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21 Coffee, Tea, Cocoa

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

Table 21.1. Production of coffee beans in 2006 (1000 t)


Continent Raw Country Raw
coffee coffee

World 7843 Brazil 2593


Viet Nam 854
Africa 922 Colombia 696
America, Central 1020 Indonesia 653
America, North 3 Mexico 288
America, South India 274
and Caribbean 4782 Ethiopia 260
Asia 2069 Guatemala 257
Europe – Honduras 191
Oceania 68 Peru 175
∑ (%)a 75
Fig. 21.1. Longitudinal section of a coffee fruit (accord-
a
ing to Vitzthum, 1976) World production = 100%.

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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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Table 21.2. Composition of green Arabica and Robusta coffeea,b


Constituent Arabica Robusta Components

Soluble carbohydrates 9–12.5 6–11.5


Monosaccharides 0.2–0.5 Fructose, glucose, galactose, arabinose
(traces)
Oligosaccharides 6–9 3–7 Sucrose (>90%), raffinose (0–0.9%),
stachyose (0–0.13%)
Polysaccharides 3–4 Polymers of galactose (55–65%),
mannose (10–20%), arabinose (20–35%),
glucose (0–2%)
Insoluble polysaccharides 46–53 34–44
Hemicelluloses 5–10 3–4 Polymers of galactose (65–75%),
arabinose (25–30%), mannose (0–10%)
Cellulose, β(1–4)mannan 41–43 32–40
Acids and phenols
Volatile acids 0.1
Nonvolatile aliphatic acids 2–2.9 1.3–2.2 Citric acid, malic acid, quinic acid
Chlorogenic acidc 6.7–9.2 7.1–12.1 Mono-, dicaffeoyl- and feruloylquinic
acid
Lignin 1–3
Lipids 15–18 8–12
Wax 0.2–0.3
Oil 7.7–17.7 Main fatty acids: 16:0 and 18:2 (9,12)
N Compounds 11–15
Free amino acids 0.2–0.8 Main amino acids: Glu, Asp, Asp-NH2
Proteins 8.5–12
Caffeine 0.8–1.4 1.7–4.0 Traces of theobromine and theophylline
Trigonelline 0.6–1.2 0.3–0.9
Minerals 3–5.4
a
Values in % of solids.
b Water content of raw coffee: 7–13%.
c Main components: 5-caffeoylquinic acid (chlorogenic acid: Arabica 3.0–5.6%; Robusta 4.4–6.6%).

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
(%) (%)

21.1.3.3 Composition of Roasted Coffee Alanine 4.75 5.52


Arginine 3.61 0
Aspartic acid 10.63 7.13
Table 21.3 provides information about the com- Cystine 2.89 0.69
position of roasted coffee. This varies greatly, de- Glutamic acid 19.80 23.22
pending on variety and extent of roasting. Glycine 6.40 6.78
Histidine 2.79 1.61
Isoleucine 4.64 4.60
Leucine 8.77 10.34
21.1.3.3.1 Proteins
Lysine 6.81 2.76
Methionine 1.44 1.26
Protein is subjected to extensive changes when Phenylalanine 5.78 6.32
heated in the presence of carbohydrates. There is Proline 6.60 7.01
a shift of the amino acid composition of coffee Serine 5.88 0.80
protein acid hydrolysates before and after bean Threonine 3.82 1.38
roasting (Table 21.4). The total amino acid con- Tyrosine 3.61 4.35
tent of the hydrolysate drops by about 30% be- Valine 8.05 8.05
cause of considerable degradation. a A loss due to roasting amounts to 17.6%.
Arginine, aspartic acid, cystine, histidine, ly-
sine, serine, threonine and methionine, being
especially reactive amino acids, are somewhat
decreased in roasted coffee, while the stable 21.1.3.3.2 Carbohydrates
amino acids, particularly alanine, glutamic acid
and leucine, are relatively increased. Free amino Most of the carbohydrates present, such as cellu-
acids occur only in traces in roasted coffee. lose and polysaccharides consisting of mannose,
galactose and arabinose, are insoluble. During
roasting a proportion of the polysaccharides are
Table 21.3. Composition of roasted coffee (medium de- degraded into fragments which are soluble. Su-
gree of roasting)
crose (cf. Table 21.2) present in raw coffee is de-
Component Content (%)a composed in roasted coffee up to concentrations
of 0.4–2.8%. Monosaccharides also hardly occur.
Arabica Robusta
Caffeine 1.3 2.4
Lipids 17.0 11.0 21.1.3.3.3 Lipids
Proteinb 10.0 10.0
Carbohydrates 38.0 41.5
Trigonelline, niacin 1.0 0.7 The lipid fraction appears to be very stable and
Aliphatic acids 2.4 2.5 survives the roasting process with only minor
Chlorogenic acids 2.7 3.1 changes. Its composition is given in Table 21.5.
Volatile compounds 0.1 0.1 Linoleic acid is the predominant fatty acid, fol-
Minerals 4.5 4.7 lowed by palmitic acid. The raw coffee waxes,
Melanoidinsc 23.0 23.0 together with hydroxytryptamide esters of var-
a Based on solids. Water content varies between 1 and ious fatty acids (arachidic, behenic and ligno-
5%. ceric) originate from the fruit epicarp. These com-
b Calculated as the sum of the amino acids after acid pounds are 0.06–0.1% of normally roasted cof-
hydrolysis. fee. The diterpenes present are cafestol (I, R =
c Calculated as the difference.
H), 16-O-methylcafestol (I, R = CH3 ), and kah-
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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

tic, tartaric, pyruvic and citric. Higher fatty acids


weol (II). Cafestol and kahweol are degraded by and malonic, succinic, glutaric and malic acids are
the roasting process. only minor constituents. Itaconic (I), citra- conic
Since 16-O-methylcafestol is found only in Ro- (II) and mesaconic acids (III) are degra- dation
busta coffee (0.6–1.8 g/kg of dry weight, green products of citric acid, while fumaric and maleic
coffee), it is a suitable indicator for the detection acids are degradation products of malic acid:
of the blending of Arabica with Robusta coffee,
even in instant coffee.

(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

21.1.3.3.7 Aroma Substances


Its precursors are polysaccharides containing
The volatile fraction of roasted coffee has arabinose, e. g., arabinogalactans, as well as
a very complex composition. Dilution analyses cysteine in the free and bound form. A consid-
(cf. 5.2.2) have shown that of the 850 volatile erable part of furfurylthiol and the other thiols
compounds identified until now, only the 40 listed in Table 21.8 is present in roasted coffee
listed in Table 21.7 contribute to the aroma. as disulfide bound to cysteine, SH-peptides
Indeed, 28 aroma substances in the concentra- and proteins. On roasting, the formation of
tions present in a medium roasted Arabica coffee furfurylthiol is promoted by the water content
drink (Table 21.8) can largely approximate its and the slightly acidic pH value of the beans
aroma. The correspondence becomes even better because under these conditions, the precursor
by the addition of 4-methoxy-2-methylbutan-2- arabinose in the polysaccharides is released by
thiol (cf.5.3.2.5), which has a concentration of partial hydrolysis.
0.022 µg/kg in the drink. Robusta coffees contain alkylpyrazines and phe-
The aroma profile of coffee is composed of nols in significantly higher concentrations than
the following notes: sweet/caramel-like, earthy, Arabica (Table 21.9). Correspondingly, the earthy
sulfurous/roasty and smoky/phenolic. Table 21.8 and smoky/phenolic notes in the aroma profile are
shows that most of the odorants can be assigned more intensive. Arabica coffees are usually richer
to these notes. The remaining odorants have in the odorants of the sweet/caramel-like group.
a fruity or spicy odor. In the aroma profile, The pea-like, potato-like aroma note of raw cof-
they are discretely detectable if their concen- fee is produced by 3-alkyl-2-methoxypyrazines,
trations are considerably higher than shown in 3-isobutyl-2-methoxypyrazine having the highest
Table 21.8. Omission experiments (cf. 5.2.7) aroma value. Being very stable compounds, they
show that 2-furfurylthiol makes the most im- easily survive the roasting process. However, this
portant contribution to the aroma of coffee. process yields very intensively smelling odor-
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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.

beverage (11) by percolation of coffee powder (54 g) 1, 2,3-Butandione; 2, 4-Hydroxy-2,5-dimethyl-3(2H)-


with water (ca. 90 ◦ C). furanone; 3, 2-ethyl-3,5-dimethylpyrazine; 4, 2-fur-
n.a.: not analyzed. furylthiol; 5, guaiacol
946 21 Coffee, Tea, Cocoa 21.1 Coffee and Coffee Substitutes 946
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946

Table 21.10. Aroma defects in coffee


Aroma defect Key aroma substance Cause

Phenolic, musty, medicinal 2,4,6-Trichloroanisole Degradation of fungicides


Mouldy Potato 2-Methylisoborneol Microorganisms
taste Fruity, Alkylmethoxypyrazines Combination of insects and bacteria
silage-like Cyclohexanecarboxylic acid ethylester Uncontrolled fermentation

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
946 21 Coffee, Tea, Cocoa 21.1 Coffee and Coffee Substitutes 947
947
947

developed in Italy, coffee is extracted briefly by


superheated water (100–110 ◦C), while filtration
is accelerated by steam at a pressure of 4–5 bar.
The exceptionally strong drink is usually turbid
and is made of freshly ground, darkly roasted
coffee. The water temperature should not exceed
85–95 ◦C in order to obtain an aromatic drink
with most of the volatile substances retained.
Water quality obviously plays a role, especially
water with an unusual composition (some
mineral spring waters, excessively hard water,
and chlorinated water) might reduce the quality
of the coffee brew. Brewed coffee allowed to
stand for a longer time undergoes a change in
flavor.
For regular brewed coffee, 50 g of roasted
coffee/l (7.5 g/150 ml cup) is used; for mocca,
100 g/l; and for Italian espresso, 150 g/l. Depen-
ding on the particle size and brewing procedure,
18–35% of the roasted coffee is solubilized. The Fig. 21.3. The flavor of roasted coffee brew as related
dry matter content of coffee beverages is 1–3%. to pH value (according to Vitzthum, 1976)
The composition is presented in Table 21.12.
The taste of coffee depends greatly on the pH of
the brew. The pH using 42.5 g/l of mild roasted ieties are higher than those of Arabica varieties.
coffee should be 4.9–5.2. At pH < 4.9 the coffee Figure 21.3 shows the relationship between pH
tastes sour; at pH > 5.2 it is flat and bitter. Cof- and extract taste for some coffees of known ori-
fees of different origins provide extracts with dif- gin.
ferent pH’s. Generally, the pH’s of Robusta var- The difference between the aroma of the beverage
and that of ground coffee is the more intensive
phenolic, buttery, caramel-like note and a weaker
roasty note. These changes are caused by shifts in
Table 21.12. Composition of coffee beveragesa the concentrations of the aroma substances dur-
Constituent Content (% dry ing brewing (Table 21.8). Compounds like 2,3-
weight basis) butandione, the furanones 6, 7 and 27, 2-ethyl-
3,5-pyrazine, the thiols 17 and 18 are extrac-
Proteinb 6 ted with yields of >75%, while only 25% or less
Polysaccharides 24
of 2-ethenyl-3-ethyl-5-methylpyrazine, 3-iso-
Saccharose 0.8
Monosaccharides 0.4
butyl-2-methoxypyrazine, 2-furfurylthiol and
Lipids 0.8 β-damascenone pass into the beverage. The low
yield of 2-furfurylthiol is partly due to reactions
Volatile acids 1.4
which occur during percolation of the coffee
Nonvolatile acids 1.6
Chlorogenic acids 14.8 powder.
Caffeine 4.8 Caffeine and the quinic acid lactones listed in Ta-
Trigonelline 1.6 ble 21.13 are the bitter substances in the coffee
Nicotinic acid 0.08 drink. Accordingly, these lactones are almost ex-
Volatile aroma compounds 0.4 clusively responsible for the bitter note of a decaf-
Minerals 14 feinated coffee drink (Table 21.13). Although the
Unidentified constituents 29.4 concentrations of the lactones III–VII, IX and X
(pigments, bitter compounds etc.) in the drink are lower than their threshold con-

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).
948 21 Coffee, Tea, Cocoa 21.1 Coffee and Coffee Substitutes 948
948
948

(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
949
949

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.

21.1.5.2 Processing of Raw Materials


21.1.4.3 Treated Coffee
The raw materials are stored as such (all cer-
The “roast” compounds, the phenolic acids and eals, figs), or are stored until processing as dried
the coffee waxes, are irritating substances in slices (e. g., root crops such as chicory or sugar
roasted coffee. Various processes have been beet). After careful cleaning, steeping, malting
developed to separate these constituents to make and steaming in steaming vats, pots or pressure
roasted coffee tolerable for sensitive people. vats take place. Roasting follows, with a final
950 21 Coffee, Tea, Cocoa 21.2 Tea and Tea-Like Products 950

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

21.1.5.3.2 Malt Coffee Coffee substitute blends and similarly designated


products are blends of the above-outlined cof-
Malt coffee is made from barley malt by roasting, fee substitutes, coffee adjuncts and coffee beans.
with or without an additional steaming step. It Caffeine-containing coffee substitutes or adjuncts
are made by incorporating plant caffeine extracts
950 21 Coffee, Tea, Cocoa 21.2 Tea and Tea-Like Products 951

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

compoundsb 30 5 4.5 (− )-Epicatechin digallate +a


Oxidized phenolic (− )-Epigallocatechin 3–6
Protein 15 15 +d
(− )-Epigallocatechin digallate +
Amino acids 4 4 3.5
Caffeine 4 4 3.2 (+)-Catechin 1–2
Crude fiber 26 26 0 (+)-Gallocatechin 3–4
Other carbohydrates 7 7 4 Flavonols and flavonolglycosides
Lipids 7 7 + (quercetin, kaempherol, etc.) +
Pigmentse 2 2 + Flavones
Volatile compounds 0.1 0.1 0.1 (vitexin, etc.) +
Minerals 5 5 4.5 Leucoanthocyanins 2–3
Phenolic acids and esters
a Brewing time 3 min. b Mostly flavanols. c Mostly (gallic acid, chlorogenic acids)
thearubigins. d Traces. e Chlorophyll and carotenoids. p-Coumaroylquinic acid, theogallin ∼
5
Phenols, grand total 25–35
a
uble in hot water; this is significantly more than Quantitative data are not available.
for roasted coffee.

to the presence of flavonols and flavones. Thus,


21.2.5.1 Phenolic Compounds (cf. 18.1.2.5)
tea which is processed into green or black tea is
chemically readily distinguishable mainly by the
Phenolic compounds make up 25–35% of the composition of phenolic compounds. Green tea
dry matter content of young, fresh tea leaves. contains 17.5% and black tea 14.4% of polyphe-
Flavanol compounds (Table 21.16) are 80% of nols (expressed in gallic acid equivalents). The
the phenols, while the remainder is proantho- main components in green tea are the catechins
cyanidins, phenolic acids, flavonols and flavones. (90% of the polyphenol fraction), which account
During fermentation the flavanols are oxidized for only 25% in black tea.
enzymatically to compounds which are respon- Changes in the content of the phenols occur dur-
sible for the color and flavor of black tea. The ing tea leaf growth on the shrub: the concentra-
reddish-yellow color of black tea extract is largely tion decreases and the composition of this frac-
due to theaflavins and thearubigins (cf. 21.2.6). tion is altered. Therefore, good quality tea is ob-
The astringent taste is caused primarily by fla- tained only from young leaves. Among the re-
vonol-3-glycosides. Quercetin-3-O-[α- L-rhamno- maining phenolic compounds theogallin (XI in
pyranosyl-(1→6)-β-D -glucopyranside] is especi-
Formula 18.14) plays a special role, since it is
ally active with a threshold value of 0.001 µmol/l.
Also of importance are (threshold values): found only in tea and is correlated with tea qual-
kaempferol-3-O-[α-L-rhamnopyranosyl-(1→6)- ity.
O-β-D -glucopyranoside] (0.25 µmol/l), querce-
tin-3-O-β-15- D-galactopyranoside (0.43 µmol/l),
quercetin-3-O-β-D -glucoside (0.65 µmol/l) and 21.2.5.2 Enzymes
kaempferol-3-O-β-D-glucopyranoside (0.67
µmol/l). The enzymes are inactivated in green
tea, hence flavanol oxidation is prevented. The A substantial part of the protein fraction in tea
greenish or yellowish color of green tea is due consists of enzymes.
952 21 Coffee, Tea, Cocoa 21.2 Tea and Tea-Like Products 954

The polyphenol oxidases, which are located


mainly within the cells of leaf epidermis, are
954 21 Coffee, Tea, Cocoa 21.2 Tea and Tea-Like Products 955

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.

21.2.5.3 Amino Acids

Free amino acids constitute about 1–3% of the


dry matter of the tea leaf. Of this, 50% is thea-
nine (5-N-ethylglutamine) and the rest consists
of protein-forming amino acids; β-alanine is also
present. (21.5)
Green tea contains more theanine than black tea.
Generally, there is a characteristic difference in
amino acid content as well as difference in pheno- 21.2.5.5 Carbohydrates
lic compounds between the two types of tea (Ta-
ble 21.17). Glucose (0.72%), fructose, sucrose, arabinose
The contribution of theanine to the taste of green and ribose are among sugars present in tea
tea is discussed. Theanine biosynthesis occurs leaves. Rhamnose and galactose are bound
in the plant roots from glutamic acid and ethy- to glycosides. Polysaccharides found include
954 21 Coffee, Tea, Cocoa 21.2 Tea and Tea-Like Products 956

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

3-Methylbutanal 0.32 1105 Compound Amounta


2-Methylbutanal 0.54 1262
Powder Brewb
Hexanal 1.60 289
(E)-2-Hexenal 0.27 2406 (Z)-1,5-Octadien-3-one 1.8 0.012
(Z)-4-Heptenal 0.051 108 3-Hydroxy-4,5-dimethyl-
(Z)-3-Hexen-1-ol 1.60 500 2(5H)-furanone (HD2F) 49 0.6
(E)-2-Nonenal 0.032 103 3-Methyl-2,4-nonandione (MND) 83 0.56
R/S-Linalool 6.60 180 (Z)-4-Heptenal 112 0.63
(E,Z)-2,6-Nonadienal 0.038 122 (Z)-3-Hexenal 101 0.28
Phenylacetaldehyde 0.65 731 (E,Z)-2,6-Nonadienal 61 0.48
(E,E)-2,4-Nonadienal 0.087 45 l-Octen-3-one 6 0.03
3-Methylnonan-2,4-dione 0.062 65 (E,E)-2,4-Decadienal 127 0.9
(E,E)-2,4-Decadienal 0.073 330 (E)-β-Damascenone 9 0.01
(E)-β-Damascenone 0.0098 125 4-Hydroxy-2,5-dimethyl-
Geraniol 0.37 3227 3(2H)-furanone (HD3F) 276 n.a.
(E,E,Z)-2,4,6-Nonatrienal 0.16 58 2-/3-Methylbutyric acid 5280 63
β-Ionone 0.17 75 2-Phenylethanol 1140 10.5
3(2H)-furanone
4-Hydroxy-2,5-dimethyl- 0.10 Linalool
a Values in µg/kg. 206 1.0
2167 b Brew (1 kg) prepared from 10 g of the powder.
aYield of the aroma substances obtained in the making n.a., not analyzed.
of the drink from 12 g tea and 1 l water (95◦ ).
956 21 Coffee, Tea, Cocoa 21.2 Tea and Tea-Like Products 957

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

XVIII: thearubigins (proanthocyanidin-type), R = H, OH; R1 = H, 3,4,5-trihydroxybenzoyl


XIX: thearubigins (polymeric catechins of unknown structure)
and an acidic environment. The undesired brown
color is obtained at higher pH’s. The astringent
character of teas is decreased by the formation
of complexes between phenolic compounds and
proteins. The firing step also affects the balance of
aroma substances. On the one hand there is a loss
of volatile compounds, on the other hand, at high
temperatures, an enhancement of the build-up of
typical aroma constituents occurs, e. g., as a result
of sugar-amino acid interactions.
(21.7)
958 21 Coffee, Tea, Cocoa 21.3 Cocoa and Chocolate 959

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

21.3 Cocoa and Chocolate


21.3.1 Introduction

Cocoa, as a drink, is different from coffee or tea


since it is consumed not in the form of an aque-
ous extract, i. e. a clear brew, but as a suspension.
In addition to stimulating alkaloids, particularly
theobromine, cacao products contain substantial
amounts of nutrients: fats, carbohydrates and pro-
teins. Unlike coffee and tea, cocoa has to be con-
sumed in large amounts in order to experience
a stimulating effect.
Cacao beans were known in Mexico and Cen-
tral America for more than a thousand years be-
fore America was discovered by Columbus. They
were enjoyed originally in the form of a slurry of
roasted cocoa beans and corn which was seasoned
with paprika, vanilla or cinnamon. In the first half
of the 17th century, cacao beans were introduced
into Germany. Cocoa became popular in the Old
World only after sugar was added to the chocolate
preparation. Initially, cocoa was treated as a lux-
ury item, until the 19th century, when production
of pulverized chocolate and defatted cocoa was
Fig. 21.4. Production of cocoa powder and chocolate
established and they were distributed extensively
as a food commodity.
The world production of cacao was 31,000 t in
1870/80, 103,000 t in 1900 and 1,585,000 t in 21.3.2 Cacao
1979. The production in 2006 and the main ca-
caoproducing countries are listed in Table 21.20. 21.3.2.1 General Information
The processing of cacao beans into cocoa pow-
der and chocolate is presented schematically in Cacao beans are the seeds of the tropical ca-
Fig. 21.4. cao tree, Theobroma cacao, family Sterculiaceae.
Originating in the northern part of South Amer-
ica and currently grown within 20 ◦C latitude of
Table 21.20. Production cacao bean in 2006 (1000 t) the Equator, the tree flourishes in warm, moist
climates with an average annual temperature of
Continent Cacao Country Cacao
24–28 ◦C and at elevations up to 600 m. The tree,
beans beans
because of its sensitivity to sunshine and wind,
World 4059 Côte d’Ivoire 1400 is often planted and cultivated under shade trees
Ghana 734 (“cacao mothers”), such as forest trees, coconut
Africa 2922 Indonesia 580 palms and banana trees. The perennial tree grows
America, Central 43 Nigeria 485 in the wild to a height of 10–15 m, but on plan-
America, North – Brazil 199 tations it is kept at 2–4 m by pruning. The tree
America, South Cameroon 165 blooms all year round and the small red or white
and Caribbean 462 Ecuador 94 flowers bear 20–50 ripe fruits per tree. The ripe
Asia 628 Togo 73
fruit or pod resembles a cantaloupe, 15–25 cm
Europe – Mexico 38
Oceania 48 Colombia 37 long and 7–10 cm wide. The pod is surrounded by
a strong 10–15 mm thick shell. Embedded within
∑ (%)a 94 the pod are pulpa, i. e. a sweet, mucilaginous
a World production = 100%. pulp containing 10% glucose and fructose. The
960 21 Coffee, Tea, Cocoa 21.3 Cocoa and Chocolate 961

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

tinesterase, polygalacturonase, proteinase, al- 21.3.2.3.5 Phenolic Compounds


kaline and acid phosphatases, lipase, catalase,
peroxidase and polyphenol oxidase activities The nib cotyledons consist of two types of
have been detected in fresh cacao beans. These parenchyma cells (Fig. 21.5). More than 90% of
enzymes are inactivated to a great extent during the cells are small and contain protoplasm, starch
processing. granules, aleurone grains and fat globules. The
larger cells are scattered among them and contain
all the phenolic compounds and purines. These
21.3.2.3.2 Theobromine and Caffeine polyphenol storage cells (pigment cells) make up
11–13% of the tissue and contain anthocyanins
Theobromine (3,7-dimethylxanthine), which is and, depending on their composition, are white
1.2% in cocoa, provides a stimulating effect, to dark purple. Data on the composition of these
which is less than that of caffeine in coffee. cells and that of the total tissue are given in
Therefore, it is of physiological importance. Table 21.22.
Caffeine is also present, but in much lower The content of phenolic compounds is also of in-
amounts (average 0.2%). A cup of cocoa con- terest from the standpoint of chemoprevention.
tains 0.1 g of theobromine and 0.01 g of caffeine. With 84 mg/g gallic acid equivalents (GAE) and
Theobromine crystallizes in the form of small
rhombic prisms which sublime at 290 ◦ C without
decomposition. In cocoa beans theobromine is
often weakly bound to tannins and is released by
the acetic acid formed during fermentation of the
beans. Part of this theobromine then diffuses into
the shell.

21.3.2.3.3 Lipids

Cocoa fat (cocoa butter), because of its abundance


and value, is the most significant ingredient of ca-
cao beans, and is dealt with in detail elsewhere (cf.
Fig. 21.5. A cross-section of cocoa cotyledon tissue
14.3.2.2.3).

Table 21.22. Composition of polyphenol storage cells


21.3.2.3.4 Carbohydrates of cacao tissue
Constituent Polyphenol Cotyle-
Starch is the predominant carbohydrate. It is
storage dons
present in nibs but not in shells, a fact useful in cell
the microscopic examination of cocoa powders (%) (%)a
in methods based on the occurrence of starch
as a characteristic constituent. Components of Catechins 25.0 3.0
the dietary fiber are amongst others pentosans, Leucocyanidins 21.0 2.5
Polymeric leucocyanidins 17.5 2.1
galactans, mucins containing galac–turonic acid,
Anthocyanins 3.0 0.4
and cellulose. Soluble carbohydrates present
include stachyose, raffinose and sucrose (0.08– Total phenols 66.5 8.0
1.5%), glucose and fructose. Sucrose hydrolysis, Theobromine 14.0 1.7
Caffeine 0.5 0.1
which occurs during fermentation of the beans, Free sugars 1.6
provides the reducing sugar pool important for Polysaccharides 3.0
aroma formation during the roasting process. Other compounds 14.4
Mesoinositol, phytin, verbascotetrose, and some
a
other sugars are found in cocoa nib. As % of dry matter.
962 21 Coffee, Tea, Cocoa 21.3 Cocoa and Chocolate 964

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

Of the organic acids (1.2–1.6%), citric, acetic,


succinic and malic acid contribute to the taste of
cocoa (Table 21.23). They are formed during fer-
mentation. The amount of acetic acid released by
the pulp and partly retained by the bean cotyle-
dons depends on the duration of fermentation and
on the drying method used. Eight brands of co-
coa were found to contain 1.22–1.64% total acids,
0.79–1.25% volatile acids and 0.19–0.71% acetic
acid.

Table 21.23. Taste substances of roasted cocoa nibs


Compound Concentration
(mmol/kg)

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

21.3.2.3.7 Volatile Compounds


and Flavor Substances

Cocoa aroma is crucially dependent on harvest-


ing, fermentation, drying and roasting. The fresh
beans have the odor and taste of vinegar. The (21.11)
characteristic bitter and astringent taste and the
residual sweet taste of fermented beans might be
impaired by various faults, such as processing of
unripe or overripe fruit, insufficient aeration, lack Table 21.24. Concentrations of potent odorants in a co-
of mixing of the fruit, infection with foreign or- coa powdera
ganisms and/or smoke damage as a result of im- Compound Concentration
proper drying. (mg/kg)
The odorants of cocoa powder are listed in Ta-
ble 21.24. A model (cf. 5.2.7) made by using Acetic acid 332
the 24 aroma substances on the basis of deodor- 3-Methylbutanal 25.8
2-Methylbutanal 14.3
ized cocoa powder reproduced the aroma of cocoa
Phenylacetaldehyde 6.60
very closely. 3-Methylbutyric acid 8.55
The taste of cocoa is described by the attributes 2-Phenylacetic acid 7.70
bitter, astringent and sour. It can be repro- Methylpropionic acid 2.80
duced by mixing 41 constituents dissolved in 2-Methylbutyric acid 1.75
water (pH 5.5). The key compounds for the 4-Hydroxy-2,5-dimethyl-3(2H )-
individual notes are the substances listed in furanone 0.62
Table 21.23. Apart from theobromine, a series of 2-Phenylethanol 0.59
diketopiperazines are involved in the bitter taste Butyric acid 0.32
(cf. Table 21.23), which are formed during the 2-Phenylethylacetate 0.32
2-Methoxyphenol 0.23
thermal degradation of proteins during roasting
4-Methylphenol 0.12
(Formula 21.10): Linalool 0.072
2-Ethyl-3,6-dimethylpyrazine 0.070
3-Methylindole 0.055
2-Ethyl-3,5-dimethylpyrazine 0.031
3-Hydroxy-4,5-dimethyl-2(5H )-
furanone 0.015
2,3-Diethyl-5-methylpyrazine 0.008
Dimethyltrisulfide 0.007
2-Acetyl-1-pyrroline 0.006
2-Methyl-3-(methylthio)-furan 0.0005
2-Isobutyl-3-methoxypyrazine 0.0009
(21.10) a Partially defatted cocoa powder (fat content: 20%),
treated with alkali.
The intensity of the bitter taste of theobromine
is increased by the interaction with certain
diketopiperazines, a molar ratio of 2:1 giving the
highest intensity. However, only those complexes
are synergistically active in which the hydrogen 21.3.2.4 Reactions During Fermentation
bridges shown in Formula 21.11 can be formed. and Drying
Thus, synergism does not occur when, e. g., in
caffeine, the N(1)-atom in the purine ring is The reactions occurring within the pulp during
methylated. fermentation of whole cacao fruit can be dis-
Apart from the compounds mentioned in Ta- tinguished from those occurring in the nibs or
ble 21.23, epicatechin contributes to the astrin-
cotyledons. The pulp sugar is fermented by yeast
gent taste and also influences the bitter note.
to alcohol and CO2 on the first day. Lactic acid
964 21 Coffee, Tea, Cocoa 21.3 Cocoa and Chocolate 966

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%.

21.3.3 Chocolate 21.3.3.2.3 Conching

21.3.3.1 Introduction The refined chocolate mass is dry and powdery


at room temperature and has a harsh, sour
Switzerland has the highest per capita consump- flavor. It is ripened before further processing
tion of chocolate at 10.2 kg (2004), followed by by keeping it in warm chambers at 45–50 ◦C
Norway (9.2), Belgium (9.1), Germany (9.0), Ire- for about 24 h. Ripening imparts a doughy
land (8.8), Great Britain (8.8). The consumption consistency to the chocolate and it may be
of chocolate is low in Italy (3.5), Greece (2.5), used for the production of baking or other
Japan (1.8), Spain (1.6) and Brazil (1.0). commercial chocolates. An additional conching
966 21 Coffee, Tea, Cocoa 21.3 Cocoa and Chocolate 968

step is required to obtain fine chocolates of 21.3.3.2.4 Tempering and Molding


extra smoothness. It is performed in oblong or
round conche pots with roller or rotary conches. Before molding, the mass must be tempered to
The chocolate mass is mixed, ground and initiate crystallization. For both the structure
kneaded. (hard nibs, filling the mold) and appearance
This process is usually run in three stages. (glossy surface that is not dull), this is an
The temperature is maximum 65 ◦C with important operation in which crystal nuclei
milk-containing chocolate and 75 ◦C with are produced under controlled conditions (pre-
milk-free chocolate. In the first, the mass is crystallization). Molten chocolate is initially
treated, depending on the recipe and process, cooled from 50 ◦C to 18 ◦ C within 10 min with
for more than 6–12 h. Loss of moisture occurs constant stirring. It is kept at this lower tempera-
(dry conching) during heating, a protion of the ture for 10 min to form the stable β-modification
volatiles is removed (ethanal, acetone, diacetyl, of cocoa butter (cf. 3.3.1.2). The temperature of
methanol, ethanol, isopropanol, isobutanol, the chocolate is then raised within 5 min to 29–
31 ◦C. The process conditions vary according to
isopentanol and acetic acid ethyl ester) and the
composition. Regardless of processing variables,
fat becomes uniformly distributed, so that each tempering serves to provide a great abundance
cocoa particle is covered with a film of fat. of small fat crystals with high melting points.
The temperature at this stage is not al- lowed During the cooling step, the bulk of the molten
to rise since important aroma substances, e. g., chocolate develops a solid, homogeneous, finely
pyrazines (cf. 21.3.2.3.7), may be lost. In the crystalline, heat-stable fat structure characterized
second stage, the mass is liquefied by the by good melting properties and a nice glossy
addition of residual cocoa butter and at a surface.
higher stirring speed homogenized further. Here, Before molding, the chocolate is kept at 30–32 ◦C
too, the time required greatly depends on the and delivered to warmed plastic or metal molds
desired product quality: about 6 to 40 h. In the with a metering pump. The filled molds pass over
third phase, which starts 2 to 3 h before the end a vibrating shaker to let the trapped air escape.
of the conching process, lecithin and other They then pass through a cooling channel where,
ingredients are added. Up to a limit of about by slow cooling, the mass hardens and, finally,
1.5%, lecithin lowers the flow rate and the at 10 ◦C, the final chocolate product falls out of
viscosity of the mass; 1 part of lecithin can the mold. Tempering, metering, filling, cooling,
replace about 8 to 10 parts of cocoa butter. wrapping and packaging machines now provide
Chemical processes involved in conching are nearly fully mechanized and automated produc-
only partially understood. tion of chocolate.
Efforts have been made to shorten this time-,
energy- and space-consuming final refinement
in conche pots. Processes have been developed 21.3.3.3 Kinds of Chocolate
that are based on the separate pre-refinement
of cocoa nibs or cocoa mass. The spray-film In a strict sense, chocolate represents a food com-
technique uses a cocoa mass with its natural modity which may be molded and which con-
water content or, in the case of highly acidic cocoa sists of cocoa nibs, nib particles, or cocoa liquor
varieties, with the continuous addition of 0.5– and sucrose, with or without added cocoa butter,
2% of water. In a turbulent film with direct natural herbs or spices, vanillin or ethyl vanillin.
heat transfer, the cocoa mass is continu- ously Chocolate contains at least 40% cocoa liquor or
dehumidified, deacidified, degassed, and a blend of liquor and cocoa butter, and up to 60%
roasted in counterflow with hot air (up to sugar. The content of cocoa butter is at least 21%
130 ◦C). For the final refinement, apart from and, when cocoa liquor is blended with cocoa but-
the time-tested conche pots, newly developed
ter, at least 33%.
intensive refiners can be used. They reduce the
The composition of the more important kinds of
conching time to 8 hours. The development of chocolates and confectionery coatings are shown
continuously operated conche pots is also being in Table 21.26.
expedited.
968 21 Coffee, Tea, Cocoa

Table 21.26. Composition of some chocolate products


Product Cocoa Skim milk Cocoa Total Butter Sugar
mass powder butter fat fat (milk)
% % % % % %

Baking chocolate 33–50 – 5–7 22–30 – 50–60


Chocolate for coating 35–60 – to 15 28–35 – 38–50
Milk cream chocolate 10–20 8–16 10–22 33–36 5.5–10 35–60
Whole milk chocolate 10–30 9.3–23 12–20 28–32 3.2–7.5 32–60
Skim milk chocolate 10–35 12.5–25 15–25 22–30 0–2 30–60
Icings 33–65 5–25 35–46 25–50

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
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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-
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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,
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dant capacity than teas and red wine. J. Agric. Food
at 30 ◦C for 6 h.
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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-
biochemistry and production of beans and bever- ages. ACS Symposium Series 754, 210 (2000)
age. The AVI Publishing Comp. Inc., Westport, Sanderson, G.W.: Black tea aroma and its formation. In:
Conn. 1985 Geruch- and Geschmackstoffe (Ed.: Drawert, F.), p.
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-
tea and other methylxanthine-containing beverages. tion of astringent taste compounds by combining in-
In: Caffeinated beverages. ACS Symposium Series strumental analysis and human bioresponse. J. Agric.
754, 111 (2000) Food Chem. 52, 3498 (2004)
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-
754, 262 (2000) broma cocoa) by means of quantitative studies and
Schuh, C., Schieberle, P.: Characterization of the key sensory experiments. J. Agric. Food Chem. 54,
aroma compounds in the beverage prepared from 5530 (2006)
Darjeeling black tea – quantitative difference be- Täupmann, R.: Tee. In: Lebensmitteltechnologie (Ed.:
tween tea leaves and infusion. J. Agric. Food Chem. R. Heiss) Springer, Berlin, 1988, p. 364
54, 916 (2006) Viani, R.: Coffee. In: Ullmann’s enzyclopedia of indus-
Speer, K., Tewis, R., Montag, A.: 16-O-Methyl-cafestol trial chemistry. 5th Edition, Volume A7, p. 315, Ver-
a quality indicator for coffee. Fourteenth Interna- lag VCH, Weinheim, 1986
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July 14–19, 1991. ASIC 91, p. 237 R. Heiss) Springer, Berlin, 1988, p. 341
22 Spices, Salt and Vinegar

22.1 Spices 22.1.1 Composition

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

Table 22.1. Spices used in food preparation/processing

Number Common name Latin name Class/order Cultivation region


family (bot)

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

H.-D. Belitz · W. Grosch · P. Schieberle, Food Chemistry 971


© Springer 2009
972 22 Spices, Salt and Vinegar 22.1 Spices 973

Table 22.1. (continued)


Number Common name Latin name Class/order Cultivation region
family (bot)

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

a Fruits and leaves, b white mustard, c black mustard.

mono- and sesquiterpenes or phenols and phenol-


ethers. Examples of the latter two classes of com-
pounds are eugenol (I), carvacrol (II), thy- mol
(III), estragole (IV), anethole (V), safrole (VI) and
myristicin (VII):

(22.1)

Biosynthesis of cinnamaldehyde (VIII) and also phenylalanine (compare biosynthesis of other


of eugenol (I) an safrole (VI) originates from plant phenols in 18.1.2.5.1). The following
972 22 Spices, Salt and Vinegar 22.1 Spices 974

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.

Some aromatic hydrocarbons are probably


generated in spices by terpene oxidation. Ex-
amples are: 1-methyl-4-isopropenylbenzene (XI,
Formula 22.3) derived from p-men-tha-1,3,8-tri-
ene (X) and (+)-ar-curcumene (XIV) from zin-
giberene (XII) or β-sesquiphel-landrene (XIII)
[cf. Formula 22.4].
The formation of (+)-ar-curcumene from the
above-mentioned precursor was detected during
storage of ginger oil.
Another aromatic hydrocarbon present in signifi-
cant amounts in essential oils of some spices (Ta-
ble 22.3) is p-cymene (XV, Formula 22.3).

(22.3)
(22.2)

(22.4)
974 22 Spices, Salt and Vinegar 22.1 Spices 975

Table 22.3. Volatile compounds of spicesa


Spiceb Componentsc
Pepper (1) 1–16% α-Pinene (XXIX∗ ), 0.2–19% sabinene (XXV∗ ), 9–30% β-caryophyllene
(XLIX∗ ), 0–20% Δ3 -carene (XXXII∗ ), 16–24% limonene (IX∗ ), 5–14% β-pinene
(XXX∗ )
Vanilla (2) Vanillin (1.3–3.8%, dry matter), (R)(+)-trans-α-ionone, p-hydroxybenzylmethylether
(XVII)
Allspice (3) 50–80% Eugenol (I), 4–7% β-caryophyllene (XLIX∗ ), 3–28% methyleugenol,
1,8-cineole (XXIII∗ ), α-phellandrene (XI∗ )
Bay leaf (5) 50–70%, 1,8-Cineole (XXIII∗ ), α-pinene (XXIX∗ ), β-pinene (XXX∗ ),
α-phellandrene (XI∗ ), linalool (IV∗ )
3
Juniper berries (6) 36% α-Pinene (XXIX∗ ), 13% myrcene (I∗ ), β-pinene (XXX∗ ), -carene (XXXII∗ )
Aniseed (7) 80–95% (E)-anethole (V)
Caraway (8) 55% (S)(+)-Carvone (XXI∗ ), 44% limonene (IX∗ )
Coriander (9) (S)(+)- and (R)(-)-Linalool (IV∗ ), linalyl acetate, citrald , 2-alkenales C10 −C14
Dill (fruit, 10) 20–40% (S)(+)-Carvone (XXI∗ ), 30–50% (R)(+)-limonene (IX∗ )
Dill (herb, 10) 70% (S)(+)-Phellandrene (XI∗ ), 17% (3R,4S,8S)(+)-epoxy-p-menth-l-ene (XVIII),
myristicin (VII), (R)-limonene (IX)
Fenugreek (11) Linalool, 3-isobutyl-2-methoxypyrazine, 2-methoxy-3-isopropylpyrazine,
3-hydroxy-4,5-dimethyl-2(5H)-furanone (HD2F)
Nutmeg (13) 27% α-Pinene (XXIX∗ ), 21% β-pinene (XXX∗ ), 15% sabinene (XXV∗ ), 9% limon-
ene (IX∗ ), 0.1–3.3% safrole (VI), 0.5–14% myristicin (VII), 1.5–4.2% 1,8-cineole
(XXII∗ )2
Cardamom (14) 20–40%, 1,8-Cineole (XXIII∗ ), 28–34% α-terpinyl acetate, 2–14% limonene (IX∗ ),
3–5% sabinene (XXV∗ )
Clove (15) 73–85% Eugenol (I), 7−12% β-caryophyllene (XLIX∗ ), 1.5–11% eugenol acetate
Saffron (16) 47% Safranal (XIV), 14% 2,6,6-trimethyl-4-hydroxy-l-cyclohexen-l-formaldehyde
(XXIII)
Ginger (18) 30% (−)-Zingiberene (XLII∗ ), 10–15% β-bisabolene (XLI∗ ), 15–20%
(−)-sesquiphellandrene (XLIII∗ ), (+)-ar-curcumene (XIV), citralc , citronellyl
acetate
Tumeric (19) 30% Turmerone (XVIa ), 25% ar-turmerone (XVIb), 25% zingiberene (XLII∗ )
Cinnamon (20) 50–80% Cinnamaldehyde (VIII), 10% eugenol (I), 0–11% safrole (VI), 10–15%
linalool (IV∗ ), camphor (XXXIII∗ )
Parsley (23) p-Mentha-1,3,8-triene (X), myristicin (VII), 2-sec-butyl-3-methoxypyrazine,
2-isopropyl-3-methoxypyrazine, (Z)-6-decenal, (E,E)-2,4-decadienal, myrcene (I∗ )
Marjoram (26) 3–18% cis-Sabinenehydrate (XXVII∗ ), 1–7% trans-sabinenehydrate,
16–36% 1-terpinen-4-ol
Origano (27) 60% Carvacrol (II), thymol (III)
Rosemary (28) 1,8-Cineole (XXIII∗ ), camphor (XXXIII∗ ), β-pinene (XXX∗ ), camphene (XXXI∗ )
Sage (29) 1,8-Cineole (XXIII∗ ), camphor (XXXIII∗ ), thujone (XXVI∗ )
Thyme (31) Thymol (III), p-cymene (XV), carvacrol (II), linalool (IV∗ )
a With the exception of vanillin and dill (herb), the quantitative values refer to the composition of the essential
oil.
b The number in brackets refers to Table 22.1.
c Roman numerals with an asterisk refer to the chemical structures of the terpenes presented in Table 5.33.

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

tion. These include aniseed with (E)-anethole,


caraway with (S)-carvone, clove with eugenol
and cinnamon with cinnamalde-hyde (cf. Ta-
ble 22.3). In the case of the following spice plants,
further details about the important aroma
substances are known.

22.1.1.2.1 Pepper

Black and white pepper are available commer-


cially. Black pepper is harvested before it is fully
ripe and then dried. After removal of the flesh, the
seed of the ripe fruit gives white pepper, which
has a milder aroma.
In the concentration range of 1 to 2 mg/kg (−)-
rotundone (cf. 5.3.2.4) is the key odorant of black
and white pepper. Further important odorants of
black pepper are given in Table 22.4. White pep-
per contains the same typical aroma substances,
but usually in lower concentrations.
The aroma of ground pepper is not stable due to
losses of important aroma substances, the extent
of which is shown in Fig. 22.1.

Table 22.4. Odorants in black peppera


No. Compound Odor Concen-
threshold tration
(mg/kg)b (mg/kg) Fig. 22.1. Storage of ground black pepper at room tem-

perature – changes in the concentrations of odorants.


(a) (•−•) 3-methylbutanal, (◦−◦) α-pinene, ( − ) myrcene,
1 Methylpropanal 0.056 1.03 (♦−♦) α-phellandrene (b) ( − ) limonene, ( − ) 1,8-
2 2-Methylbutanal 0.053 1.99 cineol, ( − ) linalool
3 3-Methylbutanal 0.032 4.18
4a (−)-α-Pinene 3.4 2070
4b (+)-α-Pinene 2.1 486 Musty/mouldy aroma defects in black pepper
5a (−)-Sabinene 50 4470 are caused by a mixture of 2,3-diethyl-5-methyl-
5b (+)-Sabinene 6.3 285
6a (−)-β-Pinene 2.9 3950
pyrazine and 3-isopropyl-2-methoxy-pyrazine.
6b (+)-β-Pinene 2.1 298 Some samples of white pepper contain up to
7 Myrcene 1.9 870 2.5 mg/kg of skatole (odor threshold on starch:
8a (R)-α-Phellandrene 1.4 227 0.23 µg/kg), which together with 3- and 4-
8b (S)-α-Phellandrene 1.1 1390 methylphenol can cause a fecal aroma defect.
9a (S)-Limonene 2.8 4000 This aroma defect arises during fermentation
9b (R)-Limonene 1.8 3280 (degradation of amino acids, e. g., trypto-
10 1,8-Cineol 0.084 22.4 phan → 3-methylindole), which is carried out to
11 (±)-Linalool 0.069 231 remove the flesh. On longer storage, this defect
12 Butyric acid 0.10 1.28
13 2-/3-Methylbutyric acid 4.27
becomes more noticeable because intensive aroma
substances, which disguise it in fresh white
pepper, volatilize.
a Origin: India.
b Odor threshold on starch.
976 22 Spices, Salt and Vinegar 22.1 Spices 977

22.1.1.2.2 Vanilla The most important aroma substance in dill fruit


is (S)-carvone, which smells of caraway. In fact,
In the capsular fruit of vanilla, incorrectly called dill seeds were used as a substitute for caraway in
vanilla bean, 170 volatile compounds have been the past.
identified. However, the only fact that is certain
is that apart from the main aroma substance
vanillin, which is released from the glucoside on 22.1.1.2.4 Fenugreek
fermentation of the fruits, and (R)(+)-trans-α-
ionone, the p-hydroxybenzyl-methylether (XVII) The most important odorants of seasoning
contributes to the aroma since its concentration (cf. 12.7.3.5) is 3-hydroxy-4,5-dimethyl-2(5H)-
(115–187 mg/kg) greatly exceeds the odor furanone (HD2F, XXI in Formula 22.6), 95% of
threshold (0.1 mg/kg, water). A mixture of 99% which is present in the S form. This compound
of sugar and 1% of ground vanilla is sold as is also the outstanding odorant of fenugreek.
vanilla sugar and a mixture of 98% of sugar and Correspondingly, the seeds or the seed extract
2% of vanillin is sold as vanillin sugar. serves as the starting material for the production
of seasoning. Other odorants are 3-amino-4,5-
dimethyl-3,4-dihydro-2(5H)-furanone (XX in
22.1.1.2.3 Dill Formula 22.6), 1-octen-3-one, linalool and
eugenol.
AEDA and sensory investigations show that The concentration of HD2F varies in fenugreek
(S)-α-phellandrene in combination with (3S,3aS, between 3 and 12 mg/kg. However, this aroma
7aR)-3,6-dimethyl-2,3,3a,4,5,7a-hexahy-droben- substance is absent in Trigonella varieties.
zo[b]furan (XVIII, dill ether, cf. Formula 22.5) If an extract of fenugreek is heated (100 ◦ C,
produce the aroma of dill. Both compounds 60 min) at pH 2.4, there is a ca. 10 fold in-
are not stable and are largely lost on drying crease in the HD2F concentration. Under these
(Table 22.5). conditions, the precursor (2S,3R,4S)-4-hydroxy-

(22.5)

(22.6)
976 22 Spices, Salt and Vinegar 22.1 Spices 978

Table 22.5. Changes in aroma substances in the drying of dill (leaves)


Dried (air) Freeze dried
Fresh 25 ◦ C/4 h 50 ◦ C/4 h −25 ◦C/59 h −25 ◦ C/65 h

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.

22.1.1.2.6 Mustard, Horseradish 22.1.1.2.8 Basil

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

Table 22.6. The most important glucosinolates of mustard and horseradish

R Name Occurrence

Sinalbin Mustard

Sinigrin Mustard, horseradish

Gluconasturtiin Horseradish

Table 22.7. Concentrations of odorants in fresh and dried basil


Compound Concentrationa
Fresh Freeze-dried Dried at 60 ◦ C

(Z)-3-Hexenal 124 0.5 <0.01


1,8-Cineol 640 112 610
4-Mercapto-4-methylpentan-2-one 0.10 0.006 <0.01
Linalool 602 33 1210
4-Allyl-1,2-dimethoxybenzene 4950 1600 9540
Eugenol 890 214 391
3a,4,5,7a-Tetrahydro-3,6-dimethyl- 0.034 0.015 n.a.
benzofuran-2(3)-one (Winelactone)b
Methylcinnamate 25 n.a. n.a.
Estragol 12 n.a. n.a.
α-Pineol 18 14.2 11.9
Decanal 0.39 n.a. n.a.
a In mg/kg solids.
b cf. 5.2.5.
n.a: not analyzed.
like/spicy notes. The compounds given in note to become undesirably evident. The inten-
Table 22.7 produce the aroma, which has been sity of the pepper-like/spicy note also greatly
reproduced by a successful simulation. Omission decreases on drying.
experiments (cf. 5.2.7) show that eugenol,
(Z)-3-hexenal, α-pinene, 4-mercapto-4-methyl-
pentan-2-one, linalool and 1,8-cineol make the 22.1.1.2.9 Parsley
largest contributions to the aroma.
Drying damages the aroma considerably. The most important odorants of parsley leaves
(Z)-Hexenal and 4-mercapto-4-methylpentan- are listed in Table 22.8. Sensory evaluations
2-one are still detectable in freeze-dried basil have shown that p-mentha-1,3,8-triene (X in For-
(Table 22.7) and the green/fresh note is still mula 22.3) and myrcene contribute to the charac-
perceptible. This note is absent in an air-dried teristic aroma. (Z)-6-Decenal and (Z)-3-hexenal
sample, and the increase in linalool (Table 22.7), are responsible for the green notes. Myristicin,
possibly through the enzymatic hydrolysis of the 2-sec-butyl-3-methoxypyrazine, (E,E)-2,4-deca
corresponding glycosides, causes the flowery dienal, methanethiol and β-phellandrene also
978 22 Spices, Salt and Vinegar 22.1 Spices 980

Table 22.8. Concentrations of potent odorants in fresh and dried parsleya


Compound Concentrationb
Fresh Driedc
Cultivar Id Cultivar IId Cultivar IIe
Methanthiol 1.2 0.972 0.067
Myrcene 83.6 133.8 135
2-Methoxy-3-isopropylpyrazine 0.007 0.01 n.a.
2-sec-Butyl-3-methoxypyrazine 0.036 0.056 0.085
Myristicin 269 991 2770
1-Octen-3-one 0.014 0.047 0.010
p-Mentha-1,3,8-triene 1829 313 1026
(Z)-3-Hexenal 0.93 1.378 0.139
(Z)-3-Hexenylacetate 0.763 0.328 n.a.
(Z)-1,5-Octadien-3-one 0.005 0.005 <0.001
(E,E)-2,4-Decadienal 4.9 4.7 0.27
(Z)-6-Decenal 27.4 16.5 2.75
Linalool 3.2 1.6 0.42
β-Phellandrene 949 1026 200
2-Methylbutanal n.a. n.a. 2.0
3-Methylbutanal n.a. n.a. 1.3
Methylpropanal n.a. n.a. 2.5
Dimethylsulfide n.a. n.a. 22.5
Methional n.a. n.a. 0.065
Acetaldehyde n.a. n.a. 8.0
Propanal n.a. n.a. 19.0
3-Methyl-2,4-nonandione n.a. n.a. 0.029
a
Only those aroma substances which showed high FD factors in dilution analyses were quantified.
b In mg/kg based on solids.
c Dried at 70 ◦ C (80 to 120 min), then stored for 3 months at −20 ◦ C in nitrogen.
d Cultivar I: Hamburger cut, cultivar II: “Mooskrause”.
e
The fresh and dried cultivar II are of different origin.

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

Piperinec Pepper (1) 1.0

Piperanine Pepper (1) 0.5

Piperylin Pepper (1) 0–1d

Gingerol Ginger (17) 0.8

Shogaol Ginger (17) 1.6


Capsaicin Capsicum (4; 7) 150–300d

Dihydro-
capsain

Capsicum (4; 7) like Capsaicin


Nordihydro- Capsicum (4; 7) 75% Capsaicin
caicin

a The numerals in brackets refer to Table 22.1.


b Reference: pungency of piperine = 1.
c The corresponding cis,trans-compound is devoid of pungent taste.
d Literature data are within the range of values presented.

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

spice constituents. Their concentrations are at the


upper limit in chillies and tobasco varieties and
at the lower limit in sweet varieties.

(22.9)

The high antioxidative activity of the two com-


pounds is probably based on the fact that they are
o-diphenols (cf. 3.7.3.2.1).
(22.7)

22.1.2 Products

22.1.2.1 Spice Powders


(22.8) Spices are marketed unground or as coarsely or
Investigations of the structure/effect relationship finely ground powders. The flavor is improved
show that the intensity of the pungency does when the spices are ground using a cryogenic
not change when 8-methyl-trans-6-nonenoic mill. After grinding the shelf life of the spices
acid in capsaicin is replaced by nonanoic acid is limited. Favorable storage conditions are
(9:0). However, it decreases when shorter, the absence of air, a relative humidity less
than 60% and a temperature less than 20 ◦ C.
e. g., 8:0 (75%), 7:0 (25%), 6:0 (5%), or longer
Crushed spices rapidly lose their aroma and
fatty acids, e. g., 10:0 (50%), 11:0 (25%), are
absorb aromas from other sources. Leaf and
introduced.
herb spices are dried before they are crushed.
The loss of aroma substances depends on the spice
and on the drying conditions (for examples, see
22.1.1.4 Pigments 22.1.1.2.3, 22.1.1.2.8 and 22.1.1.2.9). In
comparison with air-drying at a raised temper-
Paprika (red pepper) and curcuma pigments are ature, there are no changes in aroma caused by the
used as food colorants. Paprika pigments are Maillard reaction in freeze-drying. However,
carotenoids, with capsanthin as the main gentle drying leads to increased hydrolysis of
compound (cf. 3.8.4.1.2 and Fig. 3.47). Cur- chlorophylls and to dehydration of the phytol
cumin (cf. Formula 22.8) is the main pigment of released to phytadienes, e. g., to neophytadiene
curcuma, a tropical plant of the ginger family. (7,11,15-trimethyl-3-methylene-1-hexadecene):

22.1.1.5 Antioxidants

Extracts of several spices, particularly of sage and


rosemary, have the ability to prevent the autoxida-
tion of unsaturated triacylglycerols. Among the
most effective antioxidant constituents of both
spices, the cyclic diterpene diphenols, carnoso-
lic acid (XXXIII in formula 22.9) and carnosol
(XXXIV) have been identified. (22.10)
982 22 Spices, Salt and Vinegar

Contamination of spice powders with microor- 22.1.2.4.2 Mustard Paste


ganisms is often very high, hence the addition of
ground spices to food preparations may acceler- A dark yellow paste used as a pungent seasoning
ate microbial food spoilage. for food. It is made from finely ground, often de-
fatted mustard seeds, mixed into a slurry with wa-
ter, vinegar, salt, oil and some other spices (pep-
22.1.2.2 Spice Extracts or Concentrates per, clove, coriander, curcuma, ginger, paprika,
(Oleoresins) etc.) and ground repeatedly or refined. During
processing, lasting 1–4 h at a temperature not ex-

Spice extracts are being used in increasing ceeding 60 C, the mustard oil is released from
amounts in industrial-scale food preparation its glucoside, as outlined in 22.1.1.2.6. “Extra
strong” mustard is primarily made from dehulled
since they are easier to handle than spice powders
black mustard seed, while the “medium hot” or
and are free of microorganisms. The production
“hot” types are made from seeds with hull, using
of these extracts is outlined in 5.5.1.2. The flavor
varying proportions of black and white mustards.
quality depends on the solvent used and also on
the raw material.
22.1.2.4.3 Sambal
22.1.2.3 Blended Spices A spice preparation from Asia used for season-
ing rice dishes. Its base is Sambal oelek, which
Specially blended spices are offered commer- consists mainly of crushed or pulverized saltpre-
cially for some food preparations, such as liver served chili.
sausage which uses a spice blend consisting
of sweet marjoram, mace, nutmeg, cardamom,
ginger, pepper and a little cinnamon.
Smoked, saveloy sausage spice blend consists of 22.2 Salt (Cooking Salt)
coriander, ginger, mustard kernels, paprika and
pepper. Common spices for bread are aniseed, Common salt occupies a special position among
fennel and caraway. Gingerbread spice blend con- the spices. Salt is used in greater amounts than
sists of aniseed, clove, coriander, cardamom, all- all other spices to enhance the flavor and taste of
spice and cinnamon. food. Also, some foods are preserved when salted
with large amounts of NaCl (cf. 0.3.1).
Humans require a certain constant level of intake
22.1.2.4 Spice Preparations of sodium and chloride ions to maintain their vital
concentrations in plasma and extracellular fluids.
Spice preparations are obtained by the addition The daily requirement is about 5 g of NaCl; an
of spices and blended spices to other substances, excessive intake is detrimental to health.
such as salt, sugar, glutamate, yeast extract and The salty taste is stimulated by ions. In compar-
starch flour. ison with the sour taste (cf. 8.10), the cation and
the anion are significantly involved. The pure salt
taste is only produced by NaCl. In fact, the very
next chemical relative, KCl, has a sour/bitter af-
22.1.2.4.1 Curry Powder
tertaste.
A spice preparation containing a spice blend of
turmeric as the main ingredient and paprika, chili,
ginger, coriander, cardamom, clove, allspice and 22.2.1 Composition
cinnamon, mixed together with up to 10% legume
meal, starch and glucose, and with less than 5% Common (cooking or kitchen) salt is nearly
salt. entirely NaCl. Impurities are moisture (up to 3%)
22.3 Vinegar 983
and other salts, not exceeding 2.5% (magnesium used in industry or trade (raw materials, salt for
and calcium chloride; magnesium, calcium regeneration of ion-exchange resins, etc.).
and sodium sulfates). Salt also contains trace
elements.
22.2.4 Special Salt

22.2.2 Occurrence Iodized salt is produced as a preventive meas-


ure against goiter, a disease of the thyroid gland
Salt is abundant in sea water (2.7–3.7%) and in (cf. 17.1.2.9.3). It contains 5 mg/kg of sodium-,
various landlocked seas (7.9% in the Dead Sea; potassium- or calcium iodide.
15.1% in the Great Salt Lake in Utah) and also Nitrite salts are used for pickling and dry curing
in salt springs (Lueneburg, Reichenhall) and, of meat (cf. 12.6.2.4). They consist of common
above all, in salt beds formed in various geolog- salt and sodium nitrite (0.4–0.5%), with or with-
ical periods, e. g., the European Zechstein salt out additional potassium nitrate.
deposits.

22.2.5 Salt Substitutes


22.2.3 Production
Some human diseases make it necessary to avoid
In Germany salt is mainly mined as rock salt. It is excessive intake of sodium ions, so attempts have
selected, crushed and finely ground. Salt springs been made to eliminate the use of added salt as
are also an important source. Saturated brine is re- a spice or flavoring, without attempting to achieve
covered by tapping underground brine springs or completely salt-free nutrition. This “low salt” nu-
by dissolving the salt out of beds with freshwater. trition is actually only related to reduced sodium
For purification, magnesium is first eliminated as levels, hence a “low sodium” diet is a more rele-
the hydroxide with lime milk and then calcium is vant designation.
removed as calcium carbonate with soda. Gypsif- The compounds listed in Table 22.10 are used as
erous brine is treated with sodium sulfate contain- salt substitutes. Their blends are marketed as “diet
ing mother liquor from the evaporation process. salts”. Peptide hydrochlorides with a salty taste
Evaporative crystallization occurs in multistage are discussed in Section 1.3.3.
systems at 50–150 ◦ C. The salt is centrifuged and
dried. Salt obtained in such a manner is called
“boiling” salt.
In warm countries sea water is concentrated in 22.3 Vinegar
shallow flat basins by the sun, heat and wind until
it crystallizes (“solar salt”). Vinegar was known in old Oriental civilizations
The addition of 0.25–2.0% calcium or magne- and was used as a poor man’s drink and later
sium carbonate, calcium silicate, or silicic acid as a remedy in ancient Greece and Rome. Vine-
improves the flowability. Indeed, 20 ppm of gar is the most important single flavoring used to
potassium ferrocyanide prevents the formation of
lumps in the salt. The latter compound modifies
the crystallization process of NaCl during the Table 22.10. Substitutes for common salt
evaporation of salt spring water. In the pres-
Potassium, calcium and magnesium salts of adipic,
ence of potassium ferrocyanide, the salt builds succinic, glutamic, carbonic, lactic, hydrochloric,
dendrites, which have strongly reduced volume, tartaric and citric acids;
density and inclination to agglomerate. Monopotassium phosphate, adipic and glutamic
In 1975 the worldwide production of NaCl was acids and potassium sulfate;
162.2 ×106 t and 240 ×106 t in 2006. In 1974 only Choline salt of acetic, carbonic, lactic, hydrochloric,
5% of the NaCl produced in FR Germany was tartaric and citric acids;
used for consumption; the remainder, 95%, was Potassium salt of guanylic and inosinic acids
984 22 Spices, Salt and Vinegar

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

22.3.1.1 Microbiological Production Acetic acid is usually synthesized by catalytic


oxidation of acetaldehyde:
Acetobacter species are cultivated in aqueous cat.
ethanol solution or, to a lesser extent, in wine, CH3 CHO + 12O2 −−→ CH3 COOH (22.13)
fermented apple juice, malt mash or fermented
Acetaldehyde is obtained by the catalytic hydra-
whey. Ethanol, as shown in Fig. 22.2, is dehy-
tion of acetylene or by the catalytic dehydrogena-
drogenated stepwise to acetic acid; the resulting
tion of ethanol. Formic acid and formaldehyde
reduced form of the cosubstrate methoxatin
are by-products of acetic acid synthesis. They are
(PQQH2 ) is oxidized via the respiratory chain.
removed by distillation. Chemically pure acetic
Part of the energy formed by oxidation is acid is diluted with water to 60–80% by vol-
released as heat which has to be removed by ume to obtain the vinegar essence. The essence
cooling during the processing of vinegar. If is a strongly corrosive liquid and is sold with spe-
there is an insufficient supply of oxygen, the cial precautions. It is diluted further with water
microorganisms disproportionate a proportion of for production of food grade vinegar.
the acetaldehyde, the intermediate compound (cf.
Fig. 22.2) in this aerobic reaction pathway:
2CH3 CHO −→ CH3 COOH + CH3 CH2 OH
(22.12) 22.3.2 Composition

There are 5–15.5 g acetic acid in 100 g of vine-


gar. The blending (or adulteration) of fermented
vinegar with synthetic acid can be detected
by mass spectrometric determination of the
13 C/12 C-isotope ratio (cf. 18.4.3); fermented

vinegar has 5‰ more 13 C isotope than acetic


acid synthesized petrochemically. In addition
fermented vinegar can be distinguished from
synthetic vinegar by analyzing the accompanying
compounds. With this method fermented vinegars
of different origin can also be distinguished from
each other; e. g. spirit vinegar (fermented from
aqueous ethanol) from wine, apple, malt and/or
whey vinegar. The fermented vinegars contain
metabolic by-products of Acetobacter strains,
Fig. 22.2. Oxidation of ethanol to acetic acid by Aceto- such as amino acids, 2,3-butylene glycol and
bacter species (according to Rehm, 1980)
22.4 References 985
acetyl methyl carbinol, in addition to substances Maga, J.A.: Capsicum. Crit. Rev. Food Sci. Nutr.
derived from the raw materials used in vinegar 6, 177 (1975)
production. Masanetz, C., Grosch, W.: Hay-like off-flavour of dry
parsley. Z. Lebensm. Unters. Forsch. 206, 114 (1998)
Masanetz, C., Grosch, W.: Key odorants of pars-
22.4 References ley leaves (Petroselinum crispum [Mill.] Nym.
ssp. crispum) by odour activity values. Flavour
Blank, I. Lin, J., Devaud, S., Fumeaux, R., Fay, L. Fragrance J. 13, 115 (1998)
B.: The principal flavor components of fenugreek Nishimura, O.: Identification of the characteristic
(Trigonella foenum-graecum L.) ACS Symposium odorants in fresh rhizomes of ginger (Zingiber
Ser. 660, 12 (1996) officinale Roscoe) using aroma extract dilution
Boelens, M.H., Richard, H.M.J.: Spieces and condi- analysis and modified multidimensional gas
ments I and II. In: Volatile compounds in foods and chromatography-mass spectrometry. J. Agric. Food
beverages (Ed.: Maarse, H.), Marcel Dekker, Inc.: Chem. 43, 2941 (1995)
New York. 1991 Rehm, H.-J.: Industrielle Mikrobiologie. 2nd. edn.,
Chadwallader, K.R., Baek, H.H., Cai, M.: Characteriza- Springer-Verlag: Berlin. 1980
tion of saffron flavor by aroma extract dilution ana-
Risch, S.J., Ho, C.-T.: Spices. Flavor chemistry and
lysis. ACS Symposium Ser. 660, 66 (1996)
antioxidant properties. ACS Symposium Ser. 660,
Ebner, H., Follmann, H.: Acetic acid. In: Biotechnology
American Chemical Society, Washington DC, 1996
(Eds.: Rehm, H.-J., Reed, G.), Vol. 3, p. 387, Verlag
Chemie: Weinheim. 1983 Salzer, U.-J.: The analysis of essential oils and extracts
(oleoresins) from seasonings – a critical review. Crit.
Gerhardt, U.: Gewürze in der Lebensmittelindustrie.
Rev. Food. Sci. Nutr. 9, 345 (1977)
Eigenschaften, Technologien, Verwendung. B. Behr’s
Verlag: Hamburg. 1990 Sampathu, S.R., Shivashankar, S., Lewis, Y.S.: Saf- fron
Gottschalk, G.: Bacterial Metabolism. 2nd edn., (Crocus sativus Linn.) – Cultivation, process- ing,
Springer-Verlag: Heidelberg. 1985 chemistry and standardization. Crit. Rev. Food Sci.
Nutr. 20, 123 (1984)
Guth, H., Murgoci, A.-M.: Identification of the key
odorants of basil (Ocimum basilicum L.) – Effect of Schmid, E.R., Fogy, I., Schwarz, P.: Beitrag zur
different drying procedures on the overall flavour. In: Unterscheidung von Gärungsessig und synthetis-
Flavour Perception, Aroma Evaluation (Eds. H.-P. chem Säureessig durch die massenspektrometrische
Kruse, M. Rothe) Universität Potsdam, 1997, p. 232 Bestimmung des 13 C/12 C-Isotopenverhältnisses. Z.
Hall, G., Siewek, F., Gerhart, U.: Handbuch Aromen Lebensm. Unters. Forsch. 166, 89 (1978)
und Gewürze, Behr’s Verlag, Hamburg, 1999 Siewek, F.: Exotische Gewürze. Herkunft, Verwen-
Huopalahti, R., Kesälahti, E., Linko, R.: Effect of hot dung, Inhaltsstoffe. Birkhäuser Verlag: Basel. 1990
air and freeze drying on the volatile compounds of Steinhaus, M., Schieberle, P.: Role of the fermenta-
dill (Anethum graveolens L.) herb. J. Agric. Sci. Fin- tion process in off-odorant formation in white pep-
land 57, 133 (1985) per: on-site trial in Thailand. J. Agric. Food Chem.
Jagella, T., Grosch, W.: Flavour and off-flavour com- 53, 6056 (2005)
pounds of black and white pepper. Eur. Food Res. Wijesekera, R.O.B.: The chemistry and technology of
Technol. 209, 27 (1999) cinnamon. Crit. Rev. Food Sci. Nutr. 10, 1 (1978)
23 Drinking Water, Mineral and Table Water

23.1 Drinking Water as MnO2 if the pH is higher than 8.5. Biologi-


cal processes have also been developed for de-
Drinking water should be clear, cool, colorless ferrization and demanganization. Free carbonic
and odorless, free from pathogens (low in mi- acid must be removed because it attacks pipes.
croorganisms), perfect with regard to taste, cause The deacidification process applied depends on
no materials corrosion, and contain soluble sub- the hardness of the water and on the concentra-
stances only in narrow limits and minerals nor- tion of free carbonic acid. The usual process in-
mally in concentrations of less than 1 g/l. In in- volves aeration and filtration through carbonate
dividual countries, criteria have been defined by rock (e. g., marble or magnesite).
law for the quality of drinking water, especially The disinfection of water is mostly achieved
limiting values for microorganisms and contamin- by chlorination or ozonation. At a pH of 6–8,
ation. As an example, limiting values stipulated the chlorine gas passed into the water forms
in the German decree on drinking water are practically only HClO and ClO− which, together
presented in Table 23.1. with the dissolved Cl2 , are expressed as free
Drinking water is recovered from springs, chlorine. In the case of superchlorination for
groundwater, and surface water. In sparsely popu- the killing of very resistant microorganisms,
lated areas, springs and brooks provide water the excess chlorine (>0.1 mg/l of free chlo-
that can be used without further pretreatment. rine) must be withdrawn with the help of SO2 ,
Frequently, however, the water available does not Na2 SO3 , Na2 S2 O3 and filtration through calcium
fulfil the requirements and must be laboriously
sulfite or coal. Disinfection with ozone has
purified.
the advantage that due to its decomposition
In dry areas, drinking water is obtained by desalt- into oxygen, no chemicals remain in the water.
ing brackish or sea water. The usual processes ap- Interfering odor- and taste-active substances
plied are reverse osmosis with the use of semiper-
are eliminated by filtration through activated
meable membranes for slightly saline brackish
carbon.
water and multistage evaporation, mainly as flash
Overly high conventrations of nitrate (limiting
evaporation, for sea water.
value in Table 23.1) can be reduced by bacterial
denitrification, ion exchange, or reverse osmosis.
The fluoridation of drinking water is discussed
23.1.1 Treatment in 7.3.2.10.

To remove suspended particles, the water is first


filtered through gravel and sand layers of different
grain size. Humic acids, which may color water 23.1.2 Hardness
yellow to brown, are flocculated with aluminium
The total water hardness refers to the total con-
sulfate. After clarification, the quality of the water
centration of alkaline earths calcium and magne-
is improved still further, if required, by the appli-
sium in mmol/l. The concentrations of strontium
cation of the following processes.
and barium, which are usually very low, are not
Water should not contain more than 0.2 mg/l of
considered. The following is valid for conversion
iron, which is present as the bicarbonate, and to German degress of hardness (◦ d): 1 mmol/l
0.05 mg/l of manganese (Table 23.1). The iron hardness = 5.61 ◦ d. Factors for conversion to the
can be eliminated as iron (III) hydroxide by aera- degree of hardness of other countries are given in
tion. In this process, manganese also precipitates Table 23.2.

H.-D. Belitz · W. Grosch · P. Schieberle, Food Chemistry 986


© Springer 2009
23.1 Drinking Water 987
Table 23.1. Chemical and physical analysis of drinking Table 23.2. Conversion factors for degrees of hardness
water
Value Alkaline
Parameter Limiting valuea earth metal
ions (mmol/l)
General values to be measured
Temperature 25 ◦ C Hardnessa 1.00
pH Value 6.5–9.5 1 German degree of hardness (◦d) 0.18
Electrical conductivity at 25 ◦C 2000 µS · cm−1 1 English degree of hardness (◦e) 0.14
Oxidizabilityb 5 mg O2 /l 1 French degree of hardness (◦f) 0.10
Hardness –c 1 USA degree of hardness (◦US)b 0.01
Individual Constituents mg/l a Hardness is now expressed as the concentration of the
Sodium 150 amount of substance (mmol/l). The following corres-
Potassium 12 pond: 1 mg/l Ca2⊕ = 0.025 mmol/l; 1 mg/l Mg2⊕ =
Calcium –c 0.041 mmol/l.
Magnesium 50 b 1◦US = 1 ppm CaCO .
3
Iron 0.2
Manganese 0.05
Table 23.3. Classification in steps of hardness
Aluminium 0.2
Ammonium 0.5 Step Range of Degree Characteristics
Silver 0.01 hardness of hardness
Sulfate 240 (mmol/l) (◦d)
Arsenic 0.04
Lead 0.04 1 <1.3 <7 Soft
Cadmium 0.005 2 1.3–2.5 7–14 Medium-hard
Chromium 0.05 3 2.5–3.8 14–21 Hard
Nickel 0.05 4 >3.8 >21 Very hard
Mercury 0.001
Cyanide 0.05
Fluoride 1.5
On heating, the hydrogen carbonates dissolved
Nitrate 50
Nitrite 0.1
in water are converted to carbonates. On boil-
Polycyclic aromatic 0.0002 ing, a part of the calcium salts precipitates out as
hydrocarbons, slightly soluble CaCO3 . This part of the hardness
calculated as carbon is called carbonate hardness.

Chlorine-containing solvents, 0.025


sum of 1,1,1-trichloroethane,
trichloroethylene, tetrachloro-
ethylene, dichloromethane 23.1.3 Analysis
Carbon tetrachloride 0.003
Pesticides, biphenyls, terphenyls 0.0001d The extent and frequency of the analysis of drink-
Surfactants 0.2 ing water are regulated by law in many countries.

a The limiting values have been taken from the


Apart from monitoring the hygienic state of the
decree on drinking water, Dec. 5, 1990 (BGBL. I.water resources and of the treated drinking water,
p. 2612)/Jan. 23, 1991 (BGBL. I. p. 277). maintenance of limiting values is controlled. The
b Organic substances are detected on the whole by data given in Table 23.1 show that extensive ana-
oxidation, e. g., with permanganate. lysis of drinking water is a very laborious process.
c No limiting value required.
d Per individual substance.
The question of whether the drinking water sup-
ply is possibly endangered by drug residues has
risen recently. In spot checks, the concentrations
of persistent drugs, e. g., chlofibrinic acid, de-
tected in drinking water have been far below the
The assessment of water involves an evaluation in human therapeutic activity threshold. From a hy-
accordance with the steps of hardness presented gienic viewpoint, however, this situation is not
in Table 23.3. tolerable in the long run.
988 23 Drinking Water, Mineral and Table Water

Table 23.4. Classification of mineral water


Description Requirement

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

23.2 Mineral Water 23.3 Table Water


Mineral water comes from a hygienically fault- Table water is made from mineral water, drink-
less spring that is protected from contamination. ing water, and/or sea water by using NaCl, CaCl2 ,
It has a nutritional and physiological effect due to Na2 CO3 , NaHCO3 , CaCO3 , MgCO3 , and CO2. If
its mineral content. it contains at least 570 mg/l of NaHCO3 and car-
In many countries, the recovery and composition bon dioxide, it can be called soda water. Selters is
of mineral water are controlled by the state and a soda water that comes from Selters on the Lahn.
only a few processes for quality improvement are
permitted. These are: separation of iron and sul-
fur compounds, complete or partial removal of
free carbonic acid, and addition of carbon diox- 23.4 References
ide. Mineral water is bottled directly at the place
of the spring. With regard to the heavy metal con- Heberer,T.,Stan,H.-J.: Arzneimittelrückstände im aqua-
tent and possible contamination, limiting values tischen System. Wasser & Boden 50(4), 20 (1998)
have been stipulated by law. The classification of Höll, K.: Wasser, Walter de Gruyter, Berlin, 1979
mineral water is presented in Table 23.4. Quentin, K.-E.: Trinkwasser. Springer-Verlag: Berlin.
1988
In Germany, water used for therapeutic purposes
Weingärtner, H. et al.: Water. In: Ullmann’s encyclope-
(medicinal waters), because of its chemical dia of industrial chemistry. 5th Edition, Volume A28,
composition, is subject to the law governing the p. 1, VCH Verlag, Weinheim, 1996
manufacture and prescription of drugs.