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21.1 Coffee and Coffee Substitutes skin which, when ripe, turns red-violet or
deep red and encloses the sweet mesocarp or
21.1.1 Foreword the pulp and the stone-fruit bean. The latter
consists of two elliptical hemispheres with
Coffee (coffee beans) includes the seeds of crim- flattened adjacent sides. A yellowish transparent
son fruits from which the outer pericarp is com- spermoderm, or silverskin, covers each hemi-
pletely removed and the silverskin (spermoderm) sphere. Covering both hemispheres and sepa-
is occasionally removed. The seeds may be raw or rating them from each other is the strong fibrous
roasted, whole or ground, and should be from the endocarp, called the “parchment”. Occasionally,
botanical genus Coffea. The drink prepared from 10–15% of the fruit berries consist of only one
such seeds is also called coffee. spherical bean (“peaberry” or “caracol”), which
Coffee is native to Africa (Ethiopia). From there it often brings a premium price.
reached Arabia, then Constantinople and Venice. The coffee shrub thrives in high tropical al- titudes
Regardless of the prohibition of use and medical (600–1200 m) with an annual average
warnings, coffee had spread all over Europe by the temperature of 15–25 ◦ C and moderate moisture
middle of the 17th century. The coffee tree or and cloudiness. The shrubs start to bloom 3–4
shrub belongs to the family Rubiaceae. De- years after planting and after six years of growth
pending on the species, it can grow from 3–12 m they provide a full harvest. The shrubs can bear
in height. The shrubs are pruned to keep them at fruit for 40 years, but the maximum yield is
2–2.5 m height and thus facilitate harvesting. The attained after 10–15 years. Fruit ripening occurs
evergreen shrubs have leathery short-stemmed within 8–12 months after flowering. Only 3 of
leaves and white, jasmin-like fragrant flowers the 70 species of coffee are cultivated: Coffea
from which the stone fruit, cherry-like berries, arabica, which provides 75% of the world’s pro-
develop with a diameter of about 1.5 cm. The duction; C. canephora, about 25%; and C. liber-
fruit or berry (Fig. 21.1) has a green outer ica and others, less than 1%. The quantity (in
kg) of fresh coffee cherries which yields 1 kg of is adjustable. The passage of the fruit produces
marketable coffee beans is for C. arabica 6.38, a rubbing action which detaches the skin and the
C. canephora 4.35, and C. liberica 11.5. The pulp from the beans without damaging the seed.
most important countries providing the world’s The removed pulp is used as fertilizer.
coffee harvest in 1996 are listed in Table 21.1. The pulped beans still have the silver-skin, the
parchment and a very adhesive mucilaginous
layer (mucilage). Hence, such coffee is carried
into water stream fermentation tanks made of
21.1.2 Green Coffee concrete, the water is drained off and the beans are
left to ferment for 12–48 h. During this time,
21.1.2.1 Harvesting and Processing the mucilaginous layer, which consists of
84.2% water, 8.9% protein, 4.1% sugar, 0.91%
The coffee harvest occurs from about December pectic subtances and 0.7% ash, is hydrolyzed by
until February from the Equator north to the enzymes of the coffee and by similar enzymes
Tropic of Cancer, while south of the Equator to produced by microorganisms found on the fruit
the Tropic of Capricorn harvest occurs from May skins. The mucilage is degraded to an extent
until August. Harvesting is done by hand-picking which can be readily dispersed by washing with
of each ripe berry or by strip-picking all of the water. The beans are then collected, sun-dried on
berries from three branches after most of the concrete floors or dried in mechanical dryers in
a stream of hot air (65–85 ◦C). Beans dried in this
berries (often present as clusters) have matured.
way are still covered with the parchment shell
Harvesting may also be done by sweeping under (“pergament” coffee or “cafe pergmino”) and are
the tree, i. e. collecting the ripe berries from the further processed by dehulling machines as in the
ground. Processing commences with removal of dry process. This yields the green coffee beans.
the fleshy pulp by using one of the two following Premium-priced coffee beans are often polished
processes: to a smooth, glossy surface and the silverskin,
The dry or natural process used in Brazil involves except that retained in the centrecut of the beans,
rapid transport of the harvested berries to a cen-
is removed.
tral processing plant, where the whole fruit is
spread out on sun-drying terraces and dried un-
til the beans separate by shrinking from the sur-
21.1.2.2 Green Coffee Varieties
rounding parchment layer.
Dehulling machines – conical screws with a he-
lical pitch increasing toward the discharge end – About 80 varieties of the three coffee bean species
remove the dried husks and parchment from the mentioned above are known. The most important
dried berries and, as much as possible, the sil- of the species Coffea arabica are typica, bourbon,
verskin. The dehulled and cleaned coffee beans maragogips and mocca; and of Coffea canephora
are then classified according to size and packed are robusta (the most common), typica, uganda
in 60 kg bags. Often, the fresh cherries, instead and quillon. All varieties of Coffea canephora are
of being spread on the drying terrace, are piled up, marketed under the common name “robusta”.
left for 3–4 days under their own heat to fer- ment The names of green coffees may be characteris-
the fruity pulp, and are then processed as outlined tic of the place of origin; i. e. the country and the
below. In both cases unwashed beans are obtained. port of export. Important washed Arabica coffees
The wet (washing) process is more sophisticated are, for example, Kenyan, Tanzanian, Colombian,
than the dry process, and by general consent leads Salvadorian, Guatemalon or Mexican.
to better quality coffee. The method is generally Unwashed Arabica beans are the mild Santos and
used for Arabica coffee (except in Brazil) in Cen- the hard Rio and Bahia beans. All three are from
tral America, Colombia and Africa. The freshly Brazil. Robusta coffees, mostly unwashed, are, for
harvested berries are brought to a pulper in which example, those from Angola, Uganda, the Ivory
the soft fruit is squeezed between a rotating cylin- Coast and Madagascar.
der or disc and a slotted plate, the gap of which Arabica coffees, particularly those from Kenya,
Colombia and Central America, have a soft, rich,
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clean flavor or “fine acid” and “good body”. The loss in weight occurs, and there is a build-up of
Arabica Santos from Brazil is an important in- the typical roasted flavor of the beans. Simultane-
gredient of roasted coffee blends because of its ously, the specific gravity falls from 1.126–1.272
strong but mellow flavor. Robusta coffee, on the to 0.570–0.694, hence the roasted coffee floats
other hand, is stronger but harsh and rough in on water and the green beans sink. The horny,
aroma. tough and difficult-to-crack beans become brittle
The quality assessment of green coffee is based and mellow after roasting.
on odor and taste assays, as well as on the Four major phases are distinguished during the
size, shape, color, hardness and cross-section roasting process: drying, development, decompo-
of the bean. Major defects or imperfections are sition and full roasting. The initial changes occur
primarily due to objectionable off-flavored at or above 50 ◦ C when the protein in the tissue
blemished beans, which are removed by careful cells denatures and water evaporates. Browning
hand sorting. Blemished beans consist of: unripe occurs above 100 ◦C due to pyrolysis of organic
seeds (grassy beans) which stay light colored compounds, accompanied by swelling and an
during roasting; overfermented beans with an initial dry distillation; at about 150 ◦C there is
off-flavor due to the presence of acetic acid, a release of volatile products (water, CO2 , CO)
diacetyl, butanol and isobutanol; frost-bitten and which results in an increase in bean volume.
cracked beans; insect and rainfall-damaged beans; The decomposition phase, which begins at
and excessively withered beans. Even a single 180–200 ◦C, is recognizable by the beans being
blemished bean can spoil the whole coffee forced to pop and burst (bursting by cracking
infusion. Additional imperfections are the along the groove or furrow); formation of bluish
smoke; and the release of coffee aroma. Lastly,
moldy, musty flavor of insufficiently dried and
under optimum caramelization, the full roasting
prematurely sacked coffee and earthy or haylike
phase is achieved, during which the moisture
off-flavors. Coffee varieties grown at high
content of the beans drops to its final level of
altitudes are generally more valuable than those
1.5–3.5%.
from the plains or lowlands.
The roasting process is characterized by a de-
crease in old and formation of new compounds.
This is covered in section 21.1.3.3, which deals
21.1.2.3 Composition of Green Coffee with the composition of roasted coffee. The run-
ning of a roasting process requires skill and ex-
The composition of green coffee is dependent on perience to achieve uniform color and optimum
variety, origin, processing and climate. A review aroma development and to minimize the damage
of the differences between Arabica and Robusta through over-roasting, scorching or burning.
coffee is provided in Table 21.2. The constituents During roasting, heat is transferred by contact of
will be covered in more detail in the section deal- the beans with the walls of the roasting apparatus
ing with roasted coffee. or by hot air or combusted gases (convection).
Actual contact roasting is no longer of import-
ance because heat transfer is uneven and the
roasting times required are long (20–40 min). In
21.1.3 Roasted Coffee
the contact-convection roasting process (roasting
21.1.3.1 Roasting time 6–15 min), efforts are made to increase the
convection component as much as possible by
suitable process management. Centrifugal roast-
Green beans smell green-earthy, so they must
ers (rotating flat pans), revolving tube roasters,
be heat treated in a process called roasting to bring
fluid-bed roasters (ca. 90% convection) etc. are
about their truly delightful aroma. Roast- ing in
used either batchwise or continuously. In the
the temperature range between 100 and
the final temperature of ca. 200 ◦C causes pro- new short-time roasting process (roasting time
found changes. The beans increase in volume 2 to 5 min), the heating-up phase is significantly
(50–80%) and change their structure and color. shortened by improved heat transfer. Water
The green is replaced by a brown color, a 11–20% evaporation proceeds by puffing, producing
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a greater bean volume increase than conventional 21.1.3.2 Storing and Packaging
roasting processes. Therefore, the density in the
ground state of coffee roasted by this process is Roasted coffee is freed of faulty beans either by
15–25% lower. hand picking on a sorting board or, at large plants,
The roasting process is controlled electronically automatically by using photo cells. Commercially
or by sampling roasted beans. The end-product is available roasted coffee is a blend of 4–8 varieties
discharged rapidly to cooling sifters or is sprin- which, because of their different characteristics,
kled with water in order to avoid over-roasting or are normally roasted separately. Especially strong
burning and aroma loss. During roasting, vapors blends are usually designated as mocca blends.
formed and cell fragments (silverskin particles) While green coffee can be stored for 1–3 years,
are removed by suction of an exhauster and, in roasted coffee, commercially packaged (can,
larger plants, incinerated. plastic bags, pouches, bottles), remains fresh for
There are different roasting grades desired. In the only 8–10 weeks. The roasting aroma decreases,
USA and Central Europe, beans are roasted to while a stale, rancid taste or aroma appears.
a light color (200–220 ◦C, 3–10 min, weight loss Ground coffee packaged in the absence of oxy-
14–17%), and in France, Italy and the Balkan gen (vacuum packaging) keeps for 6–8 months
states, to a dark color (espresso, 230 ◦C, weight but, as soon as the package is opened, this drops
loss 20%). to 1–2 weeks. Little is known of the nature of the
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changes involved in aroma and flavor damage. Table 21.4. Amino acid composition of the acid hy-
The changes are retarded by storing coffee at drolysate of Colombia coffee beans prior to and after
low temperatures, excluding oxygen and water roasting
vapor. Amino acid Green coffee Roasted coffeea
(%) (%)
Table 21.5. Lipid composition of roasted coffee beans Table 21.6. Chlorogenic acid content as a function of
(coffee oil) the degree of roasting
Raw 6.9% 8.8%
Constituent Content Constituent Content Raw/degree of roasting Arabica Robusta
Triacylglycerols 78.8
(%) Triterpenes (%) Light 2.7% 3.5%
Diterpene esters 15.0 (sterols) 0.34 Medium 2.2% 2.1%
Diterpenes 0.12 Unidentified Dark 0.2% 0.2%
Triterpene esters 1.8 compounds 4.0
(21.3)
Chlorogenic acids are the most abundant acids
of coffee (Tables 21.2 and 21.3). The content of
these acids drops on roasting as shown in Ta-
ble 21.6.
21.1.3.3.5 Caffeine
(21.1)
The best known N-compound is caffeine (1,3,7-
A diterpene glycoside is atractyloside and its trimethylxanthine) because of its physiological
aglycon, atractyligenin: effects (stimulation of the central nervous system,
increased blood circulation and respiration). It is
mildly bitter in taste (threshold value in water is
0.8–1.2 mmole/l), crystallizes with one molecule
of water into silky, white needles, which melt
at 236.5 ◦ C and sublime without decomposition
at 178 ◦C. The caffeine content of raw Arabica
(21.2) coffee is 0.9–1.4%, while in the Robusta variety,
Sitosterol and stigmasterol are major compounds it is 1.5–2.6%. In contrast there are caffeine-free
of the sterol fraction. Coffea varieties. Santos, an Arabica coffee, is
on the low side, while Robusta from Angola
is at the top of the range given for caffeine content.
21.1.3.3.4 Acids Other purine alkaloids are theobromine (Arabica:
36–40 mg/kg, Robusta: 26–82 mg/kg)
Formic and acetic acids predominate among the
volatile acids, while nonvolatile acids are lac-
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and theophylline (Arabica: 7–23 µg/kg, Robusta: Table 21.7. Odorants of roasted coffee – results of di-
86–344 µg/kg). lution analyses
Caffeine forms, in part, a hydrophobic π-complex
Aroma substance
with chlorogenic acid in a molar ratio of 1:1. In
a coffee drink, 10% of the caffeine and about 6% Acetaldehyde, methanethiol, propanal, methyl-
of the chlorogenic acid present occur in this form. propanal, 2-/3-methylbutanal, 2,3-butandione,
The caffeine level in beans is only slightly de- 2,3-pentandione, 3-methyl-2-buten-1-thiol,
creased during roasting. Caffeine obtained by the 2-methyl-3-furanthiol, 2-furfurylthiol, 2-/3-methyl-
butyric acid, methional, 2,3,5-trimethylthiazole,
decaffeination process and synthetic caffeine are
trimethylpyrazine, 3-mercapto-3-methyl-1-butanol,
used by the pharmaceutical and soft drink indus- 3-mercapto-3-methylbutylformiate,
tries. Synthetic caffeine is obtained by methyla- 2-(1-mercaptoethyl)-furan, 2-methoxy-
tion of xanthine which is synthesized from uric 3-isopropylpyrazine, 5-ethyl-2, 4-dimethylthiazole,
acid and formamide. 2-ethyl-3, 5-dimethylpyrazine, phenylacetaldehyde,
2-ethenyl-3, 5-dimethylpyrazine, linalool,
2,3-diethyl-5-methylpyrazine, 3,4-dimethyl-2-
cyclopentenol-1-one, guaiacol, 4-hydroxy-2,
21.1.3.3.6 Trigonelline, Nicotinic Acid 5-dimethyl-3(2H)-furanone, 3-isobutyl-2-methoxy-
pyrazine, 2-ethenyl-3-ethyl-5-methylpyrazine,
Trigonelline (N-methylnicotinic acid) is present 6,7-dihydro-5-methyl-5H-cyclopentapyrazine,
in green coffee up to 0.6% and is 50% decom- (E)-2-nonenal, 5-ethyl-4-hydroxy-2-methyl-3(2H)-
posed during roasting. The degradation products furanone, 3-hydroxy-4,5-dimethyl-2(5H)-furanone,
4-ethylguaiacol, p-anisaldehyde,
include nicotinic acid, pyridine, 3-methyl pyri-
5-ethyl-3-hydroxy-4-methyl-2(5H)-furanone,
dine, nicotinic acid methyl ester, and a number 4-vinylguaiacol, (E)-β-damascenone,
of other compounds. bis(2-methyl-3-furyl)disulfide, vanillin
Table 21.8. Concentrations of potent odorants in Ara- Table 21.9. Key odorants for the difference between
bica coffee from Colombiaa – Yields of odorants in the Arabica and Robusta coffee
production of the beverageb Aroma substance Concentration
No. Group/odorant Concen- Yield (mg/kg)
tration Arabica Robusta
(mg/kg) (%) 2-Ethyl-3,5-dimethylpyrazine 0.326 0.940
2,3-Diethyl-5-methylpyrazine 0.090 0.310
Sweet/caramel-like group
Guaiacol 3.2 28.2
1 Methylpropanal 28.2 59 4-Ethylguaiacol 1.61 18.1
2 2-Methylbutanal 23.4 62 4-Vinylguaiacol 55 178
3 3-Methylbutanal 17.8 62
4 2,3-Butandione 49.4 79
5 2,3-Pentandione 36.2 85
6 4-Hydroxy-2,5-dimethyl- 120 95
3(2H)-furanone (HD3F)
7 5-Ethyl-4-hydroxy-2-methyl- 16.7 93 ants so that the odor of the methoxypyrazines
3(2H)-furanone (EHM3F)
is largely suppressed. An aroma defect, the
8 Vanillin 4.1 95
potato taste, (Table 21.10) is produced in
Earthy group roasted coffee only if the concentrations of the
9 2-Ethyl-3,5-dimethylpyrazine 0.326 79
alkyl-methoxypyrazines increase excessively.
10 2-Ethenyl-3,5-dimethylpyrazine 0.053 35
11 2,3-Diethyl-5-methylpyrazine 0.090 67 These compounds are synthesized by bacte- ria
12 2-Ethenyl-3-ethyl- 0.017 25 which penetrate into the coffee fruit after insects
5-methylpyrazine have done the groundwork. In particu- lar, 2-
13 3-Isobutyl-2-methoxy- 0.087 23 furfurylthiol and guaiacol increase with
pyrazine increasing degree of roasting (Fig. 21.2).
Sulfurous/roasty group The aroma of coffee is not stable, the fresh note
14 2-Furfurylthiol 1.70 19 is rapidly lost. Of the highly volatile odorants,
15 2-Methyl-3-furanthiol 0.064 34
16 Methional 0.239 74
17 3-Mercapto-3-methylbutyl- 0.112 81
formiate
18 3-Methyl-2-butene-1-thiol 0.0099 85
19 Methanethiol 4.55 72
20 Dimethyltrisulfide 0.028 n.a.
Smoky/phenolic group
21 Guaiacol 3.2 65
22 4-Ethylguaiacol 1.6 49
23 4-Vinylguaiacol 55 30
Fruity group
24 Acetaldehyde 130 73
25 Propanal 17.4 n.a.
26 (E)-β-Damascenone 0.226 11
Spicy group
27 3-Hydroxy-4,5-dimethyl- 1.58 78
3(5H)-furanone (HD2F)
28 5-Ethyl-3-hydroxy-4- 0.132 n.a.
methyl-2(5H)-furanone Fig. 21.2. Changes in the concentration of potent
(EHM2F) odorants in the roasting process (according to Mayer
a
Degree of roasting: medium. et al. 1999). Arabica coffee from Colombia was
b Yield of the aroma substances in the production of the slightly (♦), moderately ( ) and strongly ( ) roasted.
Table 21.11. Losses of odorants in ground and open 21.1.3.3.9 Other Constituents
stored coffee
Odorants Loss (%)a Brown compounds (melanoidins) are present in
the soluble fraction of roasted coffee. They have
Methanethiol 66 a molecular weight range of 5–10 kdal and are
Acetaldehyde 45
derived from Maillard reactions or from carbohy-
2-Methylbutanal 32
3-Methylbutanal 27
drate caramelization. The structures of these com-
2-Furfurylthiol 23 pounds have not yet been elucidated. Apparently,
3-Isobutyl-2-methoxypyrazine 21 chlorogenic acid is also involved in such brown-
Guaiacol 18 ing reactions since caffeic acid has been identified
2-Ethyl-3,5-dimethylpyrazine 12 in alkali hydrolysates of melanoidins.
4-Vinylguaiacol 5
4-Hydroxy-2,5-dimethyl- 1.4
3(2H)-furanone (HD3F)
3-Hydroxy-4,5-dimethyl- 1.1 21.1.3.4 Coffee Beverages
2(5H)-furanone (HD2F)
a In order to obtain an aromatic brewed coffee with
Loss in 30 minutes at room temperature.
a high content of flavoring and stimulant con-
stituents, a number of prerequisites must be ful-
filled. The brewing, leaching and filtration proce-
methanethiol evaporates the fastest, followed by dures used give rise to a variety of combinations.
acetaldehyde (Table 21.11). The aroma profile While in our society brewed coffee is enjoyed
changes because especially the slow-evaporating as a transparent, clear drink, in the Orient
furanones remain (Table 21.11). As a result, brewed coffee is prepared from pulverized beans
the aroma balance can be destroyed by the (roasted beans ground to a fine powder) and
spicy odor of HD2F (cf. 12.7.3.5) because it water brought to a boil, and is drunk as a turbid
is individually detectable. In the case of open beverage with the sediment (Turkish mocca).
storage of intact beans, losses of the highly Coffee extract is made by boiling the coffee
volatile aroma substances are significantly lower, for 10 min in water and then filtering. In the
e. g., evaporation of methanethiol is only 11% boiling-up procedure the coffee is added to hot
in 15 minutes at room temperature instead of water, brought to a boil within a short time
43%. and then filtered. The steeping method involves
pouring hot water on a bag filled with ground
coffee and occasionally swirling the bag in
21.1.3.3.8 Minerals a pot for 10 min. In the filtration-percolation
method, ground coffee is placed on a support
As with all plant materials, potassium is pre- grid (filter paper, muslin, perforated plastic
dominant in coffee ash (1.1%), followed by filter, sintered glass, etc.) and extracted by
calcium (0.2%) and magnesium (0.2%). The dripping or spraying with hot water, i. e. by
predominant anions are phosphate (0.2%) and slow gravity percolation. This procedure, in
sulfate (0.1%). Many other elements are present principle, is the method used in most coffee
in trace amounts. machines. In an expresso machine, which was
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a
Arabica-coffee, medium roast, 50 g/l. centrations (cf. Table 21.13), they still additively
b Calculated as sum of the amino acids after acid hy- contribute to the bitter taste (cf. 5.1.2: additive ef-
drolysis. fect).
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(21.4)
Table 21.13. Bitter quinic acid lactones in a decaf- in Switzerland in 1938. Ground coffee is batch-
feinated coffee drinka wise extracted under pressure in percolator batter-
No. Quinic acid lactone Thresholdc Concen- ies or continuously in extractors. The water tem-
(quinides)b tration perature may be as high as 200 ◦C while the tem-
perature of the extract leaving the last extraction
(mg/l) cell is 40–80 ◦C. The extracts exhibit a concen-
I 3-O-Caffeoyl-γ- 13.4 33.15 tration of ca. 15% and are evaporated in vacuum
II 4-O-Caffeoyl-γ- 12.1 19.68 film evaporators to a solids content of 35–70%.
III 4-O-Caffeoyl-muco-γ - 11.2 8.27 To minimize aroma losses, the extraction can be
IV 5-O-Caffeoyl-muco-γ - 9.7 6.12 conducted in two stages. In a gentle stage, the first
V 5-O-Caffeoyl-epi-δ - 60.5 3.28 extract is obtained with a solids content of 25–
VI 3-O-Feruloyl-γ- 13.7 6.75 27% and carries the main portion of the aroma.
VII 4-O-Feruloyl-γ- 13.7 3.03 Without concentration, it is mixed with a second
VIII 3,4-Dicaffeoyl-γ- 4.9 5.40 extract which was obtained under stronger con-
IX 4,5-Dicaffeoyl-muco-γ - 4.9 1.65 ditions and concentrated. In addition, aroma con-
X 3,5-Dicaffeoyl-epi-δ- 24.9 0.80
centrates can be isolated by stripping; they can be
a Made by the percolation of coffee powder (54 g) with added back before or after drying. The technical
water (80 ◦C, 1.1 l). extraction yields are 36–46%. Further process- ing
b The structures of the lactones I, III and V are pre-
involves spray or freeze drying. In the latter
sented in Formula 21.4. method, the liquid extract is foamed and frozen
c Threshold for the bitter taste.
in a stream of cold air or an inert gas (− 40 ◦C),
then granulated (grain size of 2–3 mm), sifted and
dried in vacuum in the frozen state. Spray-dried
coffee extract can be agglomerated in vibration
21.1.4 Coffee Products fluid beds by steam or spray.
The resultant extract powder is hygroscopic and
The coffee products which will be discussed are unstable. It is packaged in glass jars, vacuum
instant coffee, decaffeinated coffee and those packed in cans, aluminum foil-lined bags, flexi-
containing additives. ble polyethylene, laminated pouches or bags, or
packaged in air-tight plastic beakers or mugs, of-
ten under vacuum or under an inert gas.
21.1.4.1 Instant Coffee Like roasted coffee, instant coffee is marketed
in different varieties, e. g., regular roasted or as
Instant (soluble) coffee is obtained by the ex- a dark, strongly-roasted espresso, or caffeine free.
traction of roasted coffee. The first technically Instant coffee contains 1.0–6.0% moisture. The
sound process was developed by Morgenthaler dry matter consists of 7.6–14.6% minerals, 3.2–
948 21 Coffee, Tea, Cocoa 21.1 Coffee and Coffee Substitutes 949
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13.1% reducing sugars (calculated as glucose), Lendrich (1927) investigated the effect of
2.4–10.5% galactomannan, 12% low molecu- steaming green beans, without caffeine ex-
lar organic acids, 15–28% brown pigments, traction, on the removal of some substances
2.5–5.4% caffeine and 1.56–2.65% trigonelline. (e. g., waxes) and hydrolysis of chlorogenic
The products are used not only for the prepara- acid. In a process developed by Bach (1957),
tion of coffee beverages but also as flavorings for roasted coffee beans are washed with liquid
desserts, cakes, sweet cookies and ice cream. carbon dioxide. In another process, the sur-
face waxes of the raw beans are first removed
by a lowboiling organic solvent, followed by
21.1.4.2 Decaffeinated Coffee steaming, as used by Lendrich. The extent of
wax removal can be monitored by the analy-
The physiological effects of caffeine are not bene- sis of fatty acid tryptamides, which have already
ficial nor are they tolerated by everyone. Hence, been mentioned (cf. 21.1.3.3.3).
many processes have been developed to remove
caffeine (<0.1%) from coffee. The following pro-
cess steps are normally used: 21.1.5 Coffee Substitutes and Adjuncts
• Swelling of the raw coffee with water or steam
21.1.5.1 Introduction
at 22–100 ◦C up to a water content of 30–40%,
• Extraction of the caffeine-potassium-choro-
genate complex with a water-saturated sol- Coffee substitutes, or surrogates, are the parts of
vent (methylene chloride, ethyl acetate) at roasted plants and other sources which are made
60–150 ◦C, into a product which, with hot water, provides
• Treatment with steam at 100–110 ◦C to re- a coffee-like brew and serves as a coffee substi-
move the solvent (deodorization), tute or as a coffee blend.
• Drying with warm air or under vacuum at 40– Coffee adjuncts (coffee spices) are roasted parts
80 ◦C. of plants or material derived from plants, mixed
with sugar, or a blend of all three sources and,
In another indirect process, used in the USA, ini- when other ingredients are added, are used as
tially all the water-soluble compounds including an additive to coffee or as coffee substitutes.
caffeine are extracted from the green beans. The The starting materials for manufacturing such
aqueous extract is decaffeinated with an organic products vary: barley, rye, milo (a sorghum-type
solvent (e. g., dichloroethane), then added back to grain) and similar starch-rich seeds, barley and
the green beans and evaporated to dryness with rye malts and other malted cereals, chicory, sugar
the beans. beets, carrots and other roots, figs, dates, locust
Swollen raw coffee can also be decaffeinated with fruit (St. John’s bread) and similar sugar-rich
supercritical CO2 (crit. point: 31.06 ◦C; 73.8 bar) fruits, peanuts, soybeans and other oilseeds, fully
at 40–80 ◦ C and a pressure of 200–300 bar. The or partially defatted acorns and other tannin-free
high vapor pressure of carbon dioxide under nor- plant parts, and, lastly, various sugars.
mal conditions guarantees a product that is free Coffee substitutes have been known for a long
from solvent residues. Apart from the extraction time, as exemplified by the coffee brew made of
of caffeine, this process can also be applied in chicory roots (Cichoricum intybus var. sativum)
the extraction of odor- and taste-active substances or by clear drinks prepared from roasted cereals.
from hops and other plant materials.
temperature of 180–200 ◦C, and then the grains contains 4.5% moisture, 2.6% minerals, 74.7%
may be polished or coated with sugar. carbohydrates (calculated), 1.8% fat, 10.8%
For the manufacture of substitutes and adjunct crude protein, 5.6% crude fiber and provides an
essences, liquid sugar juice (cane or beet mo- extract which is 42.4% soluble in water. Poly-
lasses, syrup or starch-sugar plant extracts) is cyclic aromatic hydrocarbons are also detected.
caramelized in a cooker by heating above 160 ◦C
Rye and wheat malt coffees are manufactured
under atmospheric pressure. The dark, brown-
from their respective malts in the same way.
black product solidifies to a glassy, strongly
hygroscopic mass which is then ground.
Pulverized coffee substitutes are obtained from
the corresponding starting materials, as with true 21.1.5.3.3 Chicory Coffee
coffee, by a spray, drum, conveyor or other drying
process. Chicory coffee is manufactured by roasting the
The starch present in the raw materials is cleaned roots of the chicory plant possibly with
diastatically degraded to readily-caramelized, addition of sugar beet, low amounts of edible fats
water-soluble sugars in the manufacture of coffee or oils, salt and alkali carbonates. This is followed
substitutes during the steeping, steaming and, by grinding of the roasted product, with or with-
particularly, the malting steps. This is especially out an additional steaming step or treatment with
the case with malt coffee. Caramel substances hot water. Chicory contains on the average 13.3%
(“bitter roast”) formed in the roasting step, which moisture, 4.4% minerals, 68.4% carbohydrates,
provide the color and aroma of the brew, are 1.6% fat, 6.8% crude protein, 5.5% crude fiber
derived from carbohydrate-rich raw materials andprovides an extract which is 64.6% soluble in
(starch, inulin or sucrose). Since oilseeds readily water.
develop rancidity, processing of carbohydrate-
rich materials is preferred to oil- or protein-rich
raw materials. 21.1.5.3.4 Fig Coffee
As aroma carriers, the oils from roasted products
have been analyzed in detail, specially for malt Fig coffee is made from figs by roasting and
and chicory coffees. From the volatiles identified grinding, with or without an additional steam-
in the coffee aroma, numerous constituents are ing step or treatment with hot water. It contains
also found in these oils. However, a basic dif- 11.4% moisture, 70.2% carbohydrates and 3.0%
ference appears to be that the numerous sulfur- fat and provides an extract which is 67.9% solu-
containing substances, e. g., 2-furfurylthiol, that ble in water.
are present in roasted beans appear in consider-
ably lower amounts.
21.1.5.3.5 Acorn Coffee
21.1.5.3 Individual Products This product is made from acorns, freed from fruit
hull and the bulk of the seed coat, by the same
21.1.5.3.1 Barley Coffee process as used for coffee. It contains an average
of 10.5% moisture, 73.0% carbohydrates and
Barley (or rye, corn or wheat) coffee is obtained provides an extract which is 28.9% soluble in
by roasting the cleaned cereal grains after steep- water.
ing or steaming. The products contain up to 12%
moisture and have about 4% ash.
21.1.5.3.6 Other Products
into substitutes before, during or after the roasting year, or leaves can be plucked at intervals of
step. The content of caffeine never exceeds 0.2% 6–9 days all year round. In China there are 3–4
in such products. harvests per year.
The younger the plucked leaves, the better the
tea quality. The white-haired bud and the two ad-
jacent youngest leaves (the famous “two leaves
21.2 Tea and Tea-Like Products and the bud” formula) are plucked, but plucking
of longer shoots containing three or even four to
21.2.1 Foreword six leaves is not uncommon. Further processing
of the leaves provides black or green tea.
Tea or tea blends are considered to be the young,
tender shoots of tea shrubs, consisting of young
leaves and the bud, processed in a way traditional
to the country of origin. The tea shrub was cul- 21.2.2 Black Tea
tivated in China and Japan well before the time
of Christ. Plantations are now also found in In- The bulk of harvested tea leaves is processed into
dia, Pakistan, Sri Lanka, Indonesia, Taiwan, East black tea. First, the leaves are withered in trays or
Africa, South America, etc. Table 21.14 shows drying racks in drying rooms, or are drum dried.
some data on the production of tea. This involves dehydration, reducing the moisture
The evergreen tea shrub (Camellia sinensis, content of the fresh leaves from about 75% to
synonym Thea sinensis) has three principal vari- about 55–65% so that the leaves become flaccid,
eties, of which the Chinese (var, sinensis small a prerequisite for the next stage of processing:
leaves) and the Assam varieties (var. assamica, rolling without cracking of the leaves. Withering
◦
large leaves) are the more important and widely at 20–35 C lasts about 4–18 h. During this time
cultivated. Grown in the wild, the shrub reaches the thinly spread leaves lose about 50% of their
a height of 9 m but, in order to facilitate harvest weight in air or in a stream of warm air as in drum
on plantations and in tea gardens, it is kept drying. In the next stage of processing, the leaves
pruned as a low spreading shrub of 1–1.5 m in are fed into rollers and are lightly, without pres-
height. The plant is propagated from seeds or sure, conditioned in order to attain a uniform dis-
by vegetative propagation using leaf cuttings. It tribution of polyphenol oxidase enzymes. These
thrives in tropical and subtropical climates with enzymes are present in epidermis tissue cells, spa-
high humidity. The first harvest is obtained after tially separated from their substrates. This is fol-
4–5 years. The shrub can be used for 60 to 70 lowed by a true rolling step in which the tea leaf
years. The harvesting season depends upon the tissue is completely macerated by conventional
region and climate and lasts for 8–9 months per crank rollers under pressure. The cell sap is re-
leased and subjected to oxidation by oxygen from
the air. The rolling process is regarded as fermen-
Table 21.14. Production of tea in 2006 (1000 t) tation and proceeds at 25 ◦ C for tea leaves spread
Continent Tea Country Tea thinly in layers 3.5–7 cm thick. The traditional
fermentation takes about 2–3 h. The fermented
World 3649 China 1050 tea is dried in belt dryers counter-currently with
India 893 hot air at ca. 90 ◦C to a water content of 3 to 4%.
Africa 486 Sri Lanka 311 In this process the leaf material is heated to 80 ◦C,
America, Central 1 Kenya 311 which is sufficient to inactivate the polyphenol
America, North – Turkey 205 oxidases. The sap released during rolling and fer-
America, South Indonesia 171 mentation solidifies during drying on the fine lit-
and Caribbean 95 Vietnam 142 tle hairs on the surface of the leaf. This tea extract
Asia 3058 Japan 92 has a gold or silver color. These are the “tips”,
Europe 1 Argentina 68 which are a sign of good quality. They dissolve on
Oceania 9 Iran 59
brewing. During drying, aroma substances are
∑ (%)a 90 formed and the coppery-red color is changed to
a black (hence “black tea”).
World production = 100 %.
952 21 Coffee, Tea, Cocoa 21.2 Tea and Tea-Like Products 952
India and Sri Lanka tea factories use both rollers 21.2.4 Grades of Tea
and machines of continuous operation – the
socalled CTC machines (crushing, tearing and The numerous grades of tea found in the trade
curling). They provide a simultaneous crushing, are defined by origin, climate, age, processing
grinding, and rolling of the tea leaf, thus reduc- method, and leaf grade. They can be classified
ing the rolling and fermentation time to 1 to somewhat arbitrarily:
2 hours. Earl Grey tea is black tea perfumed with • According to leaf grade (tea with full, intact
bergamot oil. leaves), such as Flowery Orange Pekoe and
Orange Pekoe (made from leaf buds and the
two youngest, hairy, silver leaves with
21.2.3 Green Tea yellowish tips); Pekoe (the third leaf); Pekoe
Souchong (with the coarsest leaves, fourth to
In the green tea manufacture, the development of sixth, on the young twig).
oxidative processes is regarded as an adverse fac- • Broken-tea, with broken or cut leaves simi-
tor. The fresher the tea leaf used in manufacture, lar to the above grades, in which the fine
the better the tea produced. Since oxidative pro- broken or cut teas with the outermost golden
cesses catalyzed by the leaf enzymes are undesir- leaf tips are distinguished from coarse, broken
able, the enzymes are inactivated at an early stage leaves. Broken/cut tea (loose tea) is the pre-
and their reactions are replaced by thermochem- ferred product in world trade since it provides
ical processes. In contrast to black tea manufac- a finer aroma which, because of increased
ture, withering and fermentation stages are omit- surface area, produces larger amounts of the
ted in green tea processing. beverage.
There are two methods of manufacturing green • Fannings and the fluff from broken/cut leaves,
tea: Japanese and Chinese. The Japanese method freed from stalks or stems, are used preferen-
involves steaming of the freshly plucked leaf at tially for manufacturing of tea bags.
95 ◦C, followed by cooling and drying. Then the • Tea dust, which is not used in Europe.
leaf undergoes high-temperature rolling at 75 to • Brick tea is also not available on the European
80 ◦C. In the Chinese method the fresh leaves are market. It is made of tea dust by sifting, steam-
placed into a roaster which is heated by smokeless ing and pressing the dust in the presence of
charcoal, and roasted. After rolling and sifting, a binder into a stiff, compact teabrick.
firing is the final step in the production of green
With regard to the origin, teas of especially high
tea. During the processing of green tea the con-
quality are those from the Himalayan region Dar-
tent of tannin, chlorophyll, vitamin C and organic
jeeling and from the highlands of Sri Lanka.
acids decreases only slightly as a consequence of
All over the world there is blending of teas
enzyme inactivation. (e. g., Chinese, Russian, East-Friesen blends,
Green tea provides a very light, clear, bitter tast- household blends) to adjust the quality and
ing beverage. In China and Japan it is often arom- flavor of the brewed tea to suit consumer taste,
atized by flowers of orange, rose or jasmin. Yel-
acceptance or trends and to accommodate re-
low tea and red tea (Oolong) occupy an interme-
gional cultural practices for tea-water ratios. Like
diate position between the black and green teas,
coffee, tea extracts are dried and marketed in the
yellow tea being closer to green teas, and red tea
form of a soluble powder, often called instant tea.
to black teas.
Yellow tea production does not include fermen-
tation. Nevertheless, in withering, roasting, and
firing, a portion of tannins undergoes oxidation, 21.2.5 Composition
and, therefore, dry yellow tea is darker than green
tea. The chemical composition of tea leaves varies
Red tea is a partially fermented tea. Its special fla- greatly depending on their origin, age and the type
vor which is free from the grassy note of green tea of processing. Table 21.15 provides data on the
is formed during roasting and higher-temperature constituents of fresh and fermented tea leaves. In
rolling. fermented teas 38–41% of the dry matter is sol-
952 21 Coffee, Tea, Cocoa 21.2 Tea and Tea-Like Products 953
Table 21.15. Composition (%, dry weight basis) of Table 21.16. Phenolic compounds in fresh tea leaves
fresh and fermented tea leaves and of tea brew (% dry matter)
Constituent Fresh Black tea Black tea Compound Content
flush brewa
(− )-Epicatechin 1–3
Phenolic (− )-Epicatechin gallate 3–6
of great importance for tea fermentation. Their Table 21.17. Amino acids and phenolic compounds in
activity rises during the leaf withering and rolling green and black tea (% dry matter)
process and then drops during the fermentation Tea Phenolic Amino
stage, probably as a consequence of reactions compounds acids
of some products (e. g., o-quinones) with the
enzyme proteins. Green tea
5-Dehydroshikimate reductase which reversibly Prime quality (Japan) 13.2 4.8
interconverts dehydroshikimate and shikimate is Consumer quality (Japan) 22.9 2.1
Consumer quality (China) 25.8 1.8
a key enzyme in the biosynthesis of phenolic
Black tea
compounds via the phenylalanine pathway. Highlands (Sri Lanka) 28.0 1.6
Phenylalanine ammonia-lyase which catalyzes Plains (Sri Lanka) 30.2 1.7
the cleavage of phenylalanine into transcin-
namate and NH3 , is equally important for
the biosynthesis of phenols. Its activity in tea
leaves parallels the content of catechins and lamine, the latter being derived from alanine. The
epicatechins. compound is then transported into the leaves. The
Proteinases cause protein hydrolysis during analogous compounds, 4-N-ethylasparagine and
withering, resulting in a rise in peptides and free 5-N-methylglutamine, are present at very low lev-
amino acids. els in tea leaves.
The observed oxidation of linolenic acid to (Z)-
3-hexenal, which then partly isomerizes to (E)-2-
hexenal, is catalyzed by a lipoxygenase and a hy-
21.2.5.4 Caffeine
droperoxide lyase (cf. 3.7.2.3) and also occurs
by autoxidation. (Z)-3-Hexenal contributes to the
Caffeine constitutes 2.5–5.5% of the dry matter
aroma of green tea.
of tea leaves. It is of importance for the taste of
Chlorophyllases participate in the degradation of
tea. Theobromine (0.07–0.17%) and theophylline
chlorophyll and transaminases in the production
(0.002–0.013%) are also preset but in very low
of precursors for aroma constituents.
amounts. The biosynthesis of these two com-
Demethylation of pectins by pectin methyl es-
pounds involves methylation of hypoxanthine or
terase (cf. 4.4.5.2) results in the formation of
xanthine:
a pectic acid gel, which affects cell membrane
permeability, thus resulting in a drop in the rate
of oxygen diffusion into leaves during fermenta-
tion.
cellulose, hemicelluloses and pectic substances. color) are present in fermented leaves, both be-
Inositol occurs also in tea leaves. ing converted to pheophytines (black) during the
firing step.
Fourteen carotenoids have been identified in
21.2.5.6 Lipids tea leaves. The main carotenoids are xantho-
phylls, neoxanthin, violaxanthin and β-carotene
Lipids are present only at low levels. The po- (cf. 3.8.4.1). The content decreases during the
lar fraction (glycerophospholipids) in young tea processing of black tea. Degradation of neo-
leaves is predominant, while glycolipids predom- xanthin (cf. 3.8.4.4), as an example, yields
inate in older leaves. β-damascenone, a significant contributor to tea
Triterpene alcohols, such as β-amyrin, butyros- aroma (Table 21.18).
permol and lupeol are predominant in the un-
saponifiable fraction. The sterol fraction contains
7 7
only -sterols, primarily α-spinasterol and - 21.2.5.8 Aroma Substances
stigmasterol.
The aroma substances of black tea are shown
in Table 21.18. A number of aroma substances
21.2.5.7 Pigments greatly increase when the drink is brewed. It has
(Chlorophyll and Carotenoids) been proposed that a modified Strecker reaction
(cf. 4.2.4.4.7) contributes to an increase in 2-me-
thylpropanal, 2- and 3-methylbutanal. The o-di-
Chlorophyll is degraded during tea processing.
quinones, which are produced by the oxidation
Chlorophyllides and pheophorbides (brownish in
of the numerous phenolic compounds present in
tea, then take on the role of the dicarbonyl com-
pound. The increase in geraniol is probably due
Table 21.18. Concentrations of potent odorants in black to the hydrolysis of the corresponding glycosides.
tea (Darjeeling Gold Selection) – yields in the making Some aroma substances which are produced by
of the drinka
Aroma substance Concentration Yield
(mg/kg) (%) Table 21.19. Concentrations of important aroma sub-
stances in the powder and brew of green tea
2-Methyllpropanal 0.25 2300
the peroxidation of unsaturated fatty acids, play “fermentation”. This term is a misnomer and
a role in black tea and are even more important in originates from the time when the participation of
green tea (Table 21.19). Thus, (Z)-l,5-octadien-3- microorganisms was assumed. In this processing
one, (Z)-3-hexenal and 3-methyl-2,4-nonandione step, the pigments are formed primarily as
(MND) are responsible for the green and hay-like a result of phenolic oxidation by the polyphenol
notes in the aroma profile of this tea. Linolenic oxidases. In addition, oxidation of amino acids,
acid is the precursor of the first two carbonyl com- carotenoids and unsaturated fatty acids, preferen-
pounds. MND is a degradation product of furan tially by oxidized phenols, is of importance for the
fatty acids (cf. 3.7.2.1.5) and is present in tea in formation of odorants.
the concentrations shown in Table 21.19. A com- Harler (1963) described tea aroma development
parison of the values for tea and for the bever- during processing: “The aroma of the leaf
age made from it (Table 21.19) shows that the ex- changes as fermentation proceeds. Withered leaf
traction yield for most of the aroma substances has the smell of apples. When rolling (or leaf
is >50%. β-Damascenone is an exception with maceration) begins, this changes to one of pears,
a yield of 11%. which then fades and the acrid smell of the green
leaf returns. Later, a nutty aroma develops and,
finally, a sweet smell, together with a flowery
21.2.5.9 Minerals smell if flavor is present.”
The enzymatic oxidation of flavanols via the
Tea contains about 5% minerals. The major elem- corresponding o-quinones gives theaflavins
ent is potassium, which is half the total mineral (Formula 21.6, IX–XII: bright red color, good
content. Some tea varieties contain fluorine in solubility), bisflavanols (XIII–XV: colorless),
higher amounts (0.015–0.03%). and epitheaflavic acids (XVI, XVII: bright red
color, excellent solubility). The theaflavins and
epitheaflavic acids are important ben-zotropolone
derivatives that impart color to black tea.
21.2.6 Reactions Involved in the Processing A second, obviously heterogenous group of com-
of Tea pounds, found in tea after the enzymatic oxi-
dation of flavanols, are the thearubigins (XVIII,
Changes in tea constituents begin during the XIX), a group of compounds responsible for the
withering step of processing. Enzymatic protein characteristic reddish-yellow color of black tea
hydrolysis yields amino acids of which a part is extracts (cf. 18.1.2.5.2, Formula 18.21). On the
transaminated to the corresponding keto acids. whole, the phenol fraction of black tea consists of
Both types of acids provide a precursor pool the following main components (g/kg): thearubi-
for aroma substances. The induced chlorophyll gens (59.5), epigallocatechingallates (16.5), epi-
degradation has significance for the appear- gallocatechin (10.5), epicatechingallate (8.0) and
ance of the end-product. A more extensive theaflavin gallate (6.6).
conversion of chlorophyll into chlorophyllide, Aroma development during fermentation is ac-
a reaction catalyzed by the enzyme chloro- companied by an increase in the volatile com-
phyllase (cf. 17.1.2.9.1) is undesirable since it pounds typical of black tea. They are produced
gives rise to pheophorbides (brown) and not to by Strecker degradation reactions of amino acids
the desired oliveblack pheophytins. Increased with oxidized flavanols (Formula 21.7) and by ox-
cell permeability during withering favors the idation of unsaturated fatty acids and the caroti-
fermentation procedure. As already mentioned, noid neoxanthin.
a uniform distribution of polyphenol oxidases in During the firing step of tea processing, there is
tea leaves is achieved during the conditioning an initial rise in enzyme activity (10–15% of the
step of processing. theaflavins are formed during the first 10 min),
During rolling, the tea leaf is macerated and then all the enzymes are inactivated. Conversion
the substrate and enzymes are brought together; of chlorophyll into pheophytin is involved in re-
a prerequisite for fermentation. The subsequent actions leading to the black color of tea. A pre-
enzymatic oxidative reactions are designated as requisite for these reactions is high temperature
956 21 Coffee, Tea, Cocoa 21.2 Tea and Tea-Like Products 958
(21.6)
I: (− )-epicatechin, R1 , R2 = H
II: (− )-epicatechin-3-gallate, R = H, R1 = 3,4,5-trihydroxybenzoyl
III: (− )-epigallocatechin, R = OH, R1 = H
IV: (− )-epigallocatechin-3-gallate, R = OH, R1 = 3,4,5-trihydroxybenzoyl
V–VIII: o-quinones of compounds I–IV
IX: theaflavin, R, R1 = H
X: theaflavin gallate A, R = H, R1 = 3,4,5-trihydroxybenzoyl
XI: theaflavin gallate B, R = 3,4,5-trihydroxybenzoyl, R1 = H
XII: theaflavin digallate, R, R1 = 3,4,5-trihydroxybenzoyl
XIII: bisflavanol A, R = R1 = 3,4,5-trihydroxybenzoyl
XIV: bisflavanol B, R = 3,4,5-trihydroxybenzoyl, R1 = H
XV: bisflavanol C, R = R1 = H
XVI: epitheaflavic acid, R = H
XVII: 3-galloyl epitheaflavic acid, R = 3,4,5-trihydroxybenzoyl
21.2.7 Packaging, Storage, Brewing tent (0.5–1.5%), it has long been the most
important alkaloid-containing brewed plant
In the country in which it is grown, the tea is product of South America. It contains on the
cleaned of coarse impurities, graded according to average 12% crude protein, 4.5% ether-soluble
leaf size, and then packed in standard plywood material, 7.4% polyphenols and 6% minerals.
chests of 20–50 kg lined with aluminum, zinc or About one third of the total dry matter of the
plastic foils. To preserve tea quality, the foils are leaves is solubilized in a maté brew, except
sealed, soldered or welded. China, glass or metal for caffeine, which solubilizes to the extent
containers are suitable for storing tea. Bags made of only 0.019–0.028%, and is 50% bound in
of pergament or filter papers and filled with me- leaves.
tered quantities of tea are also very common.
During storage, the tea is protected from light,
heat (T < 30 ◦C) and moisture, otherwise its
aroma becomes flat and light. Other sources of 21.2.9 Products from Cola Nut
odor should be avoided during storage.
To prepare brewed tea, hot water is usually poured Cola (kola) nuts, called guru, goora and bissey
on the leaves and, with occasional swirling, left nuts by Africans, are not nuts but actually
for 3–5 min. An initial tea con- centrate or seeds of an evergreen tree of the Sterculiacea
extract is often made, which is subsequently family, genus Cola, species verticillata, nitida
diluted with water. Usually 4–6 g of tea leaves or acuminata, which grows wild in West Africa
per liter are required, but stronger extracts need up to a height of 20 m. The tree is indigenous
about 8 g. The stimulating effect of tea is due to Africa, but plantations of Cola are found on
primarily to the presence of caffeine. Madagascar, in Sri Lanka, Central and South
America. Each fruit borne by the tree contains
several red or yellow-white cola nuts, shaped
like horse chestnuts. The nuts change color
21.2.8 Maté (Paraguayan Tea) to brownish-red when dried, with the typical
cola-red color resulting from the action of
Maté, or Paraguayan tea, is made from leaves polyphenol oxidase enzymes. The nuts are on
of a South American palm, Ilex paraguariensis. the average 5 cm long and 3 cm wide and have
The palm grows in Argentina, Brazil, Paraguay a bitter, astringent taste. The fresh nuts, wrapped
and Uruguay, either wild or cultivated, and in cola leaves and moistened with water, are
reaches a height of 8–12 m. To obtain maté, the the most enjoyed plant product of Western and
palm leaves, petioles, flower stems and young Central Africa. They are consumed mostly in
shoot tips are collected and charred slightly on fresh form but are also chewed as dried nuts or
an open fire or in a woven wire drum. During ground to a powder and eaten with milk or honey.
such firing, oxidase enzymes are inactivated, Cola nuts are used in the making of tinctures,
the green color is fixed and a specific aroma extracts or medical stimulants in tablet or pastille
is formed. The dried product is then pounded form. They are also used in the liqueur, cocoa
into burlap sacks or is ground to a fine powder and chocolate industries and, especially, in the
(maté pulver, maté en pod). Maté may also making of alcohol-free soft drinks, colawines,
be prepared by an alternative process: brief etc. The stimulating effect of cola nuts is due to
blanching of the leaf in boiling water, followed the presence of caffeine (average content 2.16%),
by drying on warm floors and disintegration the main portion of which is in bound form.
of the leaves to rather coarse particles. In the In addition, cola nuts contain on the average
countries in which it is grown, maté is drunk 12.2% moisture, 9.2% nitrogen compounds,
as a hot brew (yerva) from a gourd (maté = 0.05% theobromine, 1.35% crude fat (ether
bulbshaped pumpkin fruit) using a special extract), 3.4% polyphenols, 1.25% red pigments,
metal straw called a bombilla, or it is enjoyed 2.8% sugar, 43.8% starch, 15% other N-free
simply in a powdered form. Maté stimulates extractable substances, 7.9% crude fiber and 3%
the appetite and, because of its caffeine con- ash.
958 21 Coffee, Tea, Cocoa 21.3 Cocoa and Chocolate 960
pulp surrounds 20–50 almond-shaped seeds (ca- West Africa (Ghana, Nigeria, Ivory Coast and
cao beans). The seed is oval and flattened, about Cameroon), and by Brazil (the port of Bahia) and
2 cm long and 1 cm wide, and weighs close to 1 g the Dominica Republic.
after drying. The embryo, with two thick cotyle-
dons (nibs) and a germ rootlet, 5 mm long and
1 mm thick, is under a thin, brittle seed coat. The 21.3.2.2 Harvesting and Processing
colors in the cross-section of a nib range from
white to light brown, to greyish-brown or brown- At harvest the fully ripe pods are carefully cut
violet, to deep violet. from trees, gathered into heaps, cut open and
The fruit is harvested year round but, preferen- the seeds scooped out with the surrounding pulp.
tially, twice a year. The main harvest time in Only rarely are the seeds dried in the sun without a
Mexico is from March through April; in Brazil, prior fermentation step (Arriba and Machala var-
February and, in particular, July. The summer ieties from South America). The bulk of the
harvest is larger and of higher quality. After the harvest is fermented before being dried. In this
tree is planted (progagation by seed or by vege- fermentation step the seeds with the adhering
tative methods), it begins to bear pods after five pulp are transferred to heaps, ditches or fermen-
or six years, giving a maximum yield after 20–30 tation floors, baskets, boxes or perforated barrels
years, while it is nearly exhausted after 40 years and, depending on the variety, are left to ferment
of growth. After reaching full beaning capacity, for 2–8 days. From time to time the seeds are
a cacao tree provides only 0.5–2 kg of fermented mixed to make the oxygen in the air accessible
and dried beans per year. Harvesting at the right to the fermentation process. During this time
time is of great importance for the aroma of ca- the temperature of the material rises rapidly
cao and its products. The fruit is harvested fully to 45–50 ◦C and the germination ability of the
ripe but not overripe, avoiding damage to the seed seeds is lost. First, alcoholic fermentation occurs,
during its removal from the fruit. which later turns into the production of acetic
The tree species Theobroma cacao (the only one acid. Flavor and color formation and partial
of commercial importance) is divided into two conversion of astringent phenolic compounds
major groups. The “Criollo” tree (criollo = na- also occur. The adhering pulp is decomposed
tive) is sensitive to climatic changes and to at- enzymatically and becomes liquid. It drains away
tack by diseases and pests. It bears highly aro- as a fermentation juice. In addition, there are
matic beans, hence their commercial name “fla- reactions between constituents of the seeds and
vor beans”, but they are relatively low yielding. pulp. After fermentation is completed, the seeds
The second group of trees, “Forastero” (foras- may be washed (Java, Sri Lanka), and are dried
tero = strange, inferior), is characterized by great to a moisture content of 6–8%.
vigor and the trees are more resistant to climatic Well-fermented seeds, called cocoa beans from
changes and to diseases and are higher yielding. this step, provide uniformly colored, dark-brown
The purple-red Forastero beans are less flavorful beans which are readily separated into their
than Criollo varieties. Nevertheless, the Forastero cotyledons. Inadequate or unripe fermented
bean is by far the most important commercial type beans are smooth in appearance (violetas) and
of cacao and accounts for the bulk of world cacao are of low quality.
production (Bahia and Accra cacaos). The cocoa imported by consuming countries is
Other varieties worth mentioning are the resist- processed further. The cocoa beans are cleaned
ant and productive Calabacillo and the Ecuado- by a series of operations and separated accord- ing
rian Amelonado varieties. to size in order to facilitate uniform roast- ing
Cacao beans are differentiated by their geograph- in the next processing step. Roasting is be- ing
ical origin, grade of cleanliness and the num- performed more and more as a two-step pro- cess.
ber of preparation steps to which they are sub- Roasting reduces the moisture content of the
jected prior to shipment. “Flavor beans” come beans to 3%, contributes to further oxida- tion
from Ecuador, Venezuela, Trinidad, Sri Lanka of phenolic compounds and the removal of acetic
and Indonesia, while “commercial beans” are ex- acid, volatile esters and other undesirable aroma
ported by the leading cacao-growing countries of components. In addition the eggs and lar-
960 21 Coffee, Tea, Cocoa 21.3 Cocoa and Chocolate 962
vae of pests are destroyed. The aroma of the beans of 2:1 in cocoa shells. These two tryptamides
is enhanced, the color deepens, the seed hard- can be separated by HPLC with fluorescence
ens and becomes more brittle and the shell is detection and very exactly quantified. Cocoa
loosened and made more readily removable be- shells contain 330–395 µg/g of LAT plus BAT,
cause of enzymatic and thermal reactions. The but the cotyledons only 7–10 µg/g.
ripeness, moisture content, variety and size of the
beans and preliminary processing steps done in
the country of origin determine the extent and
other parameters of the bean roasting process.
This process should be carried out in two stages.
First, a drying phase and then a phase in which
important aroma substances are formed. For in-
(21.8)
stance, African cocoa is heated to between 120
and 130 ◦ C and high-quality cocoa to less than
130 ◦C for 30 minutes. Losses induced by roast-
ing are 5–8%. As with coffee, roasted beans are 21.3.2.3 Composition
immediately cooled to avoid overroasting. The
roasters are batch or continuous. Heat transfer oc- The compositions of fermented and air-dried ca-
curs either directly through heated surfaces or by cao nib, cacao shell and germ are presented in Ta-
a stream of hot air, without burning the shell of ble 21.21.
the beans. Roasting lasts 10–35 min, depending
on the extent desired.
Roasted beans are transferred, after cooling, to 21.3.2.3.1 Proteins and Amino Acids
winnowing machines to remove the shells and
germ rootlets (these have a particularly unpleas- About 60% of the total nitrogen content of fer-
ant flavor and impart other undesirable properties mented beans is protein. The nonprotein nitrogen
to cocoa drinks). During winnowing the beans are is found as amino acids, about 0.3% in amide
lightly crushed in order to preserve the nibs and form, and 0.02% as ammonia, which is formed
the shells in larger pieces and to avoid dust for- during fermentation of the beans.
mation. Among the various enzymes, α-amylase, β-fruc-
The winnowing process provides on the aver- tosidase, β-glucosidase, β-galactosidase, pec-
age 78–80% nibs, 10–12% shells, with a small
amount of germ and about 4% of fine cocoa par-
ticles as waste. All yields are calculated on the Table 21.21. Composition (%) of fermented and air
basis of the weight of the raw beans. dried cacao beans (1), cacao shells (2) and cacao
The whole nibs, dried or roasted, dehulled and germs (3)
degermed or cracked, are still contaminated with
1.5–2% shell, seed coats and germ. The debris Constituent 1 2 3
fraction, collected by purifying the cocoa waste, Moisture 5.0 4.5 8.5
consists of fine nib particles and contains up Fat 54.0 1.5 3.5
to 10% shell, seed coating and germ. Although the Caffeine 0.2
cocoa shell is considered as waste material of Theobromine 1.2 1.4
little value, it can be used for recovery of Polyhydroxyphenols 6.0
theobromine, production of activated charcoal, Crude protein 11.5 10.9 25.1
or as a feed, cork substitute or tea substitute Mono- and
oligosaccharides 1.0 0.1 2.3
(cocoa shell tea) and, after extraction of fat,
Starch 6.0
as a fertilizer or a fuel. In the adulteration of Pentosans 1.5 7.0
cocoa, the detection of cocoa shells is promis- Cellulose 9.0 26.5 4.3
ing if based on the indicators lignoceric acid Carboxylic acids 1.5
tryptamide (LAT, Formula 21.8) and behenic acid Other compounds 0.5
tryptamide (BAT), which are present in the ratio Ash 2.6 8.0 6.3
962 21 Coffee, Tea, Cocoa 21.3 Cocoa and Chocolate 963
21.3.2.3.3 Lipids
77 mg/g epicatechin equivalents (ECE), cocoa Pro- or leucoanthocyanins are compounds which,
powder contains very high concentrations com- when heated in acidic media, yield anthocyanins
pared to, e. g., green (83 mg/g GAE, 24 mg/g and catechins or epicatechins, respectively. The
ECE) and black tea (62 mg/g GAE, 17 mg/G form present in the greatest amount is flavan-3-4-
ECE). diol (I in Formula 21.9) which, through 4 → 8 (II)
Three groups of phenols are present in cocoa: cat- or 4 → 6 (III) linkages, condenses to form dimers,
echins (about 37%), anthocyanins (about 4%) and trimers or higher oligomers (cf. 18.1.2.5.2, For-
leucoanthocyanins (about 58%). mula 18.20).
The main catechin is (− )-epicatechin, besides Leucoanthocyanins occur in fruits of various
(+)-catechin, (+)-gallocatechin and (− )-epi- plants in addition to cacao; e. g., apples, pears
gal-locatechin. The anthocyanin fraction con- and cola (kola) nuts.
sists mostly of cyanidin-3-arabinoside and
cyanidin-3-galactoside.
21.3.2.3.6 Organic Acids
Bitter Group
cis-cyclo (L-Pro-L-Val) 8.9
Theobromine 63.6
cis-cyclo (L-Val-L-Leu) 0.82
cis-cyclo (L-Ala-L-Ile) 0.64
cis-cyclo (L-Ile-L-Pro) 0.54
Astringent Group
N-[3× ,4× -Dihydroxy-(E)-cinnamoyl]-
3-hydroxy-L-tyrosine 0.9
(− )-Epicatechin 8.6
Quercetin-3-0-β-D-glucopyranoside 0.10
Quercetin-3-0-β-D-galactopyranoside 0.034
γ-Aminobutyric acid 5.0
Sour Group
Citric acid 31
Acetic acid 17
Succinic acid 1.7
Malic acid 3.6
(21.9)
964 21 Coffee, Tea, Cocoa 21.3 Cocoa and Chocolate 965
fermentation may also occur to a small extent. acids during fermentation and the extent of
Pectolytic enzymes and other glycosidases affect their degradation to aldehydes and amines. The
the degradation of polysaccharides. This is decisive step for the degradation is the roasting,
reflected in the fruit pulp becoming liquid and not the fermentation. Hence, the Strecker reaction
draining away. This improves aeration, resulting (cf. 4.2.4.4.7) has a considerably higher share
in oxidation of alcohol to acetic acid by acetic in the formation of these aroma substances (ex-
acid bacteria during the second to fourth days. The ception 2-methylbutanal) than the corresponding
pH drops from about 6.5 to about 4.5 and the enzymatic degradation reactions.
temperature increases to 45–50 ◦C. The seed cell The proper running of the fermentation process
walls become permeable, the living cacao seed prevents the growth of detrimental microorgan-
is killed and an oxidative process takes over the isms, such as molds, butyric acid bacteria and
entire mass. From the fifth to the seventh day, the putrefaction-inducing bacteria.
oxidation and condensation reactions of phenolic
compounds predominate. Amino acids and pep-
tides react with the oxidation products of the phe- 21.3.2.5 Production of Cocoa Liquor
nolic compounds, giving rise to water-insoluble
brown or brown-violet phlobaphenes (cacao- After roasting and drying, the cocoa nib is dis-
brown and red), which confer the characteristic integrated and milled in order to rupture the cell
color to fermented cacao beans. A decrease in the walls of aggregates and expose the cocoa but-
content of soluble phenols mellows the original ter. Knife-hammer mills or crushing rolls usually
harsh and astringent cacao flavor. Finally, the serve for disintegration, while rollerball, horizon-
oxidation reactions are terminated by drying the tal “stone”, steel disc or disc attrition mills are
seeds to a moisture content of less than 8%. used for fine disintegration of cocoa particles. The
The hydrolysis of the proteins and peptides resultant product is a homogeneous mobile paste,
during fermentation yields with the free amino a flowing cocoa mass or cocoa liquor.
acids the precursors of aroma substances.
Table 21.25 shows the increase in free amino
21.3.2.6 Production of Cocoa Liquor
with Improved Dispersability
Table 21.25. Formation of free amino acids, accompa-
nying Strecker aldehydes and amines in cocoa The cocoa nib or the cocoa mass is subjected to
Compound Process an alkalization process in order to mellow the
flavor by partial neutralization of free acids, im-
Without After After prove the color and enhance the wettability of co-
fermen- fermen- roastingc coa powder, improve dispersability and lengthen
tationa tationb suspension-holding ability, thus preventing for-
Amino acid (mg/kg) mation of a sediment in the cocoa drink. The pro-
L-Phenylalanine 190 1120 700 cess involves the use of solutions or suspensions
L-Leucine 170 1240 760 of magnesium oxide or hydroxide, potassium or
L-Isoleucine 140 390 280 sodium carbonate or their hydroxides. It is oc-
Aldehydes (µg/kg) casionally performed at elevated temperature and
Phenylacetaldehyde 16 34 202 pressure, usually using steam. In this process, in-
3-Methylbutanal 116 1636 8470 troduced by C.I. van Houten in 1828 (hence the
2-Methylbutanal 143 2075 3791 term “Dutch cocoa process”), the roasted nibs
Amines (µg/kg) are treated with a dilute 2–2.5% alkali solution
2-Phenylethylamine 227 1168 10,216 at 75–100 ◦C, then neutralized, if necessary, by
2-/-3-Methylbutylamine 129 1219 17,070 tartaric acid, and dried to a moisture content of
a
After washing the pulp and drying in the sun. about 2% in a vacuum dryer or by further knead-
b Fermentation (7 days) and drying in the sun. ing of the mass at a temperature above 100 ◦C.
c As in “b”, then roasting of the nibs (15 min at 95◦ ,
This treatment, in addition to acid neutralization,
increase in temperature in 20 min to 115 ◦ C, cooling). causes swelling of starch and an overall spongy
966 21 Coffee, Tea, Cocoa 21.3 Cocoa and Chocolate 967
and porous cell structure of the cocoa mass. Co- Chocolates were originally made directly from
coa so treated is often incorrectly designated as cocoa nibs by grinding them in the presence of
“soluble cocoa” – the process does not increase sugar. Chocolate is now made from nonalkalized
solubility. Finally, the cocoa is disintegrated with cocoa liquor by incorporating sucrose, cocoa
fine roller mills. The “alkalized” cocoa generally butter, aroma or flavoring substances and, oc-
contains 52–58% cocoa butter, up to 5% ash and casionally, other constituents (milk ingredients,
up to 7% alkalized mass or liquor. nuts, coffee paste, etc.). The ingredients are
mixed, refined, thoroughly conched and, finally,
the chocolate mass is molded. To obtain a highly
21.3.2.7 Production of Cocoa Powder aromatic, structurally homogeneous and stable
by Cocoa Mass Pressing form and a product which “melts in the mouth”,
a set of chocolate processing steps is required, as
To convert the cocoa mass/liquor into cocoa described below.
powder, the cocoa fat (54% of nib weight on
the average) has to be reduced by pressing,
usually by means of a hydraulic, mechanical or, 21.3.3.2 Chocolate Production
preferentially, horizontally-run expeller press at
a pressure of 400–500 bar and a temperature of 21.3.3.2.1 Mixing
90–100 ◦C. To remove the contaminating cell de-
bris, the hot cocoa butter is passed through a filter Mixing is a processing step by which ingredients
press, then molded and cooled. The bulk of the such as cocoa liquor, high grade crystalline
cocoa butter produced is used in chocolate manu- sucrose, cocoa butter and, for milk chocolate,
facturing. The “stone hard” cocoa press cake, milk powder are brought together in a mixer
with a residual fat content of 10–24%, is dis- (“melangeur”) or paster. A homogeneous,
integrated by a cook breaker, i. e. rollers with coarse chocolate paste is formed after intense
intermashing teeth. It is then ground in a peg mill mixing.
and separated into a fine and a coarse fraction by
an air sifter, the coarse fraction being recycled and
milled repeatedly. Cocoa powders are divided 21.3.3.2.2 Refining
according to the extent of defatting into lightly
defatted powder, with 20–22% residual cocoa
The refining step is performed by single or multi-
butter, and extensively-defatted powder, which
ple refining rollers which disintegrate the choco-
contains less than 20% but more than 10% butter.
late paste into a smooth-textured mass made up of
Lightly defatted powder is darker in color and
much finer particles. The rollers are hollow and
milder in flavor. Cocoa powder is widely used
can be adjusted to the desired temperature by wa-
in the manufacture of other products, e. g., cake
ter cooling. The refined end-product has a particle
fillings, icings, pudding powders, ice creams and
size of less than 30 to 40 µm. Its fat content should
cocoa (chocolate) beverages.
be 23–28%.
Baking chocolate is made by a special process. of thick sugar solution and liqueur by pouring
Other kinds of chocolates include: cream; full the mixture into mold cavities. The solid crust
or skim milk; filled; fruit, nut, almond; and crystallizes on the outer walls, while the inner
those containing coffee or candied orange peels. portion of the mixture remains liquid. The core
Cola-chocolate is a caffeine-containing product so obtained is then dipped into melted chocolate,
(maximum of 0.25% caffeine) prepared by mixing as described above. For pralines without a sugar
with extracts obtained from coffee, cola or other crust (brandy or liqueur), the processing involves
caffeine-containing plants. Diabetic- or diet- hollow-body machines in which the chocolate
chocolates are made by replacing sucrose with shell is formed, then filled with, e. g., brandy,
fructose, mannitol, sorbitol or xylitol. In- and covered with a lid in a second machine.
formation about chocolate coatings is presented The fondant may also contain invertase and,
in Table 21.26. Chocolates can also contain nuts thereby, the praline filling liquefies after several
and almonds whose oil contents are occasionally days. Plastic pastes are made by preliminary
2
reduced by pressing to reach 3
of the original pulverization of the ingredients in a mill and
amount. This is because the oil has a melting point then refiner by rollers. The oil content of the
lower than that of cocoa butter. In filled ingredients (nuts, almonds, peanuts) provides the
chocolates, the filler is first placed into a choco- consistency for a workable paste after grinding.
late cup and then closed with a chocolate lid or Chocolate for beverages or drinks (chocolate
cover. Fine crumbs of chocolate are made by powder or flour) is made from cocoa liquor or
pressing low-fat chocolate through a plate with cocoa powder and sucrose. It is customary to
orifices. Hollow figures are made in two-part incorporate seasonings, especially vanillin. The
molds, by a hollow press or by gluing together sugar content in chocolate drink powders is at
the individually molded parts. most 65%.
The term “praline” originates from the name of Chocolate syrups are made in the USA by adding
the French Marshal Duplessis-Praslin, whose bacterial amylase. The enzyme prevents the syrup
cook covered sweets with chocolate. Only from thickening or setting by solubilizing and
a few of the many processing options will be dextrinizing cocoa starch. A fat coating is a glaz-
mentioned. For pralines with a hard core, the ing like chocolate coatings made from a fat other
hot, supersaturated sugar syrup (fondant) is than cocoa butter (fat from peanuts, coconuts,
poured into molds dusted with wheat powder etc.). It is often used on baked or confectionery
and left to cool. The congealed core (korpus) is products. Tropical chocolates contain high melt-
dipped into molgen kuverture and, in this way, ing fats or are specially prepared to make the
covered with a chocolate coat (creme-praline). chocolate resistant to heat. The melting point of
The fondant can be fully or partly replaced by cocoa butter can be raised by a controlled pre-
fruit pastes like marzipan, jams, nuts, almonds, crystallization procedure. Another option is based
etc. (dessert-pralines). Such pralines are pre- on the formation of a coherent sugar skeleton
pared with or without a sugar crust. Products in which the fat is deposited in hollow or void
with a sugar crust are made from a mixture spaces. In this case, in contrast to regular choco-
21.4 References 969
late, there is no continuous fat phase to collapse Frank, O., Zehentbauer, G., Hofmann, T.: Bioresponse-
during heating. guided decomposition of roast coffee beverage and
identification of key bitter taste compounds. Eur.
Food Res. Technol. 222, 492 (2006)
Frauendorfer, F., Schieberle, P.: Identification of the
21.3.4 Storage of Cocoa Products
key aroma compounds in cocoa powder based
on molecular sensory correlations. J. Agric. Food
All products, from the raw cacao to chocolate, Chem. 54, 5521 (2006)
demand careful storage – dry, cool, well aerated Garloff, H., Lange, H.: Kaffee. In: Lebensmittel-
space, protected from light and sources of other technologie (Ed.: R. Heiss) Springer, Berlin, 1988,
odors. A temperature of 10–12 ◦C and a relative p. 355
humidity of 55–65% are suitable. Chocolate Granvogl, M., Bugan, S., Schieberle, P.: Formation of
products are readily attacked by pests, particu- amines and aldehydes from parent amino acids dur-
larly cacao moths (Ephestia elutella and Cadra ing thermal processing of cocoa and model systems:
cauteila), the flour moth (Ephestia kuhniella) new insights into pathways of the Strecker reaction.
and also beetles (Coleoptera), cockroaches J. Agric. Food Chem. 54, 1730 (2006)
(Dictyoptera) and ants (order Hymenoptera). Guth, H., Grosch, W.: Furanoid fatty acids as precursors
Chocolates not properly stored are recognized by of a key aroma compound of green tea. In: Progress
a greyish matte surface. Sugar bloom is caused in Flavour Precursor Studies (Eds.: P. Schreier, P.
Winterhalter) Allured Publishing Corporation, 1993,
by storage of chocolate in moist conditions (rela-
p. 189
tive humidity above 75–80%) or by deposition Hatanaka, A.: The fresh green odor emitted by plants.
of dew, causing the tiny sugar particles on the Food Rev. Int. 12, 303 (1996)
surface of the chocolate to solubilize and then, Ho, C.-T., Zhu, N.: The chemistry of tea. In: Caf-
after evaporation, to form larger crystals. A fat feinated beverages. ACS Symposium Series 754,
bloom arises from chocolate fat at temperatures 316 (2000).
above 30 ◦C. At these temperatures the liquid fat Lange, H., Fincke, A.: Kakao und Schokolade. In:
is separated and, after repeated congealing, forms Handbuch der Lebensmittelchemie, Bd. VI (Ed.:
a white and larger spot. This may also occur as Schormüller, J.), p. 210, Springer-Verlag: Berlin,
a result of improper precrystallization or tem- 1970
pering during chocolate production. The defect Lee, K.W., Kim, Y.J., Lee, H.J., Lee, C.Y.: Cocoa has
may be prevented or rectified by posttempering more phenolic phytochemicals and a higher antioxi-
dant capacity than teas and red wine. J. Agric. Food
at 30 ◦C for 6 h.
Chem. 51, 7292 (2003)
Maier, H.G.: Kaffee. Verlag Paul Parey: Berlin. 1981
Münch, M., Schieberle, P.: A sensitive and selective
21.4 References method for the quantitative determination of fatty
acid tryptamides as shell indicators in cocoa prod-
Bokuchava, M.A., Skobeleva, N.I.: The biochemistry ucts. Z. Lebensm. Unters. Forsch. A 208, 39 (1999)
and technology of tea manufacture. Crit. Rev. Food Poisson, L., Kerler, J., Liardon, R.: Assessment of
Sci. Nutr. 12, 303 (1979/80) the contribution of new aroma compounds found
Castelein, J., Verachtert, H.: Coffee fermentation. In: in coffee to the aroma of coffee brews. In: State
Biotechnology (Eds.: Rehm, H.-J., Reed, G.), Vol. 5, of the Art in Flavour Chemistry and Biology. T.
p. 587, Verlag Chemie: Weinheim. 1983 Hofmann, M. Rothe, P. Schieberle (eds.) Deutsche
Clarke, R.J., Vitzthum, O.G.: Coffee. Recent Develop- Forschungsanstalt für Lebensmittelchemie, Garch-
ments. Blackwell Science Ltd., Oxford, 2001, p. 1, ing, 2004, p. 495
50 and 68 Rizzi, G.P.: Formation of sulfur-containing volatiles un-
Clifford, M.N., Willson, K.C. (Eds.): Coffee, botany, der coffee roasting conditions. In: Caffeinated bever-
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Engelhardt, U.H., Lakenbrink, C., Lapczynski, S.: 65, Verlag Hans Carl: Nürnberg. 1975
Antioxidative phenolic compounds in green-black Scharbert, S., Holzmann, N., Hofmann, T.: Identifica-
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970 21 Coffee, Tea, Cocoa
Schieberle, P.: The chemistry and technology of cocoa. Stark, T., Bareuther, S., Hofmann, T.: Molecular
In: Caffeinated beverages. ACS Symposium Series definition of the taste of roasted cocoa nibs (Theo-
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22 Spices, Salt and Vinegar
Some plants with intensive and distinctive flavors 22.1.1.1 Components of Essential Oils
and aromas are used dried or in fresh form as sea-
sonings or spices. Table 22.1 lists the most im- Most spices contain an essential or volatile oil
portant spice plants together with the part of the (Table 22.2), which can be isolated by steam
plant used for seasoning. distillation. The main oil constituents are either
Fruits
1 Pepper, black Piper nigrum Piperaceae Tropical and subtropical regions
2 Vanilla Vanilla planifolia Orchidaceae Madagascar, Comore Island,
Vanilla fragans Mexico, Uganda
Vanilla tahitensis
Vanilla pompona
3 Allspice Pimenta dioica Myrtaceae Caribbean Islands, Central America
4 Paprika (bell pepper) Capsicum annuum. var. annuum Solanaceae Mediterranean and Balkan region
Chili (Tabasco) Capsicum frutescens
Brown pepper Capsicum baccatum, var. pendulum
5 Bay treea Laurus nobilis Lauraceae Mediterranean region
6 Juniper berries Juniperus communis Cupressaceae Temperate climate region
7 Aniseed Pimpinella anisum Apiaceae
8 Caraway Carum carvi Apiaceae Temperate climate region
9 Coriander Coriandrum sativum Apiaceae
10 Dilla Anethum graveolens Apiaceae
Seeds
11 Fenugreek Trigonella foenum greacum Leguminosae Mediterranean region,
temperate climate region
12 Mustard Sinapsis albab Brassicaceae
Brassica nigrac Brassicaceae Temperate climate region
13 Nutmeg Myristica fragrans Myristicaceae Indonesia, Sri Lanka, India
14 Cardamom Elettaria cardamomum Zingiberaceae India, Sri Lanka
Flowers
15 Cloves Syzygium aromaticum Myrtaceae Indonesia, Sri Lanka, Madagascar
16 Saffron Crocus sativus Iridaceae Mediterranean region,
India, Australia
17 Caper Capparis spinosa Capparidaceae Mediterranean region
Rhizomes
18 Ginger Zingiber officinale Zingiberaceae South China, India, Japan,
Caribbean Islands, Africa
19 Turmeric Curcuma longa Zingiberaceae India, China, Indonesia
Barks
20 Cinnamon Cinnamomum zeylanicum, Lauraceae China, Sri Lanka, Indonesia,
C. aromaticum, C. burmanii Caribbean Islands
Roots
21 Horseradish Armoracia rusticana Brassicaceae Temperate climate region
Leaves
22 Basil Ocimum basilicum Labiate Mediterranean region, India
23 Parsley Petroselinum crispum Apiaceae Temperate climate region
24 Savory Satureia hortensis Labiate Temperate climate region
25 Tarragon Artemisia dracunculus Compositae Temperate climate region,
Mediterranean region
26 Marjoram Origanum majorana Lamiaceae Temperate climate region
27 Origano Origanum heracleoticum, O. onites Lamiaceae Temperate climate region
28 Rosemary Rosmarinus officinalis Lamiaceae Mediterranean region
29 Sage Salvia officinalis Lamiaceae Mediterranean region
30 Chives Allium schoenoprasum Liliaceae Temperate climate region
31 Thyme Thymus vulgaris Lamiaceae Temperate climate region
(22.1)
reaction sequence is assumed: Table 22.2. Content of essential oils in some spicesa
Spice % Vol./Weight
Black pepper 2.0–4.5
White pepper 1.5–2.5
Aniseed 1.5–3.5
Caraway 2.7–7.5
Coriander 0.4–1.0
Dill 2.0–4.0
Nutmeg 6.5–15
Cardamom 4–10
Ginger 1–3
Turmeric 4–5
Marjoram 0.3–0.4
Origano 1.1
Rosemary 0.72
Sage 0.7–2.0
a For leaf spices, the values refer to the weight of the
fresh material.
(22.3)
(22.2)
(22.4)
974 22 Spices, Salt and Vinegar 22.1 Spices 975
Roman numerals without an asterisk refer to chemical structures shown in Chapter 22.
d
A mixture of neral and geranial (cf. footnote “b” in Table 5.33).
The concentrations given in Table 22.3 are 22.1.1.2 Aroma Substances
guide values which can vary greatly depend-
ing on the variety and cultivation condi- In some spice plants, the odor corresponds with
tions. that of the main components of the volatile frac-
974 22 Spices, Salt and Vinegar 22.1 Spices 976
22.1.1.2.1 Pepper
(22.5)
(22.6)
976 22 Spices, Salt and Vinegar 22.1 Spices 978
Water (w/w %) 90 11 12 16 2
Volatile compoundsa 326 49 37 188 83
Volatile compoundsa
α-Pinene 5.8 1.2 1.4 3.1 0.6
α-Phellandreneb 198.1 13.3 8.1 41.6 14.9
Limonene 10.0 0.7 0.4 2.0 0.7
β-Phellandrene 27.5 2.2 1.1 6.5 1.8
p-Cymene 5.5 1.1 0.4 4.0 0.1
3,9-Epoxy-p-ment-1-eneb 39.8 0.5 Traces 8.9 1.4
Myristicin 4.4 0.6 0.3 4.3 1.5
Neophytadiene 1.0 6.3 2.6 38.2 26.0
a
Values in mg per 100 g of dry weight.
b
Aroma substances that determine quality.
L-isoleucine (XIX in Formula 22.6) is cyclized to posed to the action of a thioglucosidase enzyme
the amine XX, which is then converted to HD2F (cf. 17.1.2.6.5), yielding isothiocyanates (mustard
via the Strecker reaction, e. g., with methylgly- oil). Allyl isothiocyanate is obtained from the glu-
oxal. coside sinigrin, a compound responsible for the
pungent burning odor and taste of both spices.
p-Hydroxybenzyl isothiocyanate obtained from
22.1.1.2.5 Saffron sinalbin is only slightly volatile and contributes
significantly to the sharp pungent taste of mus-
In aroma extract dilution analyses (cf. 5.2.2), tard.
a compound with a saffron and hay-like odor, The aroma of horseradish is also influenced
which could be 2-hydroxy-4,4,6-tri-methyl-2,5- by methyl, ethyl, isopropyl and 4-pentenyl
iso-thiocyanates which, however, are present
cyclohexadien-l-one, gave the highest FD factor.
only in very small amounts in comparison to allyl
This was followed by the terpene aldehyde
isothiocyanate.
safranal and an unknown compound, both of
which have a saffron odor. Safranal (XXIV)
is probably obtained from the bitter substance
picrocrocin (XXII) by hydrolysis and elimination 22.1.1.2.7 Ginger
of water (Formula 22.6).
The fresh ginger root has a citrus and camphor-
like, flowery, musty, fatty and green odor. In a col-
umn chromatographic preliminary separation of
an extract, the characteristic aroma substances ap-
peared in the fraction of the oxidized hydrocar-
bons. The highest FD factors in dilution analyses
were obtained for geraniol, linalool, geranial, cit-
(22.6) ronellyl acetate, borneol, 1,8-cineol and neral.
Mustard and horseradish contain glucosinolates The aroma profile of basil is characterized
(Table 22.6) which, after cell rupture, are ex- by green/fresh, flowery, clover- and pepper-
978 22 Spices, Salt and Vinegar 22.1 Spices 979
R Name Occurrence
Sinalbin Mustard
Gluconasturtiin Horseradish
exhibit high aroma values. The two cultivars 22.1.1.3 Substances with Pungent Taste
of parsley compared in Table 22.8 differ con-
siderably in the concentrations of some aroma The hot, burning pungent taste of paprika (red
substances, e. g., cultivar I contains 6 times more pepper), pepper (black pepper) and ginger is
p-mentha-1,3,8-triene. caused by the nonvolatile compounds listed in
Drying of parsley on exposure to air leads to Table 22.9.
a large decrease in (Z)-3-hexenal and (Z)-6- Black pepper contains 3–8% of piperine (XXV)
decenal (Table 22.8), resulting in a reduction of as the most important pungent substance. Pepper
the green note. In addition, sulfurous/cabbage- is sensitive to light since the trans,trans-diene sys-
like and hay-like aroma defects appear due to tem of piperine isomerizes to the cis,trans-diene
the formation of dimethylsulfide and 3-me- system of the almost tasteless isochavicin on ex-
thyl-2,4-nonandione. If drying proceeds at posure to light.
a higher temperature, methylpropanal, 2- and 3- In the processing and storage of ginger,
methylbutanal, which do not play a role in the gingerol easily dehydrates to shogaol, increas-
aroma of fresh parsley, also increase to ing the pungency (Table 22.9). A retroaldol
such an extent that their malty aroma cleavage of shogaol can also occur with the
quality can assert itself in the aroma pro- formation of sweet-spicy zingerone and hexa-
file. nal (Formula 22.7). Above a certain concentra-
980 22 Spices, Salt and Vinegar 22.1 Spices 981
Table 22.9. Compounds present in spices causing a hot burning organoleptic perception
Name Structure Occurrencea Relative
pungencyb
Dihydro-
capsain
tion, hexanal causes an aroma defect in ginger of capsicum or in various other pepper plants
oleoresins. depends on the variety, cultivation, drying and
The concentration of the capsaicinoids XXX, storage conditions, and varies between 0.01 and
XXXI, and XXXII (Table 22.9) in the fruits 1.2%. These compounds are the most pungent
980 22 Spices, Salt and Vinegar 22.1 Spices 982
(22.9)
22.1.2 Products
22.1.1.5 Antioxidants
provide or enhance the sour, acidic taste of food Fermentation of ethanol is conducted as a top fer-
(cf. 8.12.5). mentation and increasingly as a submerged oxi-
dative process. In top fermentation the bacteria are
cultivated on spongy, porous laminated car- riers
(usually beechwood shavings) with the alco- holic
22.3.1 Production solution trickling down over carrier surfaces while
a plentiful supply of air is provided from below.
Vinegar is produced microbiologically from The fermentation is stopped at a 0.3% by volume
ethanol or by dilution of acetic acid. residual ethanol level to avoid overoxi- dation, i.
e., oxidation of acetic acid to CO2 and water.
CH3 CH2 OH + O2
−→ CH3 COOH + H2 O + 494 kJ (22.11)
22.3.1.2 Chemical Synthesis
With low mineral content Solid residue = mineral matter content ≤500 mg/l
With very low mineral content Solid residue ≤50 mg/l
With high mineral content Solid residue >1500 mg/l
Bicarbonate containing Hydrogen carbonate >600 mg/l
Sulfate containing Sulfate >200 mg/l
Chloride containing Chloride >200 mg/l
Calcium containing Calcium >150 mg/l
Magnesium containing Magnesium >50 mg/l
Fluoride containing Fluoride >1 mg/l
Iron containing Divalent iron >1 mg/l
Sodium containing Sodium >200 mg/l
Suitable for preparation of infant food Sodium ≤20 mg/l, nitrate ≤10 mg/l, nitrite ≤0.02 mg/l
fluoride ≤1.5 mg/l
Suitable for low-sodium nutrition Sodium <20 mg/l
“Säuerling” Carbon dioxide of natural origin >250 mg/l