PREVENTIVE MEDICINE 21, 334-350 (1992)

Green Tea Composition, Consumption, and

Polyphenol Chemistry’
HAROLD N. GRAHAM, PH.D.’
256 Broad Avenue, Englewood, New Jersey 07631

Tea is grown in about 30 countries but is consumed worldwide, although at greatly varying
levels. It is the most widely consumed beverage aside from water with a per capita world-
wide consumption of approximately 0.12 liter per year. Tea is manufactured in three basic
forms. Green tea is prepared in such a way as to preclude the oxidation of green leaf
polyphenols. During black tea production oxidation is promoted so that most of these
substances are oxidized. Oolong tea is a partially oxidized product. Of the approximately 2.5
million metric tons of dried tea manufactured, only 20% is green tea and less than 2% is
oolong tea. Green tea is consumed primarily in China, Japan, and a few countries in North
Africa and the Middle East. Fresh tea leaf is unusually rich in the flavanol group of poly-
phenols known as catechins which may constitute up to 30% of the dry leaf weight. Other
polyphenols include flavonols and their glycosides, and depsides such as chlorogenic
acid, coumarylquinic acid, and one unique to tea, theogallin (3-galloylquinic acid). Caf-
feine is present at an average level of 3% along with very small amounts of the other
common methylxanthines, theobromine and theophylline. The amino acid theanine (5-N-
ethylglutamine) is also unique to tea. Tea accumulates aluminum and manganese. In addi-
tion to the normal complement of plant cell enzymes, tea leaf contains an active polyphenol
oxidase which catalyzes the aerobic oxidation of the catechins when the leaf cell structure
is disrupted during black tea manufacture. The various quinones produced by the enzymatic
oxidations undergo condensation reactions which result in a series of compounds, including
bisflavanols, theaflavins, epitheaflavic acids, and thearubigens, which impart the charac-
teristic taste and color properties of black tea. Most of these compounds readily form
complexes with caffeine. There is no tannic acid in tea. Thearubigens constitute the largest
mass of the extractable matter in black tea but their composition is not well known. Proan-
thocyanidins make up part of the complex. Tea peroxidase may be involved in their gener-
ation. The catechin quinones also initiate the formation of many of the hundreds of volatile
compounds found in the black tea aroma fraction. Green tea composition is very similar to
that of the fresh leaf except for a few enzymatically catalyzed changes which occur ex-
tremely rapidly following plucking. New volatile substances are produced during the drying
stage. Oolong tea is intermediate in composition between green and black teas. 0 1992
Academic Press. Inc.

INTRODUCTION
Useful consideration of the physiological and pharmacological effects of tea
requires background information concerning production, leaf composition, avail-
ability of the various types of tea, and, most importantly, the chemical changes
that take place during the manufacture of the various commercial products. Con-
sumption patterns of the different types of tea beverages should also be noted, As

i Presented at the First International Symposium on the Physiological and Pharmacological Effects
of Camellia sinensis (Tea), March 4-6, 1991, American Health Foundation, New York City. Jointly
sponsored by The Tea Council and the National Tea Association.
’ Formerly of the Thomas J. Lipton Co.

334
0091-7435192 $5.00
Copyright 0 1992 by Academic Press, Inc.
All tights of reproduction in any form reserved.
 PROCEEDINGS: PHYSIOLOGICAL AND PHARMACOLOGICAL EFFECTS OF TEA 335

polyphenols are the most significant group of tea components, their complex
chemistry should be understood in some detail. This article is intended to provide
such information.

TEA PRODUCTION
Tea is the plant, leaf, or beverage originating from what is now considered a
single species--Camellia sinensis (L.) 0. Kuntze. Two major varieties are rec-
ognized-sinensis and assamica. In the field the obvious difference observed
between the major varieties is leaf size. Var. sinensis is small-leaved (5-12 cm).
Var. assamica may have leaves up to 20 cm in length.
Much hybridization has occurred. Breeding, vegetative propagation, and selec-
tion have resulted in the emergence of thousands of lines with varying properties,
including compositional differences. In general, the China teas (var. sinensis) are
more cold resistant and therefore suited for cultivation in the more temperate
climates.
The tea plant originated in Southeast Asia and is presently cultivated in over 30
countries. The principal tea producing countries of the world are listed in Table 1
(1).
The term green tea refers to the product manufactured from fresh leaf while
preventing oxidation of the polyphenolic components. These are the substances of
the greatest importance to this symposium.
Black tea manufacture is carried out so as to ensure a high degree of enzymat-
ically catalyzed aerobic oxidation of the leaf polyphenols followed by a series of
chemical condensations. Oolong tea is partially oxidized.
World production of tea has increased steadily with only a few minor reversals.
Increased production is largely due to improved yields obtained by the implemen-
tation of modern horticultural practices and by replacement of older plants with
recently developed high yielding varieties. The establishment of these new clones
by careful plant selection or even by tissue culture also allows for the incorpora-
tion of other desirable properties that could result in modified compositions de-
signed to meet pharmacological as well as conventional crop needs. Production of
tea by major types is shown in Table 2 (1).
Green tea production is carried out in relatively few countries as shown in Table
3 (1). Oolong tea production is confined to China (approx. 50,000 tons) and Tai-
wan (approx. 10,000 tons).

TABLE 1
PRINCIPAL TEA PRODUCING COUNTRIES (1990)

India 715 USSR 110

China 540 Japan 90
Sri Lanka 230 Iran 55
Kenya 200 Bangladesh 45
Indonesia 150 Malawi 40
Turkey 130 Vietnam 40
Argentina 35

Note. Total dry wt of ten measured in thousands of tons.

336 HAROLD N. GRAHAM

TABLE 2
WORLD TEA PRODUCTION BY TYPE (1990)

Black 1940
Green 515
Oolong 60
Total 251s

Note. Total dry wt of tea measured in thousands of tons.

Aside from water, tea is the most consumed beverage in the world. Assuming
a 100: 1 ratio of water to tea for beverage preparation, world tea consumption must
be about 0.12 liter per day per capita. Consumption is far from uniform. Large
segments of the world’s population drink virtually no tea. Representative data
showing the disparate consumption patterns are shown in Table 4 (1). Green tea
is consumed primarily in Japan, China, and some parts of the Middle East and
North Africa.
As is well known, not only does tea consumption vary from country to country,
but also there is enormous variation in any given population. This ranges from no
tea at all to as many as 20 or more cups per day. This high level of consumption
is tolerable physiologically since the total caffeine content of 20 cups is less
than 1 g.
TEA COMPOSITION
Tea composition varies with climate, season, horticultural practices, variety,
and the age of the leaf, i.e., the position of the leaf on the harvested shoot. Data
shown in Table 5 reflect a representative tea but variations may be considerable
(2).
The polyphenols constitute the most interesting group of tea leaf components,
especially the catechin group of the flavanols. Six of these occur in considerable
quantities in fresh leaf. Simple catechin structures are shown in Fig. 1. Two
configurations are possible but most of the catechin mass is in the so-called “epi-”
form. When three hydroxy groups are present on the “B” ring the substances are
known as gallocatechins as shown in Fig. 2. Another variation results from the
esterification of the OH group on the pyran ring with gallic acid. The catechin
gallates are illustrated in Fig. 3. The principal catechins are present at high con-
centrations in young tea leaf as shown in Table 6 (2).
Catechin concentration is highly dependent on leaf age. The leaf bud and the

TABLE 3
GREEN TEA PRODUCTION (1990)

China 310 Taiwan 8

Japan 90 India 8
Indonesia 40 Sri Lanka 1
Vietnam 30 Bangledesh 1
USSR 20

Note. Total dry wt of tea measured in thousands of tons.

 PROCEEDINGS: PHYSIOLOGICAL AND PHARMACOLOGICAL EFFECTS OF TEA 337
TABLE 4
TEA CONSUMPTION IN SELECTED COUNTRIES

Ireland 3.04 Chile 0.86

United Kingdom 2.81 Canada 0.55
USSR 0.87 United States 0.34
Germany 0.18 Mexico ‘co.01
France 0.18 New Zealand 1.59
Italy 0.06 Australia 1.12
Turkey 2.19 Tunisia 1.43
Japan 0.96 Egypt 1.33
Pakistan 0.93 Morocco 1.11
India 0.58 South Africa 0.56
China 0.30 Nigeria 0.02
Thailand 0.01

Note. Consumption of tea measured in kilograms per capita (average for years 1987-1989).

first leaf are richest in epigallocatechin gallate (3). Catechin levels also vary
greatly with varietal differences. Green tea is often manufactured from tea leaf
with somewhat lower catechin levels than leaf used for black tea manufacture.
Catechins are the predominant group of substances in green tea and they are the
most significant of all tea components. As will be shown, they play the most
important role in the series of oxidations and condensations which occur during
the production of black tea.
The catechins are colorless, astringent, water soluble compounds. They are
readily oxidizable, although their oxidation potentials vary. This property has
been exploited through their use as food antioxidants. They retard rancidity in fats
and oils by quenching free radical peroxide activity brought about by aerobic
oxidation. Based on the concentrations required for 50% inhibition of oxidation,
the inhibitory effect of some tea leaf catechins on the aerobic oxidation of linoleic
acid is similar to that of BHA (4).
In biological systems oxygen is an important acceptor of electrons, leading to
the formation of active oxygen and hydroxyl free radicals. Scavenging effects of
green tea extracts and green tea polyphenol fractions are superior to those of
ascorbic acid (vitamin C) and tocopherol (vitamin E) with respect to some active
oxygen radicals but are less pronounced with hydroxyl free radicals (5). Effects
depend on the particular free radical system under investigation. The gallocate-

TABLE 5
COMPOSITION OF FRESH GREEN TEA LEAF

Polyphenols 36 Carbohydrates 25
Methyl xanthines 3.5 Protein 15
Amino acids 4 Lignin 6.5
Organic acids 1.5 Lipids 2
Carotenoids co. 1 Chlorophyll, etc. 0.5
Volatiles ‘co. 1 Ash 5

Note. Composition measured in % dry wt.

338 HAROLD N. GRAHAM

OH OH
OH

HO HO

(+) Catechin (-) Epicatechin

FIGURE 1

chins and the catechin gallates exhibit the strongest radical quenching properties
(6).
In recent years, with the development of more sophisticated separation and
identification techniques, other catechins and related products have been identi-
fied in fresh tea leaf but little quantitative data have been reported (7). These
include a catechin digallate and some methylated catechins. A novel group of
compounds called chalcan-flavans has also been identified. These are bimolecular
combinations of a catechin attached to a chalcone derivative.
Bisflavanols (also known as theasinensins) occur in green leaf (7). These are
dimeric gallocatechins linked by C-C bonds at the “B” rings as indicated in Fig.
4. They will be discussed further under black tea because of their additional
formation during its production.
Dimeric proanthocyanidins are also present in fresh tea leaf (7). These may also
be considered condensation products of the catechins but linked by C-C bonds
between an “A” ring and a pyran ring. They will be discussed further under black
tea. The monomeric anthocyanidins, cyanidin and delphinidin, are the flavone
equivalents of epicatechin and epigallocatechin, respectively (Fig. 5).
Flavonols occur both in the free state and as glycosides of glucose, rhamnose,
and possibly other sugars (8). Their structures are analagous to those of the
flavanols but represent a different state of oxidation. The flavonols also play a part
in the reactions which occur during black tea manufacture.
The depsides of tea are condensation products of two different hydroxy acids
(9). Examples are chlorogenic and p-coumarylquinic acids. Theogallin is derived
from gallic and quinic acids (Fig. 6). It may be unique to tea (9).
Free gallic acid is present in tea leaf and enters into interesting oxidation reac-
tions during the manufacture of black tea. Quinic acid, as would be expected from

OH OH
OH

HO HO
OH

(+) Gallocatechin (-) Epigallocatechin

FIGURE 2
 PROCEEDINGS: PHYSIOLOGICAL AND PHARMACOLOGICAL EFFECTS OF TEA 339

H”qg$$
OH
H”q$$$o 0
OH
0
OH
(-) Epicatechin gallate (-) Epigallocatechin gallate

FIGURE 3

its inclusion in tea depsides, is also found in fresh leaf, although it was not
recognized until quite recently (10).
In addition to the normal complement of amino acids in tea leaf, there is also
present an unusual amino acid known as theanine. It is an N-methylated deriva-
tive of glutamine (11). It constitutes about one half of the total amino acid content.
Its presence in green tea is said to correlate with beverage quality.
The popularity of tea is partly due to the presence of moderate amounts of
caffeine (254.5%). Other methyl xanthines, theobromine and theophylline, are
also present but in very small quantities, 0.1 and 0.02%, respectively (12).
Trigalloylglucose has been identified as a component of green leaf (7). While its
structure is reminiscent of tannic acid, the latter contains five galloyl groups
bonded to the glucose molecule with four or tive additional galloyl groups at-
tached with depside linkages. Trigalloylglucose has not been observed in manu-
factured green or black tea, perhaps because of hydrolysis to the free acid and
glucose.
The protein fraction includes the enzymes normally associated with plant cell
metabolism. The enzymes responsible for catechin synthesis have been identified.
Of greatest interest is tea polyphenol oxidase which catalyzes the aerobic oxida-
tion of the catechins. In the growing plant the enzyme is physically separated from
the polyphenol substrates contained in the leaf cell vacuoles. The molecular
weight is approximately 140,000. Copper is a required cofactor (13). Polyphenol
oxidase activity is greatest in the youngest leaf. High levels are important for
successful black tea production. Tea peroxidase has also been reported to enter
into the pathway of polyphenol oxidation during tea processing (14).
Other enzymes of interest in tea are glucosidases which catalyze the hydrolysis
of several aroma precursors (15), lipoxidases which are responsible for the gen-
eration of volatile aldehydes (16), and the enzymes responsible for methyl xan-

TABLE 6
PRINCIPAL FRESH LEAF CATECHINS
(+)-Catechin l-2 ( + )-Gallocatechin 1-3
(-)-Epicatechin 1-3 ( -)-Epigallocatechin 3-6
(- )-Epicatechin gallate 3-6 (- )-Epigallocatechin gallate 7-13
Total 16-30

Note. Catechins measured in % dry wt.

340 HAROLD N. GRAHAM

HO OH

Bisflavanols
R.H or Galloyl

FIGURE 4

thine synthesis. There is nothing exceptional about the carbohydrate, lipid, or

lignin fractions.
Carotenoids are present at low levels but they are important precursors of tea
aroma. Violaxanthine, p-carotene, neoxanthin, and lutein are among those iden-
tified (17).
The volatile fraction of fresh green tea is extremely small but important in
determining the acceptance of the tea beverage. More than 60 volatile components
have been identified in fresh tea leaf. They include alcohols, carbonyls, esters,
acids, and cyclic compounds (18). This fraction is greatly augmented in variety
and quantity during tea manufacture. Volatiles in fresh leaf have not been studied
as thoroughly as those in green and black teas. It is difficult to determine which
substances are actually present in the freshly plucked leaf and which are artifacts
of handling.
The mineral content of tea is roughly similar to that of most plants. Tea tends
to accumulate aluminum and manganese, depending on soil conditions. Copper is
essential for polyphenol oxidase activity as will be discussed. Tea is relatively rich
in potassium, calcium, magnesium, and fluoride (19).
MANUFACTURE OF GREEN TEA
The primary goal in the manufacture of green tea is the preservation of the leaf
catechins. The steps include plucking, rapid enzyme inactivation by steaming or

OH
OH

HO

dH

Cyanldin R-H

Delphinidin R=OH
FIGURE 5
 PROCEEDINGS: PHYSIOLOGICAL AND PHARMACOLOGICAL EFFECTS OF TEA 341

HO

Thwgallin

FIGURE 6

pan firing, rolling, and high temperature air drying. Glycosides of aromatic and
terpene alcohols found in the growing leafare rapidly hydrolyzed after plucking to
form the free volatile alcohols.
In Japan enzyme inactivation is generally carried out by steaming in large
rotating cylinders for 2&50 set followed by a series of twisting and drying steps
designed to produce a desirable appearance and reduce moisture gradually to
about 3%. Tea so produced is called sencha and is graded into several quality
categories (20).
Most Chinese green tea is produced by rapid pan tiring or roasting followed by
twisting and drying. In India a China-style green tea is manufactured by using
long, rotating heated cylinders for the inactivation step. Dwell time may be 7-10
min (21).
The several styles of green tea manufacture must result in compositional dif-
ferences. It would be highly desirable for all reports of feeding studies or in vitro
experimentation to specify clearly the tea processing techniques which were
utilized.
The rolling process imparts a twist which improves appearance. During the final
drying step many new aromatic compounds are formed which impart important
characteristics of green tea flavor. Green tea composition is similar to that of the
fresh leaf with regard to the major components.

GREEN TEA BEVERAGE COMPOSITION

Green tea beverage composition varies with the origin of the leaf and with
manufacturing conditions. Careful manufacture results in a light yellow-green
infusion exhibiting virtually no catechin oxidation. Many of the investigations of
dried green tea composition have been carried out by utilizing exhaustive extrac-
tion techniques with organic solvents. Little is known about the ability of a normal
hot aqueous infusion to extract some of the compounds recently reported in dried
green tea leaf. Green tea beverage composition is shown in Table 7 (22).
The tiring step at the end of manufacture generates hundreds of volatile com-
pounds. Components reported to be significant in the aroma of high quality green
tea beverage are shown in Table 8 (23).
342 HAROLD N. GRAHAM

TABLE I
COMPONENTS OF GREEN TEA BEVERAGE
Catechins 3042 Other organic acids 4-5
Flavonols 5-10 Theanine 4-6
Other flavanoids 2-4 Other amino acids 4-6
Theogallin 2-3 Methylxanthines 7-9
Other depsides 1 Carbohydrates lo-l.5
Ascorbic acid l-2 Minerals 6-8
Gallic acid 0.5 Volatiles 0.02
Quinic acid 2

Nore. Components measured in wt % of extract solids.

MANUFACTURE OF BLACK TEA

Most of the world’s tea is consumed as black tea beverage. Basic steps in black
tea production are plucking, withering, maceration (rolling), and drying. Plucking
is predominantly a hand operation but is being supplanted in some areas with
mechanical harvesters, usually with the inclusion of more coarse leaf, resulting in
decreased catechin levels. Withering lowers the moisture level and renders the
leaf more workable in preparation for the maceration step. It is that latter step
which disrupts cell structure and initiates oxidation. The processing equipment is
designed to ensure intimate contact among the polyphenol oxidase, the polyphe-
nols, and the atmospheric oxygen.
Oxidation is allowed to proceed for 45-90 min, depending on ambient temper-
ature, the nature of the leaf, and the style of tea being produced. Temperatures
between 20 and 30°C with high humidity and ample exposure of the macerated leaf
to air represent desirable oxidation conditions. During this period leaf color and
aroma change markedly (24).
The enzymatic oxidation step results in the formation of quinones and is the key
reaction that initiates all of the subsequent changes which occur (16). Until the
early part of the century the process was believed to be a microbial fermentation.
The first step in the oxidation of the catechins is illustrated in Fig. 7. The oxidation
of the gallocatechins is illustrated in Fig. 8.
The catechin quinones react in several complex manners. The quinone derived
from a simple catechin or its gallate may react with a quinone derived from a
gallocatechin or its gallate to form seven-membered ring compounds known as
theaflavins. These contain the benztropolone group. The formation of theaflavin

TABLE 8
SIGNIFICANT GREEN TEA AROMA COMPONENTS

Benzaldehyde Ionones
Benzyl alcohol cis-Jasmone
Cyclohexanones Linalool
Dihydroactinodiolide Linalool oxides
Geraniol Nerolidol
cis-Hexene-3-01 Phenylethanol
Hexenyl hexanoate Theaspirone
 PROCEEDINGS: PHYSIOLOGICAL AND PHARMACOLOGICAL EFFECTS OF TEA 343

HO HO
FIGURE 7

itself is shown in Fig. 9. The formation of the several possible theaflavin gallates
is illustrated in Fig. 10. Each of these has been identified in black tea (12).
Theaflavins are orange-red astringent compounds which contribute importantly
to black tea beverage color and taste, although they are present only at levels of
1.S2.5% in the dry leaf. They diminish in quantity if the fermentation period is
extended. Theaflavin levels are positively correlated with black tea quality (25).
There is some evidence concerning the antioxidative properties of theaflavin.
Most individual black tea fractions have not yet been investigated with regard to
that property.
Gallocatechin quinones, both in the free or gallated forms, may couple to form
a series of bisflavanols (26). As mentioned earlier these compounds have also
been found in fresh green leaf but they are synthesized additionally during the
manufacturing process as illustrated in Fig. 11. The bisflavanols (theasinensins)
are colorless compounds that are present only in very small quantities in black tea
and are assumed to undergo further changes as fermentation proceeds. Their
impact on black tea properties is probably minimal. All of the predictable bisfla-
vanols have been identified in black tea.
Gallic acid is not a substrate for tea polyphenol oxidase but its quinone can be
generated by reaction with the quinones derived from some of the catechins.
Reaction between gallic acid quinone and catechin quinones leads to the forma-
tion of other benztropolone molecules known as theaflavic acids (27) (Fig. 12).
They are analagous in structure to the theaflavins. Epitheaflavic acids are deep
red in color. All of the predicted forms are found in black tea but in very small
quantities. They are also assumed to take part in further reactions.
Compounds known as theaflagallins have also been isolated from black tea.
They contain the benztropolone structure and have been synthesized from gallo-
catechins and gallic acid under mild oxidizing conditions (28). The mechanism for
the formation of the theaflagallins is not known but they may be formed by the
condensation of two quinones both originating from trihydroxy molecules in con-
trast to the requirements for the formation of the theaflavins and the epitheaflavic
acids.

HO ti0
FIGURE 8
344 HAROLD N. GRAHAM

Ycyyc” + mqyg:

HO HO
catechin quinone gallocatechin quinone
+

OH

OH

OH + co2
HO

OH
Theaflavin
FIGURE 9

All of the well-characterized products of catechin oxidation just discussed,

together with the residual unoxidized catechins of black tea (5-10% of the original
amount), account for less than 20% of the fresh leaf catechin content. During
black tea manufacture most of the catechin mass is converted to a less well-

HO HO
+

HO HO
catechin quinone gallocatechin quinone
OH

OH

OH + co2
HO

dH
Theaflavin gallates
R=H or GaNoyl
FIGURE 10
 PROCEEDINGS: PHYSIOLOGICAL AND PHARMACOLOGICAL EFFECTS OF TEA 345
0

HO
+

Ii0 HO

gallocatechin quinone gallocatechin quinone

HO OH

Eisflavanols
R=H or Galloyl

FIGURE 11

defined group of compounds known as thearubigens. The thearubigen fraction is

a mixture of substances, red-brown in color, with a molecular weight distribution
of 1000-40,000 (22). The wide range reported may partly be the result of rapid
molecular condensation during holding in aqueous solution. Thearubigens readily

HO
HOOC -
+

OH HO
gallic acid quinone epicatechin quinone
t
OH

HO

OH + co2

bH

Epitheaflavic Acid
R=H or Galloyl
FIGURE 12
346 HAROLD N. GRAHAM

form insoluble complexes with caffeine and are primarily responsible for the
phenomenon of “creaming” when hot black tea infusions are cooled. The thearu-
bigens are separated from other tea components and partially resolved by solvent
extraction and chromatographic techniques.
The structures of the thearubigen components and the mechanism of their for-
mation are incompletely known. The high oxidation potentials of some of the
catechin quinones formed in the first steps of fermentation may be responsible for
the oxidation of theaflavins, bisflavanols, and epitheaflavic acids and the subse-
quent incorporation of their oxidation products into the thearubigen complex.
Flavonols and depsides may also be involved. Their diminuition during prolonged
fermentation supports this hypothesis (29).
Small amounts of hydrogen peroxide formed during fermentation may be acti-
vated by the tea peroxidase system to produce an additional oxidizing system that
could attack the flavanoid pyran ring and form proanthocyanidin condensation
polymers (Fig. 13). These compounds are also believed to be part of the thearu-
bigen fraction as its acid hydrolysis leads to the formation of the monomers,
cyanidin and delphinidin (30). Only a small proportion of thearubigen appears to
be so constituted. It is obvious that a large proportion of black tea components
originating from the catechins is not yet well characterized.
Enzymic activity is terminated by use of a hot air dryer in which moisture is
reduced to about 3%. Further darkening of the leaf occurs as chlorophyll is con-
verted to pheophytins and pheophorbide. Other organochemical processes occur
and many additional aromatic compounds are formed. The polyphenol oxidation

HO

Proanthocyanidin
i&H or OH
FIGURE 13
 PROCEEDINGS: PHYSIOLOGICAL AND PHARMACOLOGICAL EFFECTS OF TEA 347

and condensation products and the volatile substances are the primary determi-
nants of black tea taste.
BLACK TEA BEVERAGE COMPOSITION
It is difficult to state a definitive composition for black tea beverage as tea
varieties and style of manufacture differ markedly even within a single growing
area. Methods of beverage preparation also vary greatly. A beverage might be
prepared by extracting one part of tea with 100 parts of boiling water for about 3
min. An extract concentration of 0.30-0.35% is normally obtained. Such a bev-
erage will exhibit cloudiness and precipitation on standing. The precipitate,
known as cream, is generally correlated with good quality. It is composed
of thearubigens, thaflavins, caffeine, some occluded protein, and other large
molecules.
An approximate composition of the whole beverage is shown in Table 9 (3 1). As
indicated, unoxidized catechins are found in black tea beverage at as high a level
as 10% of the extract solids.
Black tea aroma is extremely complex and within the very small mass of volatile
compounds over 600 substances have been identified. Most of these are formed
from lipids, amino acids, carotenoids, and glucosides during the fermentation and
tiring steps (32). Some of the most significant components are shown in Table 10.
There is no tannic acid (pentadigalloylglucose) in tea leaf or beverage. Confu-
sion often arises from the use of the term “tannins” in referring to the catechins
and to black tea catechin oxidation products. Since these substances do not have
the properties of the common tanning agents used to manufacture leather, it is not
a useful term to apply to tea components and its use should be discontinued.
OOLONG TEA MANUFACTURE
The manufacture of oolong teas allows for a short period of oxidation. The
process is carried out in several different ways and products vary with respect to
the degree of catechin oxidation which is effected. Pouchong tea is considered to
be about fi fermented compared with black tea; normal oolong tea is considered
to be about ‘/t fermented (33). Oolong tea extracts contain catechins at a level of
8-20% of the total dry matter. Oolong tea composition would be expected to be
intermediate between green and black teas. During the last 3 years, however, a
large number of new flavanoids have been isolated from oolong tea and identified.
These include:

TABLE 9
PRINCIPAL COMPONENTS OF BLACK TEA BEVERAGE

Catechins 3-10 Methylxanthines 8-11

Theaflavins 34 Carbohydrates 15
Thearubigens 12-18 Protein 1
Flavonols 6-8 Mineral matter 10
Phenolic acids and depsides lo-12 Volatiles co. 1
Amino acids 13-15

Note. Components measured in wt % of extract solids.

348 HAROLD N. GRAHAM

TABLE 10
SIGNIFICANTBLACKTEAAROMACOMPONENTS
Benzyl alcohol Linalool oxides
Dihydroactinidiolide Methyl salicylate
Geraniol Nerolidol
Hexenyl hexanoate Phenylacetaldehyde
@Ionone Phenylethanol
cis-Jasmone Terpineol
Linalool Theaspirone

(a) new epigallocatechin esters (p-hydroxybenzoyl and cinnamyl) (34);

(b) new theasinensins (bisflavanols) and a new structural type called oolong
theanin, probably formed by oxidation of one of the B rings of a theasinensin (35);
(c) dimeric catechins having methylene bridges between the two pyran rings,
designated oolonghomobisflavins (36);
(d) epigallocatechin gallate esterified on the pyran ring with ascorbic acid (36);
and
(e) a series of eight dimeric proanthocyanidins composed of the common cat-
echins (36).
These compounds have not been found in the other two main tea types; not all
known black and green tea components have been found in oolong tea. It is
probable, however, that oolong tea contains most of the components of both black
and green tea although in significantly different proportions. It would be expected
that some of the more transitory products of catechin oxidation might be found
only in trace amounts in black tea. This is apparently the case for the bisflavanols
(theasinensins). It may also be more difficult to detect small amounts of some
substances in black tea than in oolong tea because of the masking effect of the
large, intractable thearubigen mass.
When the most sophisticated chromatographic and analytical tools are brought
to bear on any particular tea, as has been recently the case for the oolongs, it is
easy to see why new compounds are detected and identified. This does not pre-
clude their presence in teas previously examined with cruder procedures.
The techniques practiced in oolong tea production, i.e., controlled partial oxi-
dation, should allow for the production of teas with preferred compositions for
organoleptic or pharmaceutical purposes.
CONCLUSION
It is obvious that as much as tea has been researched, its composition is still not
adequately known. In view of its interesting pharmacological properties it would
be desirable for a program of analytical investigation to be carried out on well-
defined teas in a quantitative manner.
Teas used in pharmacological studies should be characterized with respect to
type, source, and method of manufacture. It would be desirable to specify ana-
lytical data such as caffeine and catechin contents. When extracts or fractions of
tea are used, methods of preparation should also be specified.
The ideal situation would entail the production and proper storage of large
 PROCEEDINGS: PHYSIOLOGICAL AND PHARMACOLOGICAL EFFECTS OF TEA 349

quantities of “standard” black, green, and oolong teas of several appropriate

types. The teas, along with their analytical data, should be made available to
investigators concerned with their pharmacological and biochemical properties. A
further refinement would be the preparation of standard dried aqueous extracts of
these teas, obviating variations in sample preparation for in viva and in vitro
experimentation.
REFERENCES
1. Annual Bulletin of Tea Statistics. London: International Tea Committee, 1990.
2. Lunder T. Tannings of green and black tea: Nutritional value, physiological properties and de-
termination. Farm Tijdschr Belg 1989; 66:3ti2.
3. Bhatia I, Ullah M. Qualitative and quantitative study of the polyphenols of different organs and
some cultivated varieties of tea plant. J Sci Food Agric 1968; 19:535.
4. Tanizawa H, Toda S, Sazuka Y, Taniyama T, Hayashi T, Arichi S, Takino Y. Natural antioxi-
dants. I. Antioxidative components of tea leaf (Thea. sinensis). Chem Pharm Bull 1984;
32:201 l-2014.
5. Zhao B, Li X, He R, Cheng S, Wenjuan X. Scavenging effect of extracts of green tea and natural
antioxidants on active oxygen radicals. Cell Biophys 1989; 14:175-185.
6. Uchida S, Edamatsu R, Hiramatsu M, Mori A, Nonaka G, Nishioka I, Niwa M, Ozaki M.
Condensed tannins scavenge oxygen free radicals. Med Sci Res 1987; 15:831-832.
7. Hashimoto F, Nonaka GI. Tannins and related compounds. LXXVII. Chem Pharm Bull 1989;
37:77-85.
8. Wickremasinghe R. In: Chichester C, Mrack E, Stewart G, Eds. Advances in Food Research.
New York: Academic Press, 1978:229.
9. Stagg G, Swaine D. The identification of theogallin as 3-galloylquinic acid. Phytochemistry 1971;
10:1671-1673.
10. Sakata K, Sakuraba S, Yagi A, Ina K, Hara T, Takeo T. Isolation and identification of (-)quinic
acid as an unidentified major tea component. Agric Biol Chem 1985; S&1919-1921.
11. Cartwright R, Roberts E, Wood D. Theanine, an amino acid N-ethylamide, present in tea. J Sci
Food Agric 1954; 5:597-599.
12. Graham H. Tea: The plant and its manufacture; chemistry and consumption of the beverage. In:
Spiller G, Ed. The Methyl Xanthine Beverages and Foods: Chemistry, Consumption, and
Health Effects. New York: Alan R. Liss, 1984:29-74.
13. Gregory R, Bendall D. The purification and some properties of polyphenol oxidase from tea.
Biochem J 1966; 101:56%581.
14. Dix M, Fairley C, Millin D, Swaine D. Fermentation of tea in aqueous suspension: Influence of tea
peroxidase. J Sci Food Agric 1981; 32:920.
15. Yano M, Okada K, Kubota K, Kobayashi A. Studies on the precursors of monoterpene alcohols
in tea leaves. Agric Bull Chem 1990; 54:1023-1028.
16. Owuor P. Flavour of black tea-A review. Tea 1986; 7:29-42.
17. Venkatakrishna S, Pemechandra B, Cama H. Comparative study of the effects of processing on
the carotenoid composition of Chinese and Assamese tea. Agric Biol Chem 1976; 40:2367-2371.
18. Yinfang H, er al. Study on the chemical constituents of the volatile oils from the fresh leaves of
Camellia sinensis. Acta Bot Sin 1982; 24:440-450.
19. Natesan S, Ranganathan V. Content of various elements in different parts of the tea plant of black
tea from southern India. .I Sci Food Agric 1990; 51:125.
20. Joy T. Green tea manufacture: Japanese style. Tea Coffee Trade J 1986; 158:22-23.
21. Forster K. Tea types and their processing in China. Tea Coffee Trade J 1990; 162:26-32.
22. Millin D, Rustidge D. Tea manufacture. Proc Biochem 1967; 2:9.
23. Kosuge M, Aisaka H, Yamanishi T. Flavor constituents of Japanese pan-fired green teas. Eiyo to
Shokuryo 1981; 34:545-549.
24. Reeves S, Owuor P, Othieno C. Biochemistry of black tea manufacture in Kenya. Trop Science
1987; 27~21-23.
350 HAROLD N. GRAHAM

25. Ullah M, Gogoi N, Barruah D. The effect of withering on fermentation of tea leaf and development
of liquor characters of black teas. J Sci Food Agric 1984; 35:1142-l 147.
26. Vuataz L, Brandenberger H. Plant phenols. III. Separation of fermented and black tea polyphe-
nols by cellulose column chromatography. J Chromatogr 1961; 5: 17-3 1.
27. Berkowitz J, Coggon P, Sanderson G. Formation of epitheaflavic acid and its transformation to
thearubigens during tea fermentation. Phytochemistry 1971; l&2271-2278.
28. Nonaka G, Hashimoto F, Nishioka I. Tannins and related compounds. XXXVI. Isolation and
structures of theatlagallins, new red pigments from black tea. Chem Pharm BuU 1986; 34~6145.
29. Millin D. Factors affecting the quality of tea. In: Quality Control in the Food Industry, 2nd ed.,
Vol. 4. New York: Academic Press, 1987: 127-160.
30. Cattell D, Nursten H. Phyfochemistry 1976; l&1%7-1970.
31. Sanderson G, Ranadive A, Eisenberg L, Farrel F, Simons R, Manley C, Coggon P. Contribution
of polyphenolic compounds to the taste of tea. In: Charalambous G, Katz I, Eds. Phenolic,
Sulfur, and Nitrogen Compounds in Food Flavors. ACS Symposium Series. No. 26. Washing-
ton, DC: American Chemical Society, 1976.
32. Takeo T, Manhanta P. Why CTC is less fragrant. Two and a Bud 1983; 30~76-77.
33. Yamanishi T. Tea, coffee, cocoa, and other beverages. In: Teranishi R. Ed. Recent Advances in
Flavor Research. New York: Dekker, 1981:231.
34. Hashimoto F, Nonaka G, Nishioka I. Tannins and related compounds. LVI. Isolation of four new
acylated flavan-3-01s from oolong tea. Chem Pharm Bull 1987; 35:611-616.
35. Hashimoto F, Nonaka G, Nishioka I. Tannins and related compounds. LXIX. Isolation and
structure elucidation of B,B-linked bisflavanoids, theasinensins D-G and oolongtheanin from
oolong tea. Chem Pharm Bull 1988; 36:167f&1684.
36. Hashimoto F, Nonaka G, Nishioka I. Tannins and related compounds. XC. Ascorbyl-
(- )epigallocatechin-3-0-gallate and novel dimeric flavan-3-01s: Oolonghomobisflavans A and
B, from oolong tea. Chem Pharm Bull 1989; 37:3255-3263.

Received August 21, 1991

Revised February 27, 1992
Accepted February 27, 1992