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Coffee 1

Coffee
Rinantonio Viani, Association Scientifique Internationale du Café (ASIC), 1802 Corseaux, Switzerland
Marino Petracco, illycaffé S.p.A, Trieste, Italy

1. Introduction . . . . . . . . . . . . . . . 1 6.2.1. Extraction . . . . . . . . . . . . . . . . . 15


2. History . . . . . . . . . . . . . . . . . . 2 6.2.2. Concentration . . . . . . . . . . . . . . . 15
3. Green (Raw) Coffee . . . . . . . . . . 3 6.2.3. Spray-Drying . . . . . . . . . . . . . . . 16
3.1. Botany and Culture . . . . . . . . . . 3 6.2.4. Freeze-Drying . . . . . . . . . . . . . . . 16
3.2. Harvesting and Processing . . . . . 4 6.2.5. Aromatization . . . . . . . . . . . . . . . 17
3.2.1. Arabica . . . . . . . . . . . . . . . . . . . 4 7. Composition . . . . . . . . . . . . . . . 17
3.2.2. Robusta . . . . . . . . . . . . . . . . . . . 6 7.1. Carbohydrates . . . . . . . . . . . . . 17
3.2.3. Liberica and Excelsa . . . . . . . . . . . 6 7.2. Acids . . . . . . . . . . . . . . . . . . . . 19
3.2.4. Processing at the Mill . . . . . . . . . . 6 7.3. Lipids . . . . . . . . . . . . . . . . . . . 21
3.3. Marketing . . . . . . . . . . . . . . . . 7 7.4. Nitrogen Compounds . . . . . . . . . 22
4. Decaffeination . . . . . . . . . . . . . . 10 7.4.1. Amino Acids, Peptides, and Proteins 22
4.1. Low-Moisture Processes . . . . . . . 10
7.4.2. Purines and Nucleic Acids . . . . . . . 22
4.2. High-Moisture Processes . . . . . . . 10
7.4.3. Other Bases . . . . . . . . . . . . . . . . 23
4.3. Processes Using Supercritical Media 11
7.5. Minerals . . . . . . . . . . . . . . . . . . 23
4.4. Coffee Treatments Other than
7.6. Products Formed during Roasting . 23
Decaffeination . . . . . . . . . . . . . . 12
5. Roasting . . . . . . . . . . . . . . . . . . 12 7.6.1. Volatile Aroma . . . . . . . . . . . . . . 24
5.1. Roasters . . . . . . . . . . . . . . . . . . 13 7.6.2. Brown Polymers . . . . . . . . . . . . . 24
5.2. Grinding . . . . . . . . . . . . . . . . . 14 8. Consumption and Physiology . . . . 25
5.3. Packaging . . . . . . . . . . . . . . . . . 14 8.1. Consumption . . . . . . . . . . . . . . . 25
6. Brewed and Instant (Soluble) Coffee 14 8.2. Dietary Value . . . . . . . . . . . . . . . 26
6.1. Brewing . . . . . . . . . . . . . . . . . . 14 8.3. Physiological Value . . . . . . . . . . . 28
6.2. Instant Coffee Manufacture . . . . . 15 9. References . . . . . . . . . . . . . . . . . 29

1. Introduction [1 – 3] In the wet process, the outer skin of the cherry


is squeezed through slots and the pulp surround-
Commercial coffee, the dried seed from two ing the beans is fermented and washed away. The
species of the genus Coffea, C. arabica and C. beans, still covered by the inner shell, the parch-
robusta, is grown as a short tree in the tropics ment, are dried either for a period of up to 1 week
at an altitude ranging from sea level to more in the sun or for a shorter period in a dryer. After
than 2000 m. The ripe cherries (sometimes in- mechanical removal of the parchment, the beans
correctly called “berries”), which usually con- are cleaned and bagged. The main producer of
tain two seeds – the coffee beans – are harvested wet-processed Arabicas, sold as “mild coffees”
and processed in one of two ways. or “milds”, is Colombia, followed by the Central
In the dry process, the cherries are dried in American and Eastern African countries.
the sun for a period of up to three weeks, and the Europe, North America, and Japan are the
outer and inner shells are mechanically removed main consumers. Of the producing countries,
to liberate the coffee beans (“green coffee”), Brazil is the main consumer. For consumption,
which can be cleaned and bagged. This method coffee is roasted (and ground) for sale and con-
is usually applied to Arabicas from Brazil, the sumed as a brew, or further treated by extraction,
main coffee-producing country, and Ethiopia, as concentration, and spray- or freeze-drying and
well as to all Robustas, of which Indonesia and sold as soluble (instant) coffee.
Vietnam are the main producers.

c 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim


10.1002/14356007.a07 315.pub2
2 Coffee

Caffeine, the active principle of coffee, can being roasted and consumed as a brew, kahwa,
be removed from the green bean after soaking had conquered the whole Arabian peninsula and
in water, by dissolving it in a solvent, such as reached the Mediterranean Sea. During the 16th
dichloromethane, ethyl acetate, or supercritical century, coffee became very popular throughout
carbon dioxide. Adsorption on activated carbon the Ottoman Empire.
is also employed. In addition to caffeine, ca. The stimulating properties of coffee are de-
1 % in Arabicas and 2 % in Robustas, the dry scribed by the legends reported in Abdelkadir’s
bean contains ca. 50 % carbohydrates, 8–17 % manuscript, where strength to survive in the
lipids, up to 11 % proteins and amino acids, and desert or to stay awake and pray is restored
ca. 5 % minerals. During roasting, these com- to holy people by chewing the sweet berries
ponents form the typical coffee flavor, of which or by drinking a beverage prepared by roast-
more than 1000 components, many of them fra- ing the berries to make them softer and to re-
grant or sapid, have been identified. duce their bitterness. Leonhard Rauwolf (ca.
1540–1596), physician and botanist from Augs-
burg, was one of the first Europeans to describe
2. History [4] coffee as a drink “almost as black as ink” and
to give a vivid description of Aleppo’s coffee-
Unlike most cultivated plants whose primitive houses. Prospero Alpini (1553–1617), physi-
strains have long ago disappeared by genetic cian and professor of botany at the University of
erosion, wild coffee plants, related to the ac- Padua, drew the first picture of a coffee branch
tual cultivars of C. arabica, still exist in East from a tree seen in the garden of the Bey in
Africa in the region where the main species orig- Cairo. By way of Venice, coffee from Mocha
inated. The plant spread from the rainy forests conquered Europe in the 17th century. Coffee
around Lake Victoria to the Kaffa province in culture was introduced to the Malabar coast of
the Ethiopian highlands, north to the arid Sudan, India and to Ceylon toward the turn of the 16th
where its sweet red cherries, bunna, were picked century. By the end of the 17th century the Dutch
and chewed. Dried cherries are easily stored and had succeeded in cultivating coffee on a com-
transported; thus, their use reached the coastal mercial basis in Java; they broke the Mocha
area, where they are known as m’buni or buni, monopoly in 1711, when the first coffee pro-
and are still consumed sweetened and unroasted duced in the East Indies was auctioned in Ams-
on special occasions as a ceremonial food. terdam. Seedlings from a plant brought to Am-
Intense commercial and political exchanges sterdam in 1706 were distributed to the Euro-
across the Red Sea introduced coffee use to Ara- pean botanical gardens. Due to a state of war,
bia, and its culture may have started as early as the French waited until 1713, when a plant 5 ft
the sixth century in the fertile valleys of the coun- (ca. 2 m) tall was sent to Louis XIV, the Sun
try now known as Yemen. King. It was planted in the Jardin des Plantes
The advent of Mohammedanism, forbidding in Paris and described by Antoine de Jussieu.
the use of alcoholic beverages and encouraging By royal bequest it became the ancestor, with
exchanges through pilgrimages to Mecca, to- related plants from Amsterdam, of most of the
gether with the flourishing of the Arabian and coffee trees planted during the 18th century in
Persian civilizations, asserted the strength of the Western hemisphere, which eventually led to
coffee around the harbor of Mocha and its ex- the decay of Dutch supremacy in the trading of
tension eastward. The Persian scholars Rhazes coffee.
(850–922) and Avicenna (980–1037) mention The Swedish botanist Linnaeus, a friend of
the digestive properties of coffee, probably iden- the Jussieu family, classified the plant as Coffea
tified with bunchum by the former and called bon arabica in 1753. Caffeine [58-08-2], the active
or ban by the latter. ingredient of coffee, was isolated by Runge in
According to Abdelkadir, who in 1587 wrote 1820 from a few beans received from Goethe.
the first historical account dealing specifically The formula of caffeine, which had been de-
with coffee, the expansion northward appears to termined from combustion data by Pfaff and
have been slower. It was only by the second half Liebig in 1832, was established by Medicus in
of the 15th century that coffee, which was then 1875 as 1,3,7-trimethylxanthine, C8 H10 N4 O2 ,
Coffee 3

M r 194.19, and confirmed by E. Fischer in 1897 3. Green (Raw) Coffee


by total synthesis.
3.1. Botany and Culture [5 – 7]

The genus Coffea L. (Rubiaceae) consists of


about 100 species classed as eucoffea. The sub-
genera erythrocoffea, which contains all of the
cultivated species, and argocoffea are both na-
tive to continental Africa. Mascarocoffea from
The year 1869 saw the destruction of cof- Madagascar and paracoffea from the Indian
fee culture in Ceylon (Sri Lanka) by the fun- subcontinent are low in caffeine. Two species
gus Hemileia vastatrix (coffee rust) and the only are economically important, both cultivated
spread of infection to the low-altitude planta- around the world in the tropical belt, Coffea ara-
tions in India, Java, and Sumatra. The Dutch bica L., Arabica coffee, with two main varieties,
botanist Pierre studied the sources of coffee and bourbon and typica, accounting for two-thirds of
in 1895 found a rust-resistant species in Congo, world production, and Coffea canephora Pierre,
Coffea canephora, var. robusta, now the sec- one main variety robusta, one-third of world pro-
ond most economically important type of cof- duction (Table 1). Two other species, C. liberica
fee. Roselius, a Bremen coffee merchant, de- Bull ex Hiern, Liberica coffee, and C. dewevrey
vised the technique of steaming coffee beans to De Wild., Excelsa coffee, have lost all commer-
enlarge their pores, then washing out the caf- cial importance. Arabica cultivars have been de-
feine with a solvent. A patent was issued in 1906 veloped for visual characteristics, such as “mar-
for the decaffeination of green coffee beans by a agogype”, a mutant from typica producing gi-
technique very similar to those applied currently. ant beans; productivity, such as “Mundo Novo”
From the beginning of the 20th century in Brazil; or resistance to diseases, like “Ruiru
on, coffee cooking ceased to be considered a eleven” in Kenya, resistant to the coffee berry
plain kitchen task and stimulated the ingenu- disease, but which has lost some of the typical
ity of inventors that produced a range of in- flavor of Kenyan coffee.
creasingly sophisticated and complex brewing The genetic variability of Arabica coffee has
devices. From the first steam kettle patented remained until quite recently extremely lim-
in 1901 to the lever-operated and the electri- ited; as a consequence, susceptibility to two
cal pump-driven machines, this effort culmi- fungal diseases, coffee leaf rust (CLR), caused
nated with the present-day computer-controlled by Hemileia vastatrix, now encountered world-
“espresso” machines. wide at low altitudes, and coffee berry disease
For the sake of convenience, instantly solu- (CBD), produced by Colletotrichum kahawae,
ble coffee has gained nowadays a wide diffusion. previously known as C. caffeanum, which at-
A patent for making instant coffee had already tacks the green and ripening fruits in cool areas
been granted to Gale in 1865, and commercial at high altitudes in Africa, has increased. Breed-
soluble coffee made its faint appearance at the ing programs aiming at resistance to diseases
beginning of the 20th century. It was not until and pests, increased yield, special shapes and
1938 that Morgenthaler succeeded in obtain- size of plant, and improvement of cup quality
ing the first 19 t of a free-flowing, stable, and have produced new commercial varieties. Natu-
readily soluble coffee extract, which the United ral and bred botanical interspecific hybrids, such
States army found to be very convenient dur- as “Hibrido de Timor”, a spontaneous hybrid
ing World War II. Pure coffee extract was intro- of C. arabica and C. canephora, are used to
duced in 1950, and in 1964 freeze-dried gran- create progenies that are resistant to rust like
ules appeared on the market, having a flavor that Robusta but have Arabica flavor characteristics.
approached that of brew. The introduction of This is accomplished starting from traditional
vacuum packing and the developments of home varieties with a small genetic base (Caturra, Cat-
brewers have, in the 1980s and 1990s, brought uai), and introducing genetic variability from
roast and ground coffee to a level of convenience
approaching that of soluble coffee.
4 Coffee
Table 1. Commercial coffees
spontaneous trees from Ethiopia or Sudan. Com-
mercially important ones are Catimor: a hy- Coffea arabica L. – Coffea canephora
Arabica coffee Pierre – Robusta
brid created by backcross selections of a hybrid coffee
between “Hibrido de Timor” and “Caturra ver- First described by, date Linnaeus, 1753 Pierre, 1895
melho” (a natural mutant of bourbon found in Botanical varieties typica, bourbon robusta
Indigenous to Eastern highland Eastern central
Brazil), and Icatu: an interspecific hybrid bet- rainforest
ween a colchicine-induced tetraploid Robusta Optimal growth temperate equable warm humid climate
plant and the Arabica cultivar “Mundo Novo”. climate
Altitude 700–2000 m 0–800 m
A similar progeny has also been developed in Average yearly 15–23 ◦ C 18–27 ◦ C
Colombia as ”Colombia”. The selection cycle temperature
can now be reduced from 30 years down to less Maximum temperature 25 ◦ C 30 ◦ C
Annual rainfall 1500–2200 mm/m2 2200–3000 mm/m2
than 10 years by multiplying in-vitro selected Plant self-fertile shrub or self-sterile shrub or
F1 hybrids [8]. An interesting low-caffeine so- small tree bearing small tree bearing
maclonal variation, obtained from Arabica x after 3–4 years after 2–3 years
Chromosomes (2n) 44 22
racemosa hybrids, “Aramosa”, has been found Root system deep shallow
highly resistant to drought and early ripening Leaf small, glossy, oval, large, broad,
and has good cup characteristics [9]. Coffea (12–15) × 6 cm corrugated,
(15–30) ×
canephora has a very high genetic variability (5–15) cm
and is usually propagated by cuttings in nurs- Flower after rain, small irregularly, large,
eries. white to cream white, sometimes
pink
The best soil for planting is friable, porous, Fruit, a drupe (cherry or oblong ellipsoid, 15 ellipsoid, striated
well drained, rich in organic matter, and slightly berry; it contains two mm long, several on when dry, 12 mm
acidic. The soil must be deep for Arabica. The seeds surrounded by each leaf axil in long, in tight axillary
parchment with the flat loose clusters, clusters, crimson
plants are cultivated on sheltered slopes arranged grooved faces against crimson or yellow, then black, 9–10
in squares or following the contour of the land each other) 8–9 months to ripen months to ripen,
dries on branch
protected from wind and frost also by intercrop- Seed (bean) oval, flat, deeply oval to round,
ping at early stage with various suitable crops, grooved, 5–13 mm grooved, 4–8 mm
and by rows of trees. For Arabica, the spac- long long
Trade name Arabica Robusta
ing between each plant can even be less than Relative importance 66 % 34 %
1 × 1 m, with a density of 10 000 or more trees (2006)
per hectare, depending on variety, climate, and Cup flavor of roasted and mild, aromatic, acid woody, earthy
brewed beans
the choice of either single-stem or multiple-stem Caffeine content of bean 0.6–1.4 %, average 1.7–4.0 %, average
cut. The best spacing for Robusta is 3 × 2 m. (dry basis) 1.2 % 2.2 %
Various pests attack coffee. Beside CLR and
CBD, other harmful mycetes that deserve men-
tioning are Fusarium (Gibberella) stilboides,
fusarium bark disease, and Fusarium xylari- 3.2. Harvesting and Processing [10, 11]
oides, tracheomycosis or fusarium vascular wilt,
the most serious disease affecting Robusta, also A transverse section of a coffee cherry is shown
affecting Arabica. Nematodes can invade the in Figure 1.
roots (e.g. Meloidogyne coffeicola). Among the
insects that attack coffee the most damaging are
Hypothenemus hampei, “broca”, coffee berry 3.2.1. Arabica
borer (CBB) and Perileucoptera coffeella, “bi-
cho mineiro”. Now that rust-resistant varieties Arabica coffee is harvested by selectively hand
have been introduced, CBB has become the most picking the red ripe cherries every 1–2 weeks. In
important pest, present almost in all producing some countries near the tropics, where seasons
countries, causing a premature fall of berries and are recognizable, ripening occurs in a rather uni-
damaging the seeds within the berries. form way. In such cases, when not enough la-
Coffee 5

bor is available at harvest time, immature and in the sun. They are placed in layers up to 6 cm
ripe cherries are stripped off the branches and thick, turned regularly, and sheltered from rain
collected from the ground along with the over- showers and dew. The coffee dries in 2–3 weeks,
ripe and dry ones. The leaves and twigs are win- and the husks can then be removed mechanically
nowed away in the field. Often a water siphon, from the beans.
in which the heavier cherries sink, while leaves, The wet process, which uses water flowing
twigs, and dry cherries float and are diverted, down a slight gradient, was introduced by the
is used to carry out an initial grading of the Dutch in the West Indies during the first half of
cherries. The middle fraction containing the ripe the 18th century and is used where enough water
cherries is further treated by either the dry pro- is available and the climate is humid. Harvested
cess, in which the whole cherry is dried, or the cherries are handled in bulk if they can be pro-
wet process, in which the pulp surrounding the cessed in less than one day; otherwise, they are
bean is fermented and washed away before the stored under water to avoid overheating. Where
beans are dried in their parchment [12]. Raw the water supply is abundant, cherries are pre-
beans recently processed in either of these ways graded in a washing channel or a siphon tank.
are recognized by their color: dry-processed (or Where water is scarce, the cherries are supplied
natural) beans are yellow-green to pale brown, dry to the pulper. This reduces water consump-
whereas wet-processed (or washed) beans are tion by half (60 vs. 120 L/kg). Pulping is done
green to blue-green. by squeezing the cherries through slots in drum
or disk machines to separate the outer skin and
some of the fleshy pulp (the pericarp) from the
parchment coffee (the bean surrounded by the
endocarp). Parchment coffee is then sorted by
gravity, and floaters, light parchment, peaber-
ries (oval beans from cherries containing only
one seed), and heavy parchment are sent to sep-
arate tanks. The sticky pulp still adhering to the
parchment is loosened by fermentation in a tank,
either dry in the open for 24–48 h or under water
for up to 72 h, depending on the altitude. The fine
acid taste of some of the coffees grown at high
altitudes is attributed to the long fermentation
time. Adding pectic enzymes or alkali may ac-
celerate fermentation. Fermentation is stopped
by soaking parchment coffee in water.
Pulping and fermentation are sometimes
combined in the “aquapulper,” a pulper and
Figure 1. Transverse section of a coffee cherry containing demucilager, where the pulp is rubbed off the
two seeds (courtesy Dr. E. Dentan) parchment mechanically. All pulp residues are
Pericarp: “Skin” or exocarp, red (or yellow); “Pulp” or washed away in a channel where the remaining
mesocarp, yellow-white; “Parchment” or endocarp, pale
yellow
skins and whole cherries, which are lighter, are
“Silverskin” or spermoderm, silvery flushed away and collected on wire trays. The
“Bean” or endosperm, yellow-green when dry cherries are dried in the sun for 5–10 d on wire
The site occupied by the “mucilage,” yellow-white, appears strapping, which ensures thorough air circula-
black in the figure, having been dissolved away during the
preparation of the sample.
tion, or on barbecues. Where the climate is not
A coffee cherry may contain one, two, or rarely, three seeds. sufficiently dry, sun drying can be partially or
completely replaced by artificial drying in tray
or tower air dryers for 24–36 h. Particular care
The dry process is applied where water is must be taken to avoid overheating the coffee,
scarce (as in Ethiopia and Brazil) and to the off- which results in the subsequent development of
grade cherries discarded during wet processing. a sour taste.
Freshly harvested cherries are spread out to dry
6 Coffee

3.2.2. Robusta 3.2.3. Liberica and Excelsa

Robusta cherries remain on the tree at maturity, Liberica cherries are rather pulpy and difficult
undergoing a slight fermentation, which is inter- to dry. Excelsa cherries ripen a few at a time and
rupted when the fruit dries. The ripe cherries are then drop to the soil when dry. In both cases,
selectively picked from the large shrubs by start- uncontrolled fermentation occurs, which con-
ing at the lower branches. The practice of strip- tributes to the unclean taste of their brew. Their
ping cherries off the tree at various degrees of importance is waning and they will not be dis-
maturity from green to dry, and drying, husking, cussed further.
and bagging them without sorting is becoming Coffee beans of various types are shown in
common. Figure 2.

3.2.4. Processing at the Mill

Dry cherry or parchment coffee is normally


cured in centralized mills. Impurities are re-
moved from coffee by sizing on oscillating
screens and by density differences in a pneu-
matic “catador” or on densimetric vibrating ta-
bles. Processing rate is up to 1 t/h for cherry and
2 t/h for parchment coffee. Dehulling of the dry
parchment or of the shell, which becomes brittle
when it is dried, is done by impact in a cen-
trifugal mill, usually a ribbed steel drum or a
crossbar revolving in a perforated case, which
also polishes the silverskin off the surface of
the beans and winnows away the shells. Capac-
ities are 0.1 t/h for hand-operated mills and up
to 3 t/h for motor-operated mills. The raw cof-
fee beans are graded by size, through revolving
or flat screens with round holes, at the rate of
0.1–1.5 t/h. Peaberries, which are oval, can be
separated from flat, regular beans through slot
holes or by rolling them down a conveyor belt
that runs upward at a slight angle. They are sold
separately under the name caracoli. Grading by
density is done by winnowing the beans on den-
simetric tables (capacity 1–4 t/h) or in catadors
(capacity 0.8–1.5 t/h), where sand and stones
are again removed and the product is separated
into healthy beans of full weight, medium beans,
lighter inferior beans (empty, insect damaged,
etc.), “triage” (material rejected from superior
grades), and “brisures” (bits).
Grading by color, recommended to get rid
of visible defects [13], is accomplished in sev-
eral ways: by hand picking (capacity < 1 kg/h
Figure 2. Coffee beans of various types per person); electronically with monochromatic
a) roasted Arabica; b) roasted Robusta; c) raw Arabica; equipment, used with Robustas to sort out black
d) raw Robusta
beans; bichromatically, by which both brown
Coffee 7

and bleached beans are eliminated in Arabi- Grading by cupping is sometimes performed
cas; or fluorimetrically at 360 nm, to eliminate in the producing countries, but more often it is
“stinker” beans, which have an impure taste, in done in the consuming countries. Representa-
freshly cured washed Arabicas. The beans are tive samples of coffee are examined for defective
fed into chutes on counterrotating rollers or on beans and extraneous matter, roasted and noted
belts and viewed from different angles. The re- for uniformity of roasting, ground and brewed
jected beans are driven out by compressed air in porcelain equipment, tested by smelling, and
(capacity up to 150 kg/h per channel). tasted by swiftly drawing a spoonful against the
palate [14]. Washed Arabicas are graded accord-
ing to acidity, body, and flavor. Dry-processed
Brazilian coffees are subdivided in order of de-
creasing quality as strictly soft, soft, softish,
hardish, hard, and Rioy (a typical medicinal
off-taste). The best Robustas are neutral and
clean, while defective ones are harsh, rubbery,
or earthy.
Placing 60 or 69 kg of coffee (70 kg in
Colombia) into jute bags marked with the name
of the producer and the year of harvest readies
the coffee for shipping. The shipping of Robusta
coffee in bulk containers is now practiced.
Equipment used for separating impurities and
for grading green coffee beans is shown in Fig-
ure 3.

3.3. Marketing [15]

Today one of the most important food commodi-


ties, the world green coffee market has been
characterized in the past by long periods of over-
supply alternating with brief periods of short-
age, linked to the size of the crop. A series of
short-term agreements, concluded by producing
countries in an effort to avoid wild fluctuations in
prices, finally led to the first International Coffee
Agreement (ICA), signed in 1962 by both pro-
ducing and consuming countries at the United
Nations. The agreement, which is administered
by the International Coffee Organization (ICO)
with a head office in London, has been reviewed
several times. The present (in 2006) agreement
entered into force in 2001 with the signature of
44 exporting (> 99 % of all coffee produced)
and 30 importing members of the ICO. All ma-
jor consumer countries are represented, includ-
Figure 3. Equipment used in coffee processing ing the United States as a new entry. The ob-
(courtesy of Bühler, Uzwil, Switzerland) jectives of the new ICA, which have switched in
A) Pneumatic aspirator, the catador, which classifies accord- the 1990s from regulation of supply and demand
ing to density; B) Vibrating separator, which classifies by
size through export quotas to assistance to interna-
tional trade, are:
8 Coffee

• Encouraging members to develop a sustain- (Cost Insurance Freight) selected European


able coffee economy ports.
• Promoting coffee consumption
Three consumer issues have acquired some
• Promoting quality of coffee
importance after the 1990s in the coffee trade.
• Providing a forum for the private sector for
Fair Trade coffee is a commodity produced
representatives of the private sector (traders,
in many less developed countries, sometimes in
roasters, etc.)
conditions and of a quality below current food
• Promoting training and information programs
standards, further exacerbated after liberaliza-
designed to assist the transfer of technology
tion of trade in the late 1980s and early 1990s,
relevant to member countries
when world coffee prices reached a very low
• Analyzing and advising on the preparation
level, rendering the living conditions of small
of projects to the benefit of the world coffee
coffee farmers precarious. As a reaction, a new
economy
way of trading, namely “Fair Trade”, was in-
Table 2 [16] lists the total coffee production troduced in 1988 in the Netherlands to improve
for the crop years 1993 to 1998 in thousands the working and living conditions of small farm-
of 60-kg bags – the traditional trade unit – of all ers by direct trade, a guaranteed minimum price,
ICO exporting member countries. prefinancing, and long-term contracts, and to re-
Marketing systems have involved different duce their dependence on the local wholesaler.
types of semigovernmental agencies in the pro- Direct trade has been extended in the 1990s to
ducing countries. Liberalization of trade, partic- other commodities and many importing coun-
ularly noticeable in the 1990s, has led to price tries. Although reaching only a small fraction
transparency and eliminated the monopoly of of the coffee traded, small-scale direct procure-
Marketing Boards in the sale of coffee. ment systems, now benefiting from the financial
In the consuming countries, coffee is traded backing of governmental and private funds, have
in the following ways: helped in drawing the attention of consumers in
1) The “forwards market” applies to coffee be- the developed countries to the question of redis-
fore it leaves the producing country. This is tribution of profits in the production areas. Major
usually only available to large traders and industrial users now revise their trading prac-
roasters who need to ensure large quantities tices, introducing some form of direct procure-
(thousands of bags) of well-defined grades ment, which allows them to assist farmers to pro-
and origins throughout the year. duce coffee according to their quality standards.
2) The “spot market” covers coffee once it has Organically grown coffee has picked up a few
actually landed in an importing country. Prac- percent of trade since it appeared in the 1980s
tically all origins are available at one of the among the specialty coffees in the United States
main importing ports. This is often the only with an image of wholesomeness [17]. In the
way of purchasing available to small roasters 1990s its image has moved to one of environ-
who buy a few bags at a time and wish to avoid mental protection, according to the aims of or-
price risks. ganic agriculture of working with renewable re-
3) The exchange or terminal market covers cof- sources, maintaining genetic diversity, minimiz-
fee scheduled for delivery at a set date and ing all sources of agricultural pollution, and con-
price in the future. Futures contracts are taken sidering the ecological and social impact of agri-
either to avoid (hedging) or to exploit (spec- cultural systems. Regulations for organic prod-
ulating) price fluctuations. The main markets ucts, including coffee, which must be certified
are the New York Coffee, Sugar, and Cocoa by recognized inspection agencies, have been
Exchange (NYCSCE), where lots of 37 500 issued [18].
lb (ca. 250 bags) of “milds” are traded un- Sustainability is a general approach in coffee
der the “C” contract, with prices in US cents economy that, according to a preliminary draft
per pound ex-dock, and the London Inter- wording, implies conditions of production, pro-
national Financial Futures and Optional Ex- cessing, and trade for all parties involved in the
change (LIFFE), which deals in Robustas, supply chain that:
with 5-t lots and prices in US$ per ton, CIF
Coffee 9
Table 2. Green coffee world production (thousands of 60-kg bags; source: International Coffee Organization)
Country Species* 2000 2001 2002 2003 2004 2005 Average
TOTAL 115 064 106 645 121 913 103 849 113 631 106 386 111 248
Bolivia (A) 173 118 149 125 161 115 140
Colombia (A) 10532 11999 11889 11197 12043 11900 11593
Costa Rica (A) 2253 2166 1938 1802 1726 1758 1941
Cuba (A) 313 285 239 254 257 275 271
Dominican Republic (A) 439 435 433 354 467 791 487
El Salvador (A) 1707 1667 1438 1457 1447 1372 1515
Ethiopia (A) 2768 3756 3693 3874 5000 4500 3932
Haiti (A) 420 402 374 373 355 375 383
Honduras (A) 2667 3036 2497 2968 2575 2990 2789
Jamaica (A) 37 30 38 36 26 35 34
Kenya (A) 1001 991 945 673 709 1002 887
Malawi (A) 63 60 42 48 21 25 43
Mexico (A) 4815 4200 4000 4550 3407 4000 4162
Nicaragua (A) 1595 1116 1199 1405 1127 1400 1307
Panama (A) 170 160 140 172 90 170 150
Paraguay (A) 22 20 23 20 20 23 21
Peru (A) 2596 2749 2900 2616 3355 2420 2773
Rwanda (A) 273 296 319 265 450 300 317
Venezuela (A) 956 721 869 786 701 820 809
Zambia (A) 94 100 119 101 111 117 107
Zimbabwe (A) 109 121 106 84 96 58 96
Brazil (A/R) 9:1 34 100 30 837 48 617 28 820 39 272 32 944 35 765
Burundi (A/R) 9:1 337 259 475 333 430 350 364
Guatemala (A/R) 10:0 4940 3669 4070 3610 3703 3675 3945
Papua New Guinea (A/R) 10:0 1041 1062 1085 1155 997 1267 1101
Tanzania (A/R) 6:4 809 624 824 611 763 750 730
Angola (R) 50 21 57 38 15 20 34
Benin (R) 0 0 0 0 0 1 0
Central African Rep. (R) 122 75 92 43 61 100 82
Congo, Rep. of (R) 3 3 3 3 3 3 3
Côte d’Ivoire (R) 4846 3595 3145 2689 2328 2171 3129
Gabon (R) 0 1 1 0 0 2 1
Ghana (R) 76 13 32 16 11 25 29
Guinea (R) 368 254 272 407 245 310 309
Nigeria (R) 48 43 51 45 42 45 46
Sierra Leone (R) 53 53 32 24 5 25 32
Thailand (R) 1692 548 758 846 797 764 901
Togo (R) 197 113 68 144 166 168 143
Trinidad and Tobago (R) 14 15 15 15 14 10 14
Vietnam (R) 14 939 13 133 11 555 15 230 13 844 11 000 13 284
Cameroon (R/A) 9:1 1113 686 801 900 727 1000 871
Congo, Dem. Rep. of (R/A) 5:5 362 421 319 427 360 575 411
Ecuador (R/A) 6:4 872 893 732 766 938 1125 888
India (R/A) 6:4 4516 4970 4683 4495 3844 4630 4523
Indonesia (R/A) 9:1 6978 6833 6785 6571 7536 7654 7060
Madagascar (R/A) 10:0 366 147 445 434 388 425 368
Philippines (R/A) 8:2 775 759 721 433 373 500 594
Sri Lanka (R/A) 10:0 43 32 35 36 32 35 36
Uganda (R/A) 7:3 3401 3158 2890 2598 2593 2366 2834
Total Arabica 74 783 71 927 87 278 68 460 78 805 74 067 75 887
Total Robusta 40 281 34 718 34 636 35 389 34 826 32 319 35 361
Ratio A/R 1.9 2.1 2.5 1.9 2.3 2.3 2.1
* A = Arabica, R = Robusta, A/R = predominantly Arabica, R/A = predominantly Robusta.

1) Provide an economic return that covers pro- 3) Secure social and working conditions in ac-
duction and living costs plus a further margin cordance with international standards, con-
for development, ducive to the maintenance of stable commu-
2) Treat the environment responsibly so that nat- nities.
ural resources remain available to future gen-
erations,
10 Coffee
Table 3. Decaffeination by low-moisture processes
Operation Medium Conditions
t, ◦ C Time, h
Soaking steam and water 22–100 0.25–5
Decaffeination water-saturated solvent
dichloromethane [22] 60–100 2–12
ethyl acetate [23] 80–105 3–12
fats and oils* [24, 25] 95–105 6–9
Deodorization steam 100–110 1–4
Drying heat 40–80 0.5–10
* No longer used.

4. Decaffeination [19] evaporation, or by steam stripping of the caf-


feine under vacuum. Losses due to leaching of
The stimulating effect of coffee is due to the hydrosoluble material are low, and caffeine, con-
presence of the alkaloid caffeine (structure, see taining a few percent of waxes from the surface
2); decaffeinated coffee gives a brew devoid of of the beans, is recovered and purified by suc-
this effect. The presence of water (caffeic acid cessive crystallizations to pharmaceutical grade
as a dope has been proposed [20]) is essential for use in soft drinks and medicines [21]. Typical
in decaffeination to soften and open the cellular operating conditions are given in Table 3.
structure of the beans and to ensure the diffusion
of caffeine across the cell walls by solubilizing
the caffeine – potassium chlorogenate complex. 4.2. High-Moisture Processes
The ease of decaffeination increases with the
moisture level in the beans, while the selectiv- In high-moisture processes, green or roasted cof-
ity for caffeine extraction with respect to other fee beans are soaked in water until they have
water-soluble constituents decreases. Industrial reached the required moisture level. Decaffeina-
processes, which are usually carried out with tion is carried out by dissolution with an aqueous
green beans, can be broadly divided into two solution of 10–30 % noncaffeinic, soluble cof-
main types: those performed at moisture levels fee solids. The resulting caffeine-enriched solu-
below 50 % (usually between 30 and 45 %), and tion is then decaffeinated either by liquid – liq-
those performed above 50 % (usually between uid extraction with any of the solvents used in the
55 and 65 %). low-moisture processes or by adsorption of the
caffeine on activated carbon or on ion-exchange
resin. This solution is then used to decaffeinate
4.1. Low-Moisture Processes new beans.
Alternatively, the swollen green beans may
Low-moisture decaffeination processes are ap- be decaffeinated with fresh water. After removal
plied to green coffee to avoid removing or alter- of the caffeine the solution is concentrated and
ing fragile aromatic constituents formed during reabsorbed on the predried decaffeinated beans
roasting. The beans are soaked in a mixer, col- from which it has been obtained, thus replac-
umn, or rotating drum and extracted with a non- ing noncaffeine solids otherwise lost. Losses of
polar solvent in one or more columns or rotating coffee solids are usually higher with adsorption
drums. The residual caffeine level in the beans processes than with solvent processes. Losses on
is lowered to less than 0.1 % in the dried decaf- the adsorbent may be reduced by precharging it
feinated beans by most national regulations, or with sucrose or by regenerating it with acetic
to less than 3 % of the amount initially present acid or ethanol solutions. In addition, pretreat-
(the commercial practice in some countries). ment of active carbon with formic or hydrochlo-
The beans are then deodorized (solvent traces are ric acid reduces discoloration of the beans. Table
removed by steam stripping) and dried to their 4 gives typical operating conditions.
initial moisture content in a tower or a fluidized-
bed drier under atmospheric or reduced pressure.
The solvent is recovered by batch or continuous
Coffee 11
Table 4. Decaffeination by high-moisture processes
Operation Medium Conditions
t, ◦ C Time, h
Soaking water [26] 70–100 0.2–2
Decaffeination of extract
Liquid – liquid
extraction dichloromethane [27] 80–85 10
Deodorization steam 100–110 2
Adsorption Amberlite [28] a ambient
Duolite [29] b 95
acid-activated carbon [30 – 32] 60–100 5–8
Decaffeination of beans
Same beans in a loop 60–100 5–8
New beans counter- 70–90 8
current
Drying heat 40–80 0.5–10
a
Amberlite XAD-2, 4, 7 or 8 (Rohm & Haas); not used.
b
Duolite S561 (Diamond Shamrock); not used.

Table 5. Decaffeination using supercritical media


Medium Conditions
t, ◦ C p, MPa Time, h Reference
Carbon dioxide 40–80 20–30 5–30 [33]
Nitrous oxide * 75 20–38 4 [34]
Propane * 97–120 10–15 6 [35]
* Not used.

4.3. Processes Using Supercritical Media and a scheme of decaffeination using supercrit-
ical carbon dioxide is shown in Figure 5.
Supercritical carbon dioxide, i.e., at tempera-
tures and pressures above the critical point of
31.06 ◦ C and 7.38 MPa (73.8 bar), can be used
to decaffeinate coffee by a process called de-
straction by its inventor K. Zosel. The super-
critical medium in a pressure vessel is circulated
through moist coffee, where it becomes charged
with caffeine. It is then passed through a sec-
ond pressurized vessel containing an adsorbing
medium such as activated carbon, resin, or wa-
ter, which retains the caffeine. The solubility of
caffeine increases with the density of supercrit-
ical carbon dioxide, thus increasing with pres-
sure at constant temperature and decreasing with
temperature increases at constant pressure. This
property can be used in the separation step. Be-
sides carbon dioxide, which is employed in at
least one industrial decaffeination plant, other
gases have also been proposed for decaffeina-
tion (Table 5).
Both carbon dioxide and propane can also
dissolve caffeine in the liquid state below the
critical temperature. The pressure – temperature Figure 4. Pressure – temperature diagram of carbon diox-
ide
diagram of carbon dioxide is given in Figure 4, Densities from 100 to 1200 g/L are given as the third di-
mension [36].
12 Coffee

5. Roasting [37, 38]


The stone-hard blue- to yellow-green raw cof-
fee bean of density 550–700 g/L has a sweet as-
tringent taste and a weak “green” aroma. Dur-
ing the roasting process, which occurs at ca.
200 ◦ C, the coffee bean develops a brittle struc-
ture, a dark brown color, and a characteristic fla-
vor and aroma [39]. At the beginning of roast-
ing, for temperature increases up to 120–150 ◦ C,
moisture is released while the beans contract
slightly and become paler. Browning reactions
start, and the beans begin to swell and release
some gas, mostly carbon dioxide, with moisture
and some carbon monoxide. The reaction be-
comes exothermic, and above 180 ◦ C, the main
aromatic constituents form. Pressure buildup in
the beans is said to reach 1.5–2.5 MPa, and,
when the bean has almost doubled its volume
[40], the cellular structure ruptures [41]. The
final temperature reached by the bean is 190–
240 ◦ C, with roasting losses ranging from 13
to 15 % for a light-roasted coffee, consumed in
Figure 5. Decaffeination with supercritical media [36] northern Europe, and up to 20–22 % for a dark
A) Caffeine is washed off the fluid with water in a washing roast, typical of southern Europe.
tower and recuperated; B) Caffeine is adsorbed on a column
containing activated carbon or resin, and the fluid is contin-
uously recycled
a) Moist green beans; b) CO2 + caffeine; c) washing tower;
d) heat exchanger; e) distillation chamber; f) degassing
chamber; g) active carbon or adsorbing resin column

4.4. Coffee Treatments Other than


Decaffeination

Coffees processed by methods other than decaf-


feination are marketed in Germany. Green cof-
fee beans are either treated for several hours
with supersaturated steam (the Lendrich pro-
cess) or washed with dichloromethane. Roast
coffee beans can be washed with liquid carbon
dioxide (the Bach process). All of these pro-
cesses are claimed to make coffee more easily di-
gested by removing irritating substances formed
at roasting or their precursors in the green bean.
Clinical and epidemiological research does not
show a direct relationship between the removal
Figure 6. Changes occurring in coffee beans during
of specific constituents other than caffeine (and roasting
cafestol/kahweol) and the physiological effects (courtesy Dr. G. Pictet)
of drinking coffee.
Coffee 13

Figure 6 shows the temperature profile, roast- up to 20 % more extractable matter when brewed
ing losses, moisture content, apparent bulk den- and a more pronounced taste. Less spectacu-
sity, and volatile aroma released by Arabica lar results can also be attained by using tradi-
beans with an initial moisture content of 10 %, tional conduction – convection roasters at high
heated up to 240 ◦ C in 12 min. Similar graphs final temperature conditions and low gas vol-
are obtained with roasting cycles of 6–18 min umes [44 – 46]. Figures 7, 8, and 9 show exam-
by adjusting the ratio of beans to hot air. With ples of batch and continuous industrial roasters
faster roasting cycles, down to less than 2 min, (courtesy of Probat, Emmerich, Germany).
uniformity of roasting throughout the bean is re-
duced. For a given roasting loss, the apparent
bulk density, quantity of aroma released, and
extractable solids at brewing increase. Robus-
tas need longer roasting times to attain the same
roasting losses as Arabicas. On subsequent cool-
ing, which may be accelerated by quenching the
roasted beans with water, residual carbon diox-
ide is still present in the beans and is slowly
released over a period of days.

5.1. Roasters [42]


Figure 7. Conduction – convection drum batch roaster;
Green coffee is delivered either in palletized roasting cycle 8–12 min and hourly capacity up to 3 t, a
bags or in bulk. After the coffee is cleaned, it versatile model
a, b) Raw coffee supply; c) Roasting drum with mixing
is stored in silos and then automatically con- vanes and central quenching system; d, e) Burner with roast-
veyed for volumetric or gravimetric dosage and ing gas at 550 ◦ C; f – k) Recirculation with cyclone for chaff
roasting. Roasters can be subdivided into con- removal; exhaust fumes are vented through a catalyzer; l –
duction roasters, with direct flame heating, and n) Air flow to cool the roasted coffee, which is fluidized
through a destoner; o) output
convection roasters, employing preheated gas ei-
ther in a laminar or a turbulent flow (fluidiza-
tion). There are many roaster models, operat-
ing both batchwise or continuously, with capac-
ities ranging from a few kilograms to more than
5 t/h. These range from manual to fully auto-
matic, some having the capability of program-
ming the roasting cycle. They are operated with
either gas or fuel oil, consuming energy at the
rate of 1–2 GJ per ton of green coffee. Mod-
els with gas recirculation and catalyzers can re-
duce gas emission below 50 mg/m3 . Odors and
emissions are suppressed by a water spray last-
ing 10–15 s and by passing steam through the
catalyzer [43]. Regular automatic cleaning cy-
cles in some models avoid the buildup of tars.
In the newer convection models, roasted coffee Figure 8. Convection tangential batch roaster; roasting cy-
with a density of 300–450 g/L can be prepared cle 1–5.5 min and hourly capacity of 750 kg, a high-yield
by modulation of the temperature and the ra- model
tio between the hot gas and beans. That is, a a) Raw coffee supply; b) Tangential roaster; c – g) Burner
with high-velocity roasting air mixed for the desired temper-
roasting temperature ca. 300 ◦ C, short exposure ature; h – o) Recirculation with cyclone for chaff removal;
time (2–3 min), and high air : bean ratios pro- exhaust fumes are vented through a catalyzer; p – u) Air
duce low-density roasted coffees; this so-called flow to cool the roasted coffee, which is fluidized through a
high-extraction or fast-roasted coffee can yield destoner; v) output
14 Coffee

in non-airtight packs or allowed to degas for up


to 48 h and then filled under vacuum in metal
cans or in plastic containers impermeable to air
and to carbon dioxide. Coffee is more often pre-
pared for market preground and packed in brick
packs or cans after degassing or under an initial
slight vacuum in flexible bags with a one-way
degassing valve. In this case, 2–4 h of degassing
is sufficient [50]. In pressure-tight cans, optimal
aroma is reached after a few weeks if packeged
Figure 9. Convection continuous roaster; roasting time up in a protective atmosphere of inert gas.
to 6 min and hourly capacity up to 4 t, suitable for regular
production in instant coffee plants
a) Raw coffee inlet; b) Roasting drum with small batch com-
partments; c – h) Air cooling of roasted coffee; i – p) Burner 6. Brewed and Instant (Soluble)
with high-velocity roasting air, which can be adjusted in one
or more heating stages between 240 and 350 ◦ C; recircula- Coffee
tion with cyclone for chaff removal; exhaust fumes vented
through a catalyzer Roasted coffee is either sold as whole beans or
already ground for brewing and immediate con-
sumption, or further processed at the coffee plant
5.2. Grinding [47] where, after extraction, the soluble solids are
Grinding of the brittle beans is easily done in concentrated and dried to produce instant cof-
mills that vary in capacity from a few grams for fee.
household equipment to 4 t/h for industrial roll
mills. The average particle size of the ground
coffee depends on the extraction equipment to 6.1. Brewing [51]
be used. Characteristic particle sizes in millime-
ters for various brewing methods follow: In spite of the apparent simplicity of coffee
brewing–just a pinch of grounds dispersed in
Industrial extracts 1.0 to bean halves
hot water–a bewildering array of domestic and
U.S. drip, percolator 0.7–1.0 professional brewing tools have made their ap-
Filter 0.4–0.6 pearance, giving origin to different consumption
Espresso 0.3–0.4
styles and cultures. The traditional brewing tech-
Middle East < 0.1
nique, still applied in several parts of the world,
consists of boiling coarsely ground coffee (in
the Nordic countries) or very finely ground cof-
5.3. Packaging [48] fee (in the Middle East) in water, infusing it for
several minutes (up to 30), and serving it without
Unlike raw beans, roasted coffee spoils rela- separation of the grounds.
tively quickly if unprotected from oxygen and The main problem being the separation of
moisture. At ambient temperature, some detri- the unpleasant spent grounds from the beverage,
mental changes in brew flavor occur. various ingenious filtering devices–sometimes
lined with filter paper or cloth–evolved, fitting to
Beans Ground plain or reversible pots. For example, in a typical
Fresh roast 6d 48 h household percolator, hot water is continuously
Weaker aroma 10–12 d 4–6 d
Stale 4–6 weeks 2 weeks
recirculated through a bed of coarsely ground
coffee (average particle diameter 0.7–1.0 mm).
The presence of residual carbon dioxide of ca. The extract is then filtered when it has reached
4 cm3 /g, which corresponds to an overpressure the desired concentration of soluble solids. In
of 0.5 MPa [49] in the beans, precludes packing more recent automatic drip coffee machines, sol-
of freshly roasted coffee in airtight packages. uble solids can be leached from a bed of ground
Coffee is either prepared for market as beans coffee (average diameter 0.4–0.6 mm) kept on a
Coffee 15

filter at slightly above atmospheric pressure for


up to 15 min with or without recirculation.
The request for faster preparation of a cup
arose around the beginning of the 20th century,
when the first so-called “espresso” machine was
built by Bezzera. Speed of percolation was in-
creased at that time by steam-generated water
pressure. By use of overpressure, as in house-
hold and food service espresso machines, the
water passes through a bed of coffee (average
diameter 0.3–0.4 mm) at a temperature depend-
ing on the desired pressure. A nimbler control
of brewing conditions was made possible using
compressed air boosters (as in a patent by Illy
[52]), or lever-operated pistons or electrically-
driven pumps. In all of these instances, produc-
tion of water pressure is disconnected from the
temperature, which remains slightly below its
boiling point. The yield of soluble solids can at-
tain 20–30 %, depending on the grind and the
technique employed [53].

6.2. Instant Coffee Manufacture [54, 56]


6.2.1. Extraction
Figure 10. Extraction battery of six percolators with
temperature profile [56]
In an instant coffee plant, coarsely ground cof-
fee (average diameter 1.0 mm to bean halves) is
extracted with softened water in a battery of five The major manufacturers now use shorter
to eight percolation columns, with cell capac- percolators with more finely ground roast cof-
ity from a few kilograms up to 1 t. The process fee. The shorter extraction times thus obtained,
operates semicontinuously, with water at 160– together with new techniques to protect and rec-
180 ◦ C passing as a countercurrent to the coffee tify the volatile aroma, improve quality, which
from the most extracted cell to the one just filled now approaches that of a brew, even at extraction
with freshly ground, roasted coffee. The cells yields around 50 % [57].
are divided into two groups: the hot cells at a
temperature of 140–180 ◦ C under a pressure of
1.4–1.6 MPa (14–16 bar), and the cold cells at 6.2.2. Concentration
a temperature of ca. 100 ◦ C. In the hot cells, the
extraction of difficult material, carbohydrates in Extract at a concentration of 30 % or more can
particular, takes place; in the cold cells, the most be dried directly, but with a high loss of aro-
flavorful material is extracted. Extract is with- matic constituents. The extract coming out of the
drawn from the fresh cell, cooled to 4–5 ◦ C in hot section contains fewer volatile aromatic con-
a heat exchanger, and then sent into a scale in stituents than cold extract. The hot extract can
amounts that depend on the desired yield (35– be evaporated to a concentration of 50–60 % af-
55 %) from the roast and ground coffee and on ter flashing or steam stripping the volatile aroma
the concentration of the extract. At the end of or by separating hot from cold extracts; it then
the withdrawal period, a fresh cell enters the cir- can be mixed with diluted aroma or cold extract
cuit, while the spent grounds are evacuated from to reach a standardized extract at ca. 40 % con-
the bottom of the most extracted cell. Figure 10 centration. A more gentle concentration process
shows an extraction battery with six cells [56].
16 Coffee

involves freezing the extract and then mechani- 6.2.4. Freeze-Drying


cally separating the almost pure ice crystals. By
this technique, coffee extract can be efficiently During this operation, extract is frozen with sep-
concentrated up to 35–40 % with relatively low aration of ice crystals, which are then sublimated
flavor or product losses. under vacuum. The process entails several steps:

Primary Freezing. Cold extract at 4–5 ◦ C is


6.2.3. Spray-Drying prechilled to soft ice slush at − 6 to − 8 ◦ C. The
bulk density and, to some extent, the color of the
Cooled and clarified extract is nebulized through final product depend on the degree and nature of
a rotary or static pressure nozzle into the top of foaming, with nitrogen giving a lighter product
a spray tower, dried by a cocurrent flow of hot than carbon dioxide.
air at ca. 250 ◦ C, and collected in the conical
bottom of the tower at a temperature ca. 50 ◦ C. Secondary Freezing. The soft ice is cooled
Coarse, free-flowing nondusty powders with a down stepwise to − 40 to − 50 ◦ C on a steel
mean size of 200–300 µm and a residual mois- belt, on trays, or on drums. The size and the rate
ture of 2–4 % are obtained. Bulk density can be of formation of ice crystals influence the color
adjusted between 230 and 280 g/L by foaming and aroma retention of the product. Larger crys-
the extract with an inert gas, usually carbon diox- tals give a darker product, with freezing times of
ide or nitrogen. The powder can be agglomerated 10–180 min, while light-colored products can be
to a coarse structure by rewetting, which makes obtained by fast freezing for 30–120 s on freez-
it easy to spoon and mix with hot water. A spray- ing drums.
drying tower is shown in Figure 11.
Grinding. The ice slabs at a temperature of
− 40 to − 45 ◦ C are ground and sieved to the
desired size. Undersized or fine particles are re-
worked. The frozen particulate is put into trays,
which are loaded on carriers and introduced into
the drying section.

Drying. The drying chamber may be a batch


type, where the trays remain fixed on heating
plates through the drying operation, or a semi-
continuous type, in which the tray carriers move
through a vacuum lock into a drying tunnel,
where they pass through successive temperature
zones and exit through another vacuum lock. In
a fully continuous freeze dryer, the frozen cof-
fee particulate is fed directly into the vacuum
chamber from a feed tank, progressing through
the dryer to a discharge tank. The drying cham-
ber is fitted with heating plates, which provide
Figure 11. Spray-drying tower
the sublimation energy to convert ice into wa-
(courtesy of Niro Atomizer, Copenhagen) [58] ter vapor. The vapor is collected on cooled con-
a) Cooled and clarified coffee extract (30–50 % solids); densers, and a pumping device keeps the cham-
b) Nozzle assembly; c) Hot air (ca. 250 ◦ C); d) Transition ber pressure lower than the triple point of water
cone for uniform spray – air mixing flow in the upper region
of the dryer; e) Exhaust air to dry collector for fines recovery
(613 Pa). A product with 1–4 % moisture at a
by cyclone or bag filter (reslurried in the feed or agglom- temperature of 45–50 ◦ C is obtained.
erated); f) Chamber cone; g) Powder discharge (over 90 %
recovery)
Coffee 17
Table 6. Composition of dried raw coffee beans *
Constituent Proportion, wt %* Components
Arabica Robusta
Carbohydrates 48.3–54.0 48.6–55.0
Monosaccharides 0.2–0.4 0.5–0.7 fructose, glucose, galactose, arabinose
Oligosaccharides 5.1–8.6 2.2–6.6 sucrose
Polysaccharides 43.0–45.0 46.9–48.3 soluble and insoluble polymers containing mannose,
galactose, glucose, arabinose
Acids and phenols 8.2–11.0 10.1–16.3
volatile traces to 0.06 acetic, formic acids
nonvolatile aliphatic 2.0–2.9 1.3–2.2 citric, malic, oxalic, quinic acids
phenolic 6.2–8.1 8.8–14.1 depsides of caffeic, ferulic, p-coumaroyl acids, and quinic
acid; in Robustas also with amino acids
Lipids 8–17
15 average 10 average fatty acids as triglycerides, diterpene esters, sterol esters,
free acids
Amino acids 10.3 mainly as proteins
free 0.5 0.8
Methylxanthines 1.2 2.2 caffeine, traces of other purines
Trigonelline 1.0 0.7
Minerals 4.2 4.4
potassium 1.7 1.8
* The contribution of the analytical error to inter- and intraspecies variations may be larger than natural variation.

6.2.5. Aromatization proteins and the chlorogenic acids, the structure


of the cell walls [61]. Table 7 lists the makeup
Volatile aroma from grinding gas, or from steam- of the carbohydrate portions of raw Arabica and
ing of ground, roasted coffee prior to extraction Robusta coffee beans. Some structures that have
is emulsified with oil from pressed, roasted cof- been partially identified are listed in Table 8
fee or spent grounds and sprayed on the powder,
at a level of 0.3–1 % during the filling operation. Table 7. Carbohydrates in dried raw beans
Fraction Proportion, wt %
Arabica Robusta
7. Composition [59] Monosaccharides * 0.2–0.4 0.5–0.7
Oligosaccharides * 5.1–8.6 2.2.–6.6
Polysaccharides, 43.0–45.0 46.9–48.3
The main differences in the composition of Ara- composed of:
bica and Robusta raw beans lie in the relative Mannose 21.3–22.5 21.7–22.4
amounts of lipids and trigonelline, which are Galactose 10.4–11.9 12.4–14.0
Glucose 6.7–7.8 7.8–8.7
higher in Arabicas, and of chlorogenic acids and Arabinose 3.4–4.0 2.8–4.1
caffeine, which are higher in Robustas. Table 6 Total 48.3–54.0 48.6–55.0
shows the composition of Arabica and Robusta Fructose, glucose, galactose, and arabinose (traces). ** Mainly
coffees. sucrose.

Roasting favors polysaccharide depolymer-


ization, improving mannan extractability at
7.1. Carbohydrates [60]
high temperature (180 ◦ C), liberation of oligo-
Carbohydrates constitute ca. 50 % of the raw and monosaccharides, reaching a maximum at
bean. Although their content appears to be medium roasting, followed by pyrolysis at dark
marginally higher in Robustas than in Arabi- roasting. Table 9 lists the carbohydrate makeup
cas, there are no major qualitative differences of roasted coffee beans.
between the two botanical species. Sucrose is During high-temperature industrial extrac-
the main oligosaccharide, and polymers of ara- tion, polysaccharides are partially hydrolyzed to
binose, galactose, glucose, and mannose con- mono- and oligosaccharides [63] independently
stitute both the soluble polysaccharides in the of species. Tables 10 and 11 show the extraction
cells and the insoluble ones, which form, with behavior as a function of roasting degree of the
18 Coffee
Table 8. Carbohydrate structures that have been partially identified in dried raw coffee beans
Fraction Proportion, wt % Structure
Arabica Robusta
[Galacto]mannan 22 Mainly mannose as straight chains of β-(1-4)-mannan, with little
galactose. Storage carbohydrates of molecular mass range 800–800
000; extremely hard and poorly soluble.
Arabinogalactan 14–15 16–17 Polymers composed of β-(1-3)-arabinogalactan, probably
covalently linked to proteins. In Arabica there is a higher branching
frequency and a higher level of terminal mannose than in Robusta.
Structural cell-wall components of molecular mass range 200–200
000
Cellulose 8 β-(1-4)-Homoglucan. Structural cell-wall components.
Hemicelluloses traces Contain rhamnose (0.3 %), xylose (0.2 %) from residual parchment.

Table 9. Carbohydrates in dry roasted beans


Fraction Proportion, wt % Components Behavior during roasting
Monosaccharides 0–2.0 glucose, fructose, arabinose disappear at dark roasting
(traces), and galactose
Oligosaccharides 0.4–2.8 sucrose decreases, disappearing at dark roasting
Polysaccharides [62] mannan is depolymerized to a molecular mass range of
200–80000 and its high-temperature extraction
behavior improves sharply
arabinogalactan is depolymerized to a molecular mass range of
200–50000 with a decrease in the degree of
substitution of galactan chains from 1:7 to 1:12
arabinose:galactose
cellulose rather stable

Table 10. Carbohydrates in soluble extract from coffee roasted at three different degrees, wt % by monosaccharide constituents and by their
polymers (glycans) (determined as single sugars)
Components Light roast Medium roast Dark roast
Arabinose 2.4 1.7 1.5
Galactose 20.0 17.8 13.9
Glucose 0.9 10.4 0.7
Mannose 8.7 10.4 16.0
Total 32.6 31.2 32.7

Table 11. Carbohydrates in soluble extract from coffee roasted at three different degrees, wt % by degree of polymerization observed
(determined as total monosaccharide)
Components Light roast Medium roast Dark roast
Monosaccharides 3.34 2.89 2.01
Oligosaccharides 8.03 9.57 7.38
Polysaccharides 20.85 18.46 23.22

carbohydrates of an Arabica coffee at extraction degree of high-temperature hydrolysis that was


yields of around 39 %. applied during industrial extraction to be esti-
While the amount of mannan in a coffee mated. The free and total carbohydrate content
brewed at ca. 95 ◦ C is rather low, it increases to of commercial soluble coffees is given in Table
up to two-thirds of the amount present in green 12.
beans when coffee is extracted at 180 ◦ C. This The amount of specific free and total carbo-
material is, however, poorly soluble and precip- hydrates in a soluble coffee indicates if extra-
itates on standing [64]. The molecular mass pro- neous material, such as cheap maltodextrins or
file of the carbohydrates in a commercial soluble worthless husk and hulls, discarded during dry
coffee allows inferences to be made about the processed green coffee production, were used,
way it was manufactured, and, in particular, the either dry or roasted [66, 67] (Table 13).
Coffee 19
Table 12. Free and total carbohydrate content of soluble coffee, wt % [65]
Component Free Total
Range Average Range Average
Xylose 0.11–0.28 0.17
Arabinose 0.75–2.01 1.17 2.35–5.80 3.908
Fructose 0.05–0.42 0.12
Mannose 0.13–2.62 0.53 10.2–19.7 14.2
Glucose 0.00–0.43 0.12 0.57–1.51 0.97
Galactose 0.27–0.72 0.47 13.5–24.7 19.5

caffeic acid (0.2–0.3 % free in the raw bean) and


Table 13. Carbohydrates used to determine the purity of
commercial soluble coffees, wt %
ferulic acid (also present free in trace amounts
Pure soluble coffee Maximum tolerable in the raw bean).
level
Free
Fructose 0.05–0.42 0.60
Glucose 0–0.43 0.50
Sucrose 0.01–0.64 0.80
Maltose 0 absent
Total
Glucose 0.57–1.51 1.80
Xylose * 0.11–0.28 0.40
Sugar alcohol 0.11–0.28 0.40
Mannitol ** 0.02–0.22 0.30 The ratio of monochlorogenic to di-
* Xylose makes up around 50 % of the woody parchment chlorogenic acids is related to the quality of a
surrounding the beans.
** From husks [68] somewhat unstable on roasting. cup of coffee. It is lower in Robusta than in Ara-
bica beans, and in immature or discolored beans,
in which an excess of dichlorogenic acids may
be responsible for the lingering metallic taste of
7.2. Acids [69] the roasted infusion. During roasting, many re-
actions occur, such as decarboxylation, dehydra-
A series of aliphatic acids, common in cellu-
tion of the quinic acid moiety, lactonization, iso-
lar metabolism, has been identified in the raw
merization, polymerization, and reactions with
bean. The concentration of some increases dur-
sugars like sucrose. The feruloylquinic acids are
ing uncontrolled fermentation, and the C2 – C6
thermally stable and survive roasting, while free
aliphatic acids with their ethyl esters may con-
quinic acid increases. At short roasting times
tribute to the fruity and impure off-flavor of the
(< 120 s), dCQAs are hydrolyzed into CQA
“stinker” beans, which survives roasting. Table
and CA. 5-CQA rapidly undergoes esterifica-
14 lists the aliphatic acids in dried raw coffee
tion with carbohydrates and proteins, produc-
beans.
ing bound chlorogenic acid. On longer roasting
Volatile acids are formed during roasting by
times, phenolic and quinic moieties start degrad-
thermal degradation of carbohydrates and non-
ing, generating phenols (4-ethylcatechol, cate-
volatile acids. Table 15 shows the aliphatic acids
chol, phenol hydroquinone, pyrogallol [74]. The
in roasted coffee beans. Phosphoric acid (Ara-
proportion of chlorogenic acids in beans of var-
bica 1.55 g/kg, Robusta 2.8 g/kg) increases with
ious roasting degrees is shown in Table 17.
roasting degree, particularly in Robusta [70].
Between 50 and 90 % of the chlorogenic acids
More characteristic are the phenolic acids,
pass into domestically brewed coffee and up to
which exist as depsides (i.e. intermolecular es-
100 % into industrial extracts, where neochloro-
ters of aromatic hydroxycarboxylic acids, where
genic acid becomes the most important phe-
the carboxyl group of one acid is esterified with
nolic acid present (30 % of the total). Fur-
the phenolic OH group of the other) with quinic
ther isomerization or hydrolysis of the lactones
acid and are known as chlorogenic acids (see Ta-
formed at roasting may be responsible for this
ble 16). Quinic acid itself is also present in un-
increase. Three stable lignan-like acidic dimers
usually large quantities in the free state (0.55 %
and trimers, named caffeicins, are formed on
in Arabica and 0.35 % in Robusta beans), with
20 Coffee
Table 14. Aliphatic acids in dried raw beans
Acid fraction Proportion, wt %
Arabica Robusta Component
Volatile acids traces – 0.1 mostly acetic acid traces – 0.06
Nonvolatile acids 2–2.9 1.3–2.2 citric acid 0.7–1.4
malic acid 0.3–0.7
oxalic acid 0–0.2
quinic acid 0.3–0.5
Total 2–3 1.3–2.2

Table 15. Aliphatic acids in roasted bean


Acid fraction Proportion, wt % Components Behavior at roasting
Volatile acids 0.4–1.0 formic acid 0.1–0.3 amount is maximum at medium roast
acetic acid 0.3–0.7 amount is maximum at high roast
C2 – C10 acids traces
Nonvolatile acids 1.4–3.6 [71] lactic acid 0–0.3 amount increases slowly
glycolic acid 0.1–0.3 amount increases
pyruvic acid 0–0.2 amount decreases at high roast
malic acid 0.1–0.4 amount decreases
citric acid 0.3–1.1 amount decreases
pyroglutamic acid 0.1–0.2 amount increases
quinic acid 0.6–1.2 amount increases
Total 1.8–4.6

Table 16. Depsides of quinic acid in raw beans [72, 73]


Component Proportion, wt % R3 R4 R5
Arabica Robusta
n-Chlorogenic acid [372-97-7] 5.4–6.2 4.9–6.4 H H caffeoyl
Cryptochlorogenic acid [17608-52-5] 0.4–0.7 0.9 H caffeoyl H
Neochlorogenic acid [906-33-2] 0.1–1.0 0.4–0.8 caffeoyl H H
5-Feruloylquinic acid [40242-06-6] 0.2–0.3 0.6–1.0 H H feruloyl
4-Feruloylquinic acid traces 0.1 H feruloyl H
3-Feruloylquinic acid [1899-29-2] traces 0.1 feruloyl H H
4,5-Dicaffeoylquinic acid [14534-61-3] 0.3–0.4 0.2–1.1 H caffeoyl caffeoyl
3,5-Dicaffeoylquinic acid [2450-53-5] 0.2–0.4 0.3–0.9 caffeoyl H caffeoyl
3,4-Dicaffeoylquinic acid [57378-72-0] 0.1–0.2 0.1–0.8 caffeoyl caffeoyl H
p-Coumaroylquinic acid 0.03–0.07 0.05–0.06
p-Caffeoyltryptophan 0 0.2–0.3
p-Coumaroytryptophan 0 0.14–0.17
Caffeoyltyrosin 0 0.13–0.48
“Angola II” 0 0.19–0.37
* Only in Angola Robusta.

Table 17. Chlorogenic acids in roasted Arabica and Robusta beans, wt % [75]
Species State of the bean
Raw Light roast Medium roast Dark roast
Arabica 6.9 2.7 2.2 0.2
Robusta 8.8 3.5 2.1 0.2

roasting, and are present in roasted and instant 5.5, is less clear; for example, pH is lower for
coffees [76]. Table 18 shows the proportion of washed coffees than for natural coffees and for
chlorogenic acids in industrial extracts. extracts than for household infusions. The sour
A good correlation exists between titratable taste of infusions that have been kept warm for a
acidity of the roasted coffee infusion, to which period of time is due to an increase in free acids,
phosphoric acid (0.2–0.3 %) also contributes, in particular quinic acid formed by hydrolysis of
and the acid taste of the cup of coffee. The corre- esters, depsides, and lactones, as well as to loss
lation with pH, which may vary between 4.7 and of pyridine.
Coffee 21
Table 18. Chlorogenic acids in industrial extracts, wt % [77]
Component Quantity
n-Chlorogenic acid 0.7–1.9
Cryptochlorogenic acid 0.8–2.3
Neochlorogenic acid 1.0–3.5
Sum 2.5–7.7
3-Feruloylquinic acid 0.3–0.8
4-Feruloylquinic acid 0.3–0.8
5-Feruloylquinic acid 0.2–0.4
Sum 0.8–2.0
3,4-Dicaffeoylquinic acid traces – 0.5
3,5-Dicaffeoylquinic acid 0.1–0.3
4,5-Dicaffeoylquinic acid 0.1–0.4
Sum 0.2–1.2

7.3. Lipids [78]

Lipids constitute 15–18 %, average 15 %, of


Arabica and 8–12 %, average 10 %, of Robusta
raw beans. The actual range may be smaller.
The content of unsaponifiable matter is rela-
tively high. The lipids can be subdivided into two
chemically different fractions: the wax, which
constitutes the outermost layer of the bean (0.2 –
0.3 %), and the oil, located inside the endosperm. Table 19 shows the composition of lipids in dried
The qualitative lipid composition differs only raw coffee beans.
slightly between Arabicas and Robustas.
Table 19. Composition of the lipid fraction of dried raw beans
The main fatty acids are linoleic (40–45 %)
and palmitic (25–35 %) acids. The fatty acid Lipid fraction Proportion, Components
wt %
composition of the outside wax layer, rich in Triglycerides 70–80 mainly esters of linoleic and
the stable saturated arachidic, behenic and lig- palmitic acids
noceric acids, differs from that of the oil, which Free fatty acids 0.7–2.7 higher in Robusta [83]
Diterpene esters 15–18.5 mainly esters of palmitic and
contains mostly the C16 – C18 acids. Triglyc- linoleic acids
erides remain virtually unchanged during roast- Triterpene, sterol, and 1.4–3.2
ing. The free fatty acid content, higher in un- methylsterol esters
Free diterpenes 0.1–1.2
washed beans than in washed beans, increases Free triterpenes and 1.3–2.2 mainly sitosterol,
during storage and roasting. sterols stigmasterol, and
Fatty acid esters of diterpenes from the kau- campesterol
Phospholipids 0.1
rane family are cafestol, present both in Arabica Hydrocarbons traces mainly squalene and
and in Robusta coffees, 16-O-methylcafestol, nonacosane
present only in Robusta beans, and kahweol, 5-Hydroxytryptamides 0.3–1.0 amides of arachidic, behenic,
and lignoceric acids
present mainly in Arabica beans. These three Tocopherols 0.3–0.7 α, β-, and γ-isomers
compounds are specific to coffee and constitute
about 20 % of the lipid fraction[79]. The pres- The free alcohols are liberated from the esters
ence of 16-O-methylcafestol in a commercial during roasting, and cafestol and kahweol are
roast and ground coffee sample indicates that further decomposed to volatile dehydro deriva-
the blend contains Robusta coffee [80]. Another tives, while 16-O-methylcafestol is stable even
diterpene of the kaurane family present in small at high roasting temperatures. Free atractyli-
amounts in coffee is atractyligenin, bound in var- genin is formed by decomposition of its glyco-
ious glycosides [81]. sides.
The composition of the sterol fraction is vir-
tually unaffected during roasting and it was also
22 Coffee

proposed as a means to evaluate the relative pro- Values range from 8.7–12.2 % of the dry
portions of Arabica and Robusta beans in com- weight. No major differences exist between Ara-
mercial roasted coffee blends. bica and Robusta, although the higher concen-
Small quantities of the antioxidants, α-, β- tration of sulfur-containing amino acids in Ro-
and γ-tocopherols, and 5-hydroxytryptamides bustas may be responsible for the differences
have been identified. The content of tryptamides perceived in the volatile flavor between the two
in the wax increases with ripening of the cherry species. Table 20 shows amino acids and pro-
at the expense of tryptophan and decreases on teins in dried raw bean.
storage and also after various treatments of the
bean. For example, the reduced level in treated Table 20. Amino acids and proteins in dried raw beans
coffee (by steaming or by solvent washing) is Nitrogenous Proportion,Components
claimed to be an index of the reduction of ir- fraction wt %
Free amino 0.2–0.8 glutamic acid, aspartic acid,
ritating substances in coffee. Tryptamides are acids γ-aminobutyric acid, alanine, proline,
decomposed by roasting, and their relationship, and serine
if any, to health effects of the brew is at least are the most important; total
concentration is possibly lower in
doubtful [84]. Arabicas than in
Robustas
Proteins 7.9–12 composition near that of the free amino
acids, with 20 % of glutamic acid and
10 % each of both aspartic acid and
leucine; histidine, cysteine, and
methionine
are also present in small quantities
Soluble 25–40 % isoelectric point at pH 5.7 for Arabicas
proteins and pH 6.3 for Robustas
Structural 60–75 % linked with polysaccharides and
proteins chlorogenic acids in the cell wall
(15–25 %
soluble
in alkali)

The content of lipids in a cup of coffee de- Only traces of free amino acids remain after
pends on the brewing method and can reach a roasting since they are thermally unstable, un-
few percent in brews made from finely ground dergoing Maillard reactions with reducing sug-
Turkish coffee or when ground coffee is boiled ars, to release volatile components and form
with water; it is insignificant in filtered coffee in- melanoidins, a polymeric material. Up to 40 %
fusions (for physiological significance, see Sec- of the proteins are denaturated and decompose
tion 8.3). Small amounts of oil (between 0.2 and during roasting, although one-half of the ami-
1 %), obtained from roast and ground coffee or no acids present in the raw bean remain as ap-
from spent grounds, are often used as support for parent polypeptides with the exception of argi-
the reincorporation of volatile aroma into an in- nine, which is completely degraded. All avail-
stant coffee powder, but the amount of oil present able polypeptides are extracted at 30 % extrac-
in the cup is usually negligible. tion yield and constitute 10–12 % of an industrial
extract.

7.4. Nitrogen Compounds


7.4.2. Purines and Nucleic Acids
7.4.1. Amino Acids, Peptides, and Proteins
[85] Several purines have been identified in the raw
bean. Among them, only caffeine, a physio-
The estimated sum of free and bound amino logically active ingredient of coffee, is present
acids present in the raw bean is based on the in appreciable amounts. Nucleic acids of un-
total Kjeldahl nitrogen: known structure have also been isolated. These
Protein % = totalnitrogen − are shown in Table 21.
(purinicnitrogen+betainicnitrogen)×6.25 %
Coffee 23
Table 21. Nucleic acids and purine bases of raw bean
Fraction Proportion, wt % Components
Arabica Robusta
Nucleic acids 0.7 0.8
Purine bases 0.9–1.4 1.7–4.0 caffeine, theobromine (0.2 mg/100 g),
theophylline (0.06 mg/100 g), adenine, guanine, and hypoxanthine

Part of the caffeine is present as the free crys- of preparation, and crop year. The mineral com-
talline base in the cytoplasm surrounding the cell position of dry coffee beans is shown in Table
vacuole. Part of it is in the cell wall, where it may 22.
be bound as a 1 : 1 π-complex with potassium
chlorogenates, although the complex may also Table 22. Minerals in raw beans
be an artifact formed during extraction [86]. Mineral Proportion,
Caffeine is thermally stable, and only a small wt %
Potassium 1.68–2.00
part of the quantity present in the raw bean Milds 1.68–1.70
is lost by sublimation during roasting. About Brazils 1.77–1.88
85 % passes into the domestic brew and almost Robustas 1.84–2.00
100 % into industrial extracts. The caffeine con- Calcium 0.07–0.35
Magnesium 0.16–0.31
tent of industrial extracts varies between 3.0 and Phosphate 0.13–0.22
5.1 % (dry basis) for spray-dried powders, which Sulfate 0.13
usually contain mainly Robustas, and between
2.5 and 3.7 % for milder freeze-dried products, Sodium and chloride content are low, un-
which contain more Arabicas. less the coffee has been contaminated by sea-
water during transport. About 90 % of the ash
is water-soluble and passes into the brew with
7.4.3. Other Bases only insignificant losses at roasting. The extrac-
tion yield of instant coffee can be estimated by
Trigonelline [535-83-1] (Arabica 0.6–1.2 %, the measure of the potassium content, when the
Robusta 0.3–0.9 %) and traces of betaine and blend and manufacturing losses are known [87].
choline are present in the raw bean. Some Trace metal concentrations in the bean, par-
trigonelline decomposes on roasting to nico- ticularly of manganese, may be correlated with
tinic acid (niacin or vitamin PP), pyridine, cup quality [88]
and other volatile aroma constituents. Residual
trigonelline is easily extracted and constitutes
0.9–1.7 % of industrial extracts. 7.6. Products Formed during Roasting
The principal thermally reactive constituents of
the raw bean are the monosaccharides and su-
crose, the chlorogenic acids, the free amino
acids, and trigonelline (Table 23). The termi-
nal arabinose and galactose units of polysac-
Traces of diamines, putrescine, spermine, and charides are split off, and the basic, sulfur-con-
spermidine have also been identified in the raw taining, and hydroxyamino acids are also eas-
bean. They are easily decomposed during roast- ily decomposed. The lipids are relatively stable,
ing. apart from an increase in free fatty acids due to
hydrolysis of the esters and some degradation of
linolenic acid and unsaponifiable matter. During
roasting, volatile aromatic compounds and poly-
7.5. Minerals
meric brown pigments are formed, while water
and carbon dioxide are liberated.
The ash content of green coffee averages 4.0 %,
Caramel, melanoidins, caffeine, and several
varying between 3.0 and 5.4 % (dry basis) due
aromatic constituents are responsible for the
to the botanical or geographical origin, method
characteristic bitter taste of roasted coffee.
24 Coffee
Table 23. Main reactive constituents lost during roasting
the green coffee volatile compounds, and those
Constituent Proportion in Fraction reacted, that together constitute the aroma of roasted cof-
raw bean, wt % wt %
Carbohydrates fee.
Monosaccharides 0.2–0.5 ≈100 A process [96] for improving the quality of
Sucrose 2–7 70–80 Robusta coffee proposes the removal of MIB by
Polysaccharides 20–25
Mannose 4–6 20–30
steam heating. Since roasting destroys MIB, the
Galactose 3 25–30 Robusta flavor character of a brew may be due
Glucose 1 5–10 to a combination of several factors [97].
Arabinose 1 50–60 The coffee aroma obtained by extracting ei-
Chlorogenic acids 4.7–8.6 40–98
Nitrogen compounds ther the roasted beans or the brew with selec-
Free amino acids 0.2–0.8 100 tive solvents, or by concentrating the headspace
Trigonelline 0.1–0.8 30–80 over the coffee or the brew, is separated in a gas
Lipids 1 3–5
chromatograph (GC). The smell of each peak is
evaluated by sniffing the exit port of the GC, and
7.6.1. Volatile Aroma [89] described by notes such as burnt, cocoalike, but-
tery, floral, etc. (Figure 12). Once the key aroma
Two hundred and thirty volatile compounds have components have been identified by mass spec-
been identified in the aroma of green coffee [90]. trometry, their relative impact can be measured
The majority of these compounds survives roast- by the aroma dilution technique, which consists
ing and may contribute to the roasted coffee fla- of injecting an increasingly diluted aroma into
vor [91]. Albeit made up of almost one thousand the GC until only a few peaks are still perceptible
volatile compounds so far identified (most of to the nose [98]. The most potent odorants iden-
them common to all roasted foods [92]), aroma tified in Arabica and Robusta brews are listed in
constitutes just 0.1% of the weight of roasted Table 25 [99].
ground coffee [93]. Various sensors, the so-called electronic
noses, have become available for the detection of
Table 24. Important off-flavors of (green) coffee odors: chemical families such as α-dicarbonyls,
Flavor Odor threshold Responsible chemical pyrazines, and sulfur compounds can be recog-
characteristics in water nized in the headspace when present at relatively
Medicinal, rioy 1.0 ng/L 2,4,6-trichloroanisole
(TCA) [93] *
high concentrations (at least 20 µg/L).
Earthy, robusta 2.5 ng/L 2-methylisoborneol The cup profile can be presented as a star di-
(MIB) [94] * agram (Figure 13) [100], in which each flavor
Musty 5.0 ng/L geosmin *
is semi-quantitatively described by a panel of
Fruity, rotten, stinker 5–10 mg/L ethyl esters of 2- and
3-methylbutanoic and expert tasters. Star diagrams are very useful for
cyclohexanoic acids comparing samples.
[95]
An important key aroma component is 3-
* Musty/earthy off-flavors in green coffee are usually due to
different combinations of these substances and of
mercapto-3-methylbutyl formate, which as a
methoxypyrazines; all these substances are probably of pure substance has a catty/blackcurrant smell,
microbiological origin and apparently occur more readily in but when added at very high dilution to a (sol-
dry-processed beans.
uble) coffee infusion it strongly enhances the
roasted coffee note [101].

7.6.2. Brown Polymers [102]

In the 1990s the focus of coffee aroma re- The nature of this heterogeneous class of yellow-
search has switched from the mere identification brown to almost black pigments is still sub-
of more and more volatile substances to the se- ject to speculation. They are formed by two
lection of those that constitute the flavor of cof- main routes. In the first, small molecules in the
fee. Two types of aroma impact substances are cells, e.g., monosaccharides and sucrose, poly-
recognized: those that contribute to specific de- merize to yellow- to dark-brown caramel, which
fects (Table 24), usually already present among reacts with chlorogenic acids to form red- to
Coffee 25
Table 25. Concentrations of the most potent odorants in Arabica and Robusta brews
Odorant Arabica, µg/L Robusta, µg/L Odor threshold in
water, µg/L
2-Furfurylthiol 19.1 39.0 0.01
(E)-β-Damascenone 1.3 1.5 0.00075
3-Mercapto-3-methylbutyl formate 5.5 4.3 0.0035
3-Methylbutanal 550 925 0.35
Methylpropanal 800 1380 0.7
Methanethiol 210 600 0.2
5-Ethyl-4-hydroxy-2-methyl-3(2H)-furanone 840 670 1.15
2-Methylbutanal 650 1300 1.3

black-brown humic acids [103]. These sugars rial, composed of intact mannose units linked
also react with amino acids via the Maillard together by galactose, arabinose, free phenolic
reaction [104] to form yellow- to black-brown acids, free amino acids, and peptide side chains,
melanoidins [105]. can be identified. These form the matrix on
In the second, similar reactions may also oc- which the brown pigments are fixed. These pro-
cur in the cell wall following thermal degrada- cesses are depicted in the following diagram:
tion of the constituents. Partially soluble mate-

Table 27. Coffee consumption in some producing countries


8. Consumption and Physiology
Country National Average individual
[106 – 108] consumption, intake, kg per capita
thousands of 60-kg per annum
bags
Brazil 15 540 5.10
8.1. Consumption Colombia 1400 1.76
Indonesia 2000 0.55
India 1134 0.06
The leading coffee-consuming countries with Ethiopia 1833 1.40
Mexico 1500 0.84
annual per capita consumption and green coffee
Guatemala 300 1.39
disappearance are listed in Table 26 [109]. The Thailand 500 0.44
Nordic countries have the largest per capita con-
sumption, while the European Union is by far the Among the producing countries, consump-
main importer, followed by the United States, tion is high in Brazil and most of Latin Amer-
where the decline in consumption has now been ica, intermediate in Asia, and very low in Africa
stopped by the improved quality introduced with the exception of Ethiopia (Table 27), where
with specialty coffees, particularly Italian-style domestic consumption nearly approaches the ex-
espresso. ported share of national production.
26 Coffee

Figure 12. Odor profile of a dry ground roasted coffee. The vertical axis gives the mass spectrometric abundance. Known odor
thresholds are indicated on the peaks (courtesy Dr. H. Brévard)

8.2. Dietary Value tributes, via nicotinic acid, a fraction of the daily
nutritional requirement for niacin (vitamin B3
or PP), in amounts increasing with the degree of
Coffee is consumed at breakfast and between
roast, and might play a role in the diet of under-
meals as a stimulant, or after a meal as an aid
nourished people. The composition of a cup of
to digestion, particularly in Latin cultures. The
coffee is given in Table 28.
nutrient profile shows that a cup of coffee con-
Coffee 27

Figure 13. Sensory profile of a coffee brew. This sample has been characterized by a trained panel as possessing an intense
overall aroma and flavor, a roasted/burnt/smoked note, and an off-flavor described as stale/oxidized (courtesy Dr. S. Bobillot)

Table 26. Green coffee disappearance in the principal importing countries [thousands of 60-kg bags (source: International Coffee
Organization)] and consumption (kilograms per capita per year)
Country 2000 2001 2002 2003 2004 2005 Average kg per capita
Austria 862 1029 945 753 1032 809 905 6.64
Belgium 1304 987 1635 1719 1458 1307 1402 8.26
Cyprus 68 55 53 54 57 71 60 4.48
Czech Republic 550 655 646 556 546 534 581 3.27
Denmark 784 863 806 725 849 814 807 9.17
Estonia 99 110 112 118 133 150 120 5.42
Finland 896 941 962 988 1030 1048 978 11.21
France 5446 5474 5627 5360 4972 4952 5305 5.28
Germany 9283 9475 9064 9076 10177 8052 9188 6.90
Greece 713 578 864 1003 928 911 833 4.65
Hungary 733 740 709 611 561 394 625 3.83
Ireland 83 147 143 152 220 224 161 2.50
Italy 5164 5252 5180 5503 5405 5460 5327 5.57
Latvia 112 156 151 169 167 166 154 3.60
Lithuania 172 203 207 189 234 251 209 3.67
Malta 19 15 26 34 26 23 24 3.66
Netherlands 1911 1732 1641 1827 1599 1454 1694 6.26
Norway 658 711 692 682 710 743 699 9.17
Poland 1765 1958 1952 2096 2202 2133 2018 3.06
Portugal 723 750 743 745 771 749 747 4.54
Slovakia 262 308 298 318 319 368 312 3.28
Slovenia 177 193 201 182 195 200 191 5.66
Spain 3058 2869 2907 2826 2791 2959 2902 4.45
Sweden 1182 1259 1235 1181 1242 1162 1210 8.03
United Kingdom 2381 2261 2134 2196 2423 2174 2261 2.29
European Union 38 405 38 719 38 935 39 064 40 045 37 107 38 713 5.10
Switzerland 859 876 778 891 714 1056 862 7.06
USA 21 524 19 148 19 193 20 275 20 368 20 363 20 145 4.21
Japan 6876 6919 7209 6786 7167 7441 7066 3.32
Total (including 67 664 65 662 66 114 67 015 68 294 65 968 66 786 0.63
others)
28 Coffee
Table 28. Composition of a cup of coffee, mg
stimulates the central nervous system, shortens
Component Brew a Instant b reaction time, improves alertness, and reduces
Monosaccharides 0–150 15–150
Sucrose 0–200 0–200
mental fatigue [118].
Aliphatic acids 130–350 60–175 It is a cardiac muscle stimulant, a smooth
Chlorogenic acids 100–250 150–200 muscle relaxant, and improves physical perfor-
Lipids traces 0–10 mance [119], but not up to the point to be con-
Volatile aroma traces traces
Caffeine 50–150 50–100 sidered as a doping agent by the International
Trigonelline 30–60 15–35 Olympic Committee (2004). It does not induce
Minerals 100 200 addiction [121] and is neither mutagenic nor
Potassium 50 100
Niacin traces traces
teratogenic for humans at normal dosages and
Polymeric substances c consumption levels. At excessive levels, other
(by difference) 390–1230 920–1500 symptoms occur, such as stimulation of gastric
a
7.5 g of ground roasted coffee at 22 % extraction yield. acid secretion, increase of heart rate, sweating,
b
c
2.0 g of soluble coffee. nervousness, and sleeplessness. To date, the evi-
Polymeric substances contribute to the bitter taste in the cup
[110] and to the retention of aroma constituents in the soluble dence gathered from many studies “does not sug-
powder [111]; although measured as proteins and carbohydrates, gest that caffeine at present levels of consump-
they are unavailable as such after roasting. tion poses a hazard to public health” according to
the FDA, which has kept it on the GRAS (Gen-
erally Recognized As Safe) list [122].
8.3. Physiological Value
Other Physiologically Active Substances.
Coffee has been the subject of extensive sci- An association between coffee consumption and
entific research addressing its potential impact serum cholesterol levels, reported in 1983 [123],
on human health [112], caffeine attracting over is linked with the presence of cafestol (and kah-
90 % of it. weol) esters in the beverage [124]. The amount
present depends on the brewing technique (par-
Caffeine. Caffeine is the principal active in- ticularly on fineness of grinding, means of sep-
gredient in coffee, and its stimulating action is aration of grounds) and is independent of tech-
the basis for the popularity of coffee and the nological parameters (decaffeination, industrial
other caffeine-containing beverages [113, 114]. high-temperature extraction). The ester content
Indicative caffeine contents of coffee prod- is high for boiled, French press, and Middle
ucts are given in Table 29. Eastern coffees, where there is no separation
of grounds, intermediate in espresso coffee, and
negligible in instant and filtered coffees.
Table 29. Caffeine content of different coffee products
In recent years, more and more epidemi-
Product Portion, mL Caffeine, mg
Filter coffee 100–200 35–175
ologically evident positive effects on human
Filter decaffeinated 100–200 3–6 health deriving from a regular coffee consump-
Espresso coffee 20–60 30–75 tion have been highlighted [125]. Preventative
Instant coffee 100–200 35–115
effects against diabetes [126], hepatic cirrhosis
Instant decaffeinated 100–200 2–3
Ready-to-drink 225–285 60–200 and cancer [127], and Parkinson’s disease [128]
have been demonstrated by a large number of
Within minutes from ingestion, caffeine is studies. Regrettably, explanations for the under-
readily adsorbed and distributed through all of lying mechanisms are still missing. On the other
the tissues and organs, then it is degraded to sev- hand, a chemoprotective effect against colon
eral methylxanthines and excreted via the kid- cancer has been associated with the presence in
neys within a few hours [120], with only a minor coffee, beside cafestol and kahweol esters [129],
proportion appearing in the urine as unchanged of antioxidants [130] and enhancers of endoge-
caffeine. Metabolization time is longer in chil- nous detoxifying mechanisms [131].
dren and in pregnant women. The physiologi-
cal effects of caffeine at normal dose levels are Contaminants. Several types of contami-
well known [115], even if important individual nants are sometimes encountered in coffee. Pes-
variations exist [116, 117]. It is a diuretic that ticides [132], present in trace amounts in green
Coffee 29

coffee, disappear during storage, roasting and Quality, Elsevier Academic Press, Oxford
brewing. Paraffins used in the manufacture of 2005, pp. 87–178.
jute/sisal bags may contaminate the green beans 12. ISO 3509:2005 Coffee and coffee products –
[133]. Polycyclic hydrocarbons are formed dur- Vocabulary, International Organization for
ing roasting [134]; if allowed to accumulate in Standardization, Geneve 2005.
the cold spots of the roaster and of the cooler, 13. ISO 10470:2004 Green coffee – Defect
where they tend to co-sublime with caffeine, reference chart, International Organization for
forming whitish deposits, they may constitute Standardization, Geneve 2004.
14. ISO 6668:1991 Green coffee – Preparation of
a work health hazard. Ochratoxin A, a myco-
samples for use in sensory analysis,
toxin formed during cherry processing, storage
International Organization for Standardization,
or transport of the beans if moisture is uncon- Geneve 1991.
trolled, may be present in trace amounts in com- 15. Marketing and Processing of Coffee: Areas of
mercial coffee products [135], although the sub- International Cooperation, UNCTAD, Geneva
stance is partially destroyed during processing TD/B/C.1/PSC/31 1983.
[136]. Relatively high levels of ochratoxin A 16. ICO: Trade Statistics, International Coffee
may be present in instant coffees adulterated Organization, London, 2006,
with husks [137]. www.ico.org/trade statistics.asp (accessed
Acrylamide, a Maillard product derived by July 2006).
heating sugars with asparagine and present in 17. “Organic coffees”, World Coffee & Tea, 1994,
baked potato products and in bread crust [138], is Oct. 19.
formed in coffee during the early phases of roast- 18. Council Regulation (EEC) No 2091/91 of 24.
ing but largely destroyed during the last ones June 1991, Official J. Europ. Communities No
[139]. Its carcinogenic effects, while observable L 198.1, 22.7.91; Council Regulation (EC) No
in rats, have not been evidenced in humans. 1935/95 of 22. June 1995, Official J. Europ.
Communities No L 186/1, 5.8.95.
19. W. Heilmann: “Decaffeination of Coffee” in R.
J. Clarke, O. G. Vitzthum (eds.): Coffee Recent
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Colloids 1

Colloids
Gerhard Lagaly, Institut für Anorganische Chemie der Universität Kiel, Kiel, Germany

1. Definitions . . . . . . . . . . . . . . . . . . . 1 5. Colloid Stability . . . . . . . . . . . . . . . . 11


2. Colloids in Industrial Uses . . . . . . . . . 2 6. Factors Controlling Colloid Stability . . 20
3. Preparation of Colloidal Particles . . . . 4 7. Heterocoagulation . . . . . . . . . . . . . . 29
4. Properties of Colloidal Systems . . . . . 5 8. References . . . . . . . . . . . . . . . . . . . 31

1. Definitions Table 1. Classification of colloidal systems

Dispersed Continuous Descriptive names


Colloid chemistry involves a number of disci- phase phase
plines, including chemistry, physics, material liquid gas aerosol, fog, mist
sciences, and biology. solid gas smoke, aerosol
The particle dimension is the primary param- gas liquid foam
liquid liquid emulsion, microemulsion
eter that governs the properties of colloidal sys- solid liquid dispersion, suspension,
tems. In a practical sense, any particle that has sol, colloidal solution
a linear dimension in the range 10−3 to 1 µm gas
liquid
solid
solid
solid foam
solid emulsion, solid foam
can be defined as a colloidal particle. Very small solid solid solid sol, solid – solid
colloidal particles (nanoparticles) have received dispersion, alloy
increasing attention [1].
Colloidal particles can consist of finely Lyophilic dispersions are true solutions in a
subdivided bulk matter or of more or less thermodynamic sense and are thus one-phase
flexible macromolecules. Particulate colloids systems. The dispersed and continuous phases
are broadly classed as lyophobic (hydropho- are considered as solute and solvent, respec-
bic when dispersed in water) or lyophilic (hy- tively. The colloidal particles are formed by coils
drophilic). In addition, micellar solutions can be of macromolecules. The macromolecules may
considered as associative colloids because the be a long thread, more or less stretched, rolled
micelles formed by association of surface active up, or folded. In any case, the coil is open to
agents often have colloidal dimensions [2]. This the dispersion medium, and large parts of the
type of colloidal system is not considered here macromolecules are in contact with it. Thus, the
(see → Surfactants, → Laundry Detergents [3]). shape and size of the coils can change consid-
Lyophobic and lyophilic colloids differ pri- erably with changes in solvent properties. The
marily in the relationship that exists between the system is governed by the laws of macromolec-
colloidal particle and the medium in which it is ular solutions [4–7].
dispersed. Lyophobic colloidal particles form a Lyophobic and lyophilic colloids are also
two- (or multi-) phase system with the medium, called electrocratic and solvatocratic colloids,
and a phase boundary exists between the parti- reflecting the important role of electrostatic in-
cles (dispersed phase) and the medium (contin- teractions in the former and of solvent – particle
uous phase) (Table 1). interactions in the latter.
The interactions between the particles and Dispersions of lyophilic colloids form spon-
between the particles and the medium are gov- taneously when solute and solvent are brought
erned by the structure of the particle surface, in together, as is characteristic of true solutions. In
particular the surface charge density and the ex- the case of lyophobic colloids, dispersions may
tent to which it responds to changes in system or may not be produced spontaneously when
parameters such as salt concentrations, organic finely subdivided matter is added to the dis-
materials, and pH. persion medium. For these reasons, the terms

c 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim


10.1002/14356007.a07 341