated as compared to room tempera-
tritional value to the consumer as well as to potential legal ture (12).
action by the Food and Drug Administration because of label
noncompliance. Vitamin destruction can occur through nu- Overview
merous mechanisms such as hydrolysis or scission due to light,
heat, or acid (e.g., amines or riboflavin), direct oxidation by The key to the aoolication of kinetics to mediction of
0 2 (vitamins C, E, D, or A), or participation in other redox quality loss is select& of the major mode of Aeterioration,
reactions. The most lahile is vitamin C, especially a t higher measurement of some quality factor related to this mode, and
moisture content and temperatures. Labuza ( I ) has reviewed then application of mathematical models to make the needed
the losses of vitamins during processing and has summarized predictions. Two main sources of error associated with these
the storage stability data available. predictions are the inability to identify some quality index
related to the major mode of deterioration and the analytical
Color Changes errors involved in when it is measured. For most food analyses
Since the colors of foods are due both to water-soluhle and the analytical precision even with modern instrumentation
fat-soluble compounds, there is a vast array of reactions is a t best +5-10% where
leading to loss of natural color during storage a~ndprocessing. 0
For example, under arid ronditions, the cmtml Mg'* ion in %precision = f - X 100 (1)
Tx'
i n structure of chlorunhvll is released with
the ~ o r r ~ h v r rine
a change in color a lighter gray/~een. when 20-30% of the and a = standard deviation of method, and F = mean value.
Ma9+ is lost. manv veeetahles become unacce~tablefrom a When there is relatively poor precision, much error can he
q"ality standpoint. ~ o L isr also lost through d&rt oxidation introduced into orediction of aualitv loss as a function of time
of carotenoids or co-oxidation of lioids. Nonenzmatic and (13). This is co£ed by &e fait that many foods become
enzymatic browning both darken fdods. unacceotahle after a chanee of onlv 20-30% in the initial value
of the 'chemical index."?be choice of the test to he used so
Enzymatic Actiuity as to minimize wtential errors should he based on the answers
t o the following questions:
If the food is not heat-treated to inactivate enzymes, then
during storage, even in food with fairly low moisture content,
some enzymes can catalyze certain reactions leading to un- 1) What are the key labile ingredients (e.g., unsaturated fats, re-
desirable flavor. color. or texture. Examules of this include free ducing sugars, vitamin C, or natural color)?
fatty acid prodktionin cereal grains add dried dairy products 2) What are the characteristics of the package system being pro-
(lioase), volatile off-flavor develooment in manv cereal and posed or used (oxygen permeable, water permeable, odor per-
drledlfrozen vegetable and dairy products (lipoxidase), and meabile, vacuum versus air versus nitrogen)?
darkening of manv foods hv - .nolvohenol
.. oxidase. What is 3) How will the product he shipped and stored?
needed are data both on the activity of the enzyme as afunc- 4) Will the foodlpackage system be subjected to high humidities
tion of reaction phase conditions and on the kinetics of inac- whereby it can gain moisture or low humidities where it will lose
tivation as a function of pH, temperature, and water activity moisture? If so, what consequenceswill a change in a, have on
chemical reactions or physical quality (e.g., as a reduction in
lau). With this knowledae, orocessinn -stem
. can he desiened crisoness)?
to denature the enzyme such that it will not cause deteGora- 5) Whnr i> the pussihle temperature rang? the product will expe-
tion during storage. rience during dtatrihution? Will this temperature range rmap
the product to go through a phase change (i.e., melting fat or
Sensory Changes thawing a frozen food),or will the product, if frozen, he held too
In many cases it is impossible to identify the exact chemical close to the freezing.point
. which could cause rate aceelera-
tion?
reaction leading to loss of quality. In these cases many re- 6 ) Is the product susceptible to light (e.g.,UV-catalyzedlipid ox-
searchers have made sensory evaluations of the food quality idation or riboflavin degradation)?
using trained or untrained panelists toevaluate the food and 7) If no chemical test exists, would a sensorytest be hothfeasible
assign it some numerical value. This value (e.g., a hedonic and statistically appropriate?
Labuza (1)has outlined in detail the Hpp~icationof these 1the slope of the line is the zero-order rate constant ho {hie
mathematics to the shelf-life testing of foods based on both in Figure 2, using loglo for the ordinate,
temperature and humidity abuse, and Labuza and Kamman
(18) have reviewed some of the computer solutions for analysis
of shelf-life data. Only a brief review of the critical parameters
can he presented here. What should be made clear is that there Thus to get h l one should multiply the value of the slope by
are two general ways to approach shelf-life testing. The most
common method is to select some single abuse condition such
as high temperature, analyze the product two or three times
during some specified storage period, and then extrapolate
the results to normal storage conditions by using some "fudge
factor," perhapsgained by experience with similar foods. The
..
better annroach is to assume that certain nrinci~lesof
r
chemical kinetics apply with respect to temperatureacceler- 0
ation.. ex..
- . the Arrhenius rrlationshiu. ..and w h r e kinetir de- 6 so-
sign to produce a more accurate prediction. a
Y
using eqn. (9) for zero order, The next step then in this approach is to get an estimate of
[Ao] - [A] = -100 - 50 = -
50 quality unit the error ink from these regression calculations. Basically the
ko = - =1 true slope (8) is the measured slope (k) f the confidence
t 50 50 d limits
For a first-order reaction (eqn. (16)) the same data give
Basis:A=IOOatt= Od
A = 50att=50d Table 2. Estlrnate of Percent Error In Reactlon Rate Constant, k
Calculated QualityValues ~.
Analvtical
~~
Time (d) Zero Order First Order Precision -Change in reactant species monitored.-,
(%) 1% 5% 10% 20% 30% 40% 50%
I . m . 3 . n . a . &
-0 O
. 110 180 0 20 40 60 80 100
D% DAYS
Figure 3. Zerwrder plot of extent of browningof nanhygr-plc whey powder F i w e 4. Firstader plot of extent of bmwning of omhygroscopicwhey powder
held at water activity of 0.44 for three temperawes. held at 35% and a water activw of 0.44 (data from Fig. 3.)
I -1
0.
0.2 0.4 0.6 0.11 1.0 es so 3.1 3.2 3.3 M
W01.r AcIIYII~ I/T * K X 103
Figure 5. lilustratiMl of the ettect on increasing water activity (a,) on the shelf Figure 6 . Typical Arrhenius plot of log k versus inverse absolute temperature
life of a food at three differem temperatures ( T , < <
T2 T3). showing projection to lower temperature.
W g o s c o p i c whey P o d r
Nonenzymatic browning
(25) square wave 25/4SC
a. = 0.44 *
0.019 0.0004 ODld 0.015 ODId
6-DNP lysine loss a, = 0.44 0.018 f 0.001 d-' 0.026 d-'
Relative nuhitianal valve a, = 0.44 0.0123 f 0.0004 d-' 0.0155 d-'
Nonhyqoscopic Whey P O W (25)
Nonenzymatic browning a. = 0.44 0.0069 f 0.0002 ODld 0.0076 OD/d
a. = 0.44 0.0189 f 0.004 dC' 0.0223 d-'
6DNP lysine
Relative nuiritionai value a,= 0.44 0.0116 *
0.001 d-' 0.0153 d-'
pasta
Thiamin (43 square wave 25145'C
a, = 0.44 0.0012 f 0.0002 d-' 0.0016 d-'
a. = 0.54 0.0019 f 0.0003 d-' 0.0023 d-'
a, = 0.65 0.0028 f 0.0002 d-' 0.0037 d-'
Thiamin ( 45) sine wave 25145C
a, = 0.49 0.0016 f 0.0003 d-' 0.0013 d-'
Lysine Iwslprotein quality 144) square wave 35/55-C
a. = 0.44 0.033 f 0.006 wk-' 0.022 wk-'
a. = 0.65 0.063 f 0.012 wk-' 0.063 wk-'
Browning Square wave 35155C
a, = 0.44 2.69 f 0.7 ODldl100g 2.15
a. = 0.65 4.00 f 0.8 O D / d / 1 0 0 g 2.93
a-ONP lysine loss* I55) sine wave 25145'C
a, = 0.49 0.0104 wk-' 0.0073 wk-'
Relative nutritional value 0.0118 f 0.0013 wk-' 0.0093 f 0.0013 wk-'
potato chips 15s) sine wave 25145%
peroxide iormatlon a,= 0.11 0.115 f 0.006 PVW 0.1 19 f 0.002 PVld
conducted studies of quality loss for a series of different food In some cases, the actual rate was faster than the predicted
oroducts stored for uo to one vear under square wave and sine rate indicating a positive-historyeffect while in other cases the
wave temperature distributions. Integrated mathematical opposite was true. These studies illustrated that, although one
models based on the Arrhenius eauation were used and the may be able to develop elegant mathematical models based
equations were corrected for reaction order. In addition, sta- on kinetics and may use elegant statistical models to get
tistics were applied to some of the results of these studies straight line ~ l o t sthe
, errors involved in analysis plus the
where enough data were available. The actual measured k was possi%le changes in mechanism with changingtemperature
compared to the predicted k based on constant temperature may preclude one from accurately predicting the quality loss
studies from a t least three temperatures. of a food undergoing a temperature distribution. This does
Using eqn. (26) as the basis, the group developed the fol- not mean we should not utilize kinetic principles nor apply
lowing equations for the theoretical rate constants. statistics, rather these results indicate the need for better
analytical tools and better experimental design, including
Square waue more temnerature measures and samoline times. and the need
toexamiie the Arrhenius plot (or s h h k to determine
if a chanee in kinetics occurs with temoerature. As our "Latta
chemist"may have found, sometimesone should not draw a
Sine waue straight line.
Acknowledgment
This project was supported in part by the University of
Spike w o w Minnesota Agricultural Experiment Station Grant No. 18-78
and NSF Grant No. 7910370.
(31) Dauies, 0. L., and Budgeti, D. A., J Phorrn. Phormocol., 82,155 (1980) (55) Chen, J. Y., Bohnsack. K., and Labuza,T. P., J F w d Sci, 48,460 (19831.
(321 Co1e.B. R.,andLasdbsfer,L., J. Phorm.Phormocol.,18.101(1966). (56) Lsbula,T.P.,and Bergguiat, S., J FoodSci,48,712 (19831.
I331 Garrett, E. R., J Amen Phorm. Asaoc., 45Bl,171i1956).