Eur Food Res Technol (2000) 211 : 272276

 Springer-Verlag 2000

O R IG IN AL P AP E R

Florian Mayer Michael Czerny Werner Grosch

Sensory study of the character impact aroma compounds

of a coffee beverage

Received: 13 December 1999 / Revised version: 31 January 2000

Abstract The more potent odorants in a sample of

medium-roasted Arabica coffee and in the corresponding brew were quantified. Large amounts ( > 75 %) of
acetaldehyde,
2,3-butanedione,
2,3-pentanedione,
vanillin and some furanones were extracted from the
coffee brew, whereas the yields of the more unpolar
compounds, such as 3-isobutyl-2-methoxypyrazine,
(E)-b-damascenone and the unstable 2-furfurylthiol
were low ( < 25 %). On the basis of quantitative data
an aroma model was prepared for the brew. In triangle tests, models containing the complete set of 24
odorants were compared with a model missing one or
more odorants. These experiments indicated that the
aroma of the brew was mainly caused by some
alkylpyrazines, furanones and phenols, and by 2-furfurylthiol, methional and 3-mercapto-3-methylbutyl formate. The higher impact of both methional and the
formate on the aroma of the brew and the lower
aroma activity of 4-vinylguaiacol were in contrast to
results obtained in a previous study for ground coffee
of the same provenance and roast degree.
Key words Coffee brew Aroma compounds
Quantification Extraction yield Aroma model
Omission experiments

Introduction
The flavour of coffee changes when a brew is prepared from ground roasted coffee. Caramel-like, buttery and phenolic notes become more intense. Screening for potent odorants, the results of which have

F. Mayer M. Czerny W. Grosch ())

Deutsche Forschungsanstalt fr Lebensmittelchemie,
Lichtenbergstrasse 4, 85748 Garching, Germany
e-mail: Werner.Grosch@Lrz.tu-muenchen.de
Tel.: +49-89-28914170
Fax: +49-89-28914183

been reviewed [1], indicates that these changes are not

caused by the formation of new odorants. Charm analysis of a coffee brew [2] confirms this conclusion.
Quantification of 22 potent odorants in ground
roasted Arabica and Robusta coffee and in the corresponding brews indicates that the change in aroma
is caused by a shift in the concentrations of the odorants [3]. The polar odorants, e.g. 4-hydroxy-2,5-dimethyl-3(2H)-furanone, are preferentially extracted
whereas the yield of the unpolar ones, e.g. 3-isobutyl2-methoxypyrazine, is low [3].
On the basis of the quantitative data obtained for
the odorants of the brews, synthetic mixtures (aroma
models) were formulated for Arabica and Robusta
coffee brews [3]. The models smelled clearly coffeelike and reproduced the differences in the odour profiles of the original brews.
Also, in the case of ground roasted Arabica coffee
we were successful in imitating the aroma using a synthetic mixture of 27 odorants [4]. A sensory panel
evaluated the changes in the overall odour after omission of one or more odorants. These omission experiments indicated that 2-furfurylthiol, 4-vinylguaiacol,
several alkylpyrazines, furanones, acetaldehyde, propanal, methylpropanal and 2- and 3-methylbutanal had
the greatest impact on the flavour of ground coffee. In
contrast, the absence of 2,3-butanedione, 2,3-pentanedione, b-damascenone and vanillin in the aroma
model was not noticed by the assessors.
The aim of the present study was to clarify which
of the potent odorants screened by dilution experiments [1] were actually contributing to the coffee
brew aroma. These odorants were therefore quantified
in a medium-roasted Arabica coffee powder and in
the corresponding brew. On the basis of the results,
an aroma model was prepared duplicating the odour
profile of the brew. Omission experiments, analogous
to those reported for ground roasted coffee [4], were
then performed.

273

Materials and methods

Materials
Coffee beans (Coffea arabica), cultivated in Colombia, were
medium roasted in a Neotec RFBS fluidized bed roaster, packed
under vacuum, sealed in 800 g portions, stored at 35 C and
ground as described previously [4]. The coffee brew (1.0 l) was
prepared by extracting coffee powder (54.0 g) with boiling water
(1.1 l) according to Semmelroch and Grosch [3]. The brew was
cooled down to 20 C.

Quantification of odorants in coffee powder

Odorants 125 were quantified in coffee powder according to
Mayer et al. [7].

Chemicals
Pure samples of the odorants listed in Table 1 were purchased
from the sources given in parentheses or synthesized according
to the cited literature: 17, 9, 11, 12, 14, 16, 1921 (Aldrich,
Steinheim, Germany), 8, 10 [5], 13 (Givaudan-Roure, Duebendorf, Switzerland), 15 (Haarmann & Reimer, Holzminden, Germany), 17, 18 (Lancaster, Muehlheim/Ruhr, Germany), 22 [4],
23 [6], 24 [3], 25 (Fluka, Neu-Ulm, Germany). Stable isotopomers of the odorants used as internal standards were obtained as
reported [7]. Sodium dihydrogen phosphate, disodium hydrogen
phoshapate and p-hydroxymercuribenzoic acid were purchased
from Aldrich (Steinheim, Germany), and cysteine was obtained
from Merck (Darmstadt, Germany).
Methods
High-resolution gas chromatography mass spectrometry
Static headspace analysis mass spectrometry (SHA-MS) and
multidimensional gas chromatography mass spectrometry
(MDGC-MS) were carried out according to Mayer et al. [7].
Table 1 Concentrations of the
odorants in coffee powder and
coffee brew, and extraction
yields of the compounds

Using MDGC-MS, the effluents eluting from the precolumn

DB-FFAP (30 m 0.32 mm, 0.25 mm film thickness; J & W Scientific, Folsom, USA) at various retention index ranges
(14201500: 7, 9, 20, 21; 15001540 11, 22; 15201600 8, 10;
18001900 15, 16; 20002100 12, 13, 17; 21502200 14, 18;
25502600 19) were transferred onto the main column OV-1701
(30 m 0.32 mm, 0.25 mm film thickness; J & W Scientific, Folson, USA). MS spectra were recorded for analytes, and internal
standards and calibration factors were determined as recently
described [7].

Quantification of odorants in coffee brew

Odorants 16. Coffee brew (5 ml) was placed into a waterjacket headspace vessel (300 ml) which was sealed with a septum. The labelled internal standards of the analytes were
injected through the septum by a syringe. The vessel was heated
at 40 C for 1 h, and an aliquot of the headspace (5 ml) was
used for SHA-MS.
Odorants 722. The Following amounts of the coffee brew were
used for analysis: 10 ml for compounds 12, 13, 18; 50 ml for 7,
14, 16, 17, 19, 20; 500 ml for 811, 15, 21, 22. Each sample of
coffee brew was spiked with the corresponding labelled internal
standards and then stirred for 15 min. The amounts of the standards varied between 0.5- and 3-fold concentrations of the odorant to be estimated. Distillation under high vacuum was performed using the apparatus designed by Engel et al. [8]. The
distillate obtained was extracted with dichloromethane
(3 50 ml). The extract was dried over anhydrous Na2SO4 and
concentrated to 0.1 ml using a Vigreux column (40 1 cm) and

Compound

Acetaldehyde (1)
Methylpropanal (2)
2-Methylbutanal (3)
3-Methylbutanal (4)
2,3-Butanedione (5)
2,3-Pentanedione (6)
2-Ethyl-3,5-dimethylpyrazine (7)
2-Ethenyl-3,5-dimethylpyrazine (8)
2,3-Diethyl-5-methylpyrazine (9)
2-Ethenyl-3-ethyl-5-methylpyryzine (10)
3-Isobutyl-2-methoxypyrazine (11)
4-Hydroxy-2,5-dimethyl-3(2H)-furanone (12)
2(5)-Ethyl-4-hydroxy-5(2)-methyl-3(2H)-furanone (13)
3-Hydroxy-4,5-dimethyl-2(5H)-furanone (14)
(E)-b-Damascenone (15)
Guaiacol (16)
4-Ethylguaiacol (17)
4-Vinylguaiacol (18)
Vanillin (19)
2-Furfurylthiol (20)
Methional (21)
3-Mercapto-3-methylbutyl formate (22)
2-Methyl-3-furanthiol (23)
3-Methyl-2-buten-1-thiol (24)
Methanethiol (25)
a
b

Concentrationa

Extraction

Powder
(mg/kg)

Brew
(mg/l)

yieldb

120000
124000
126000
117000
149000
135000
111400
111153
111100
111115
111120
140000
116000
111900
111260
112400
111800
145000
114100
111700
111250
111130
111160
111113
114400

4700
1760
1870
1570
2100
1600
1117
1111.0
1113.6
1110.2
1111.5
7200
1800
1180
1111.6
1120
1148
1740
1210
1117
1110
1115.7
1111.1
1110.6
1170

73
59
62
62
79
85
79
35
67
25
23
95
93
78
11
65
49
30
95
19
74
81
34
85
72

Data are means of at least two assays that did not vary by more than 10 %
Percentage ratio of the odorant amount in 1 l coffee brew and in 54 g coffee powder

274
microdistillation [9]. An aliquot was then analysed by MDGCMS.
Odorants 23 and 24. Coffee brew (500 ml) was spiked with
known amounts of the labelled internal standards and extracted
with dichloromethane (2 250 ml). The organic layers were isolated by centrifugation and concentrated to 80 ml by distilling
off the solvent at 40 C under reduced pressure (60 kPa). p-Hydroxymercuribenzoic acid (2.5 mmol/l in disodium hydrogen
phosphate/sodium dihydrogen phosphate buffer, 0.1 mol/l, pH
8.5, 3 25 ml) was added to the extract and stirred at 600 rpm
for 15 min to trap all of the thiols as salts [10]. After separation,
the combined aqueous layers were concentrated to 10 ml by distillation under reduced pressure (60 C, 15 kPa). Subsequently,
cysteine as displacing agent was added and the liberated thiols
were trapped by a dynamic headspace technique and analysed
by HRGC-MS according to Kerscher an Grosch [6].
Odorant 25. Coffee brew (50 ml) was put into a vessel (300 ml)
which was sealed with a septum. A known amount of [2H3]methanethiol [11] was injected by a gas-tight syringe. The vessel was
kept at 20 C for 30 min, and an aliquot of the headspace
(10 ml) was analysed by SHA-MS.
Sensory experiments
Sensory analyses were performed as described previously [4].
Models
Stock solutions, in which the concentrations of the odorants
were 1000-fold higher than in coffee brew (Table 1), were prepared as follows: compounds 16, 12 and 13 were dissolved in
water. The following odorants were available in various solvents:
9, 11, 14, 1622 (ethanol), 7, 8 (diethyl ether), 15, 24 (dichloromethane), 23 (pentane). The amount calculated for the stock
solution was diluted with water.
Pyrazine 10 was compensated for by increasing correspondingly the concentration of pyrazine 8 [4]. The stock solution of
25 was prepared by dissolving 7.8 ml of gas in water (100 ml).
To prepare the aroma model, 1 ml of each stock solution was
pipetted into phosphate buffer (disodium hydrogen phosphate/
sodium dihydrogen phosphate, 0.1 mol/l, pH 5.4), the volume of
which was adjusted to 1 l. The solutions (20 ml) were poured
into glass beakers (diameter 40 mm, capacity 45 ml) and
coloured dark brown with odourless sugar colour (0.1 ml; Kattus, Maisach, Germany).
Odour profile
Samples were presented to a test panel consisting of 10 experienced participants: six males and four females aged 2635
years. They scored the intensities of the odour attributes sweetish/caramel-like, earthy, roasty/sulfurous and smoky on a
scale from 0 (absent) to 3 (very strong). Furthermore, the assessors evaluated the similarity of the aroma of the model to that
of the coffee brew on a scale from 0 (no similarity) to 3 (identical with coffee brew). After an outlier test according to Nalimov
[12], the results were expressed as means  standard deviations.
Omission experiments
One or more compounds (Table 3) were omitted in the aroma
model of coffee brew. Each reduced model was presented
together with two complete models to 10 assessors who, by sniffing the sample, had to find out what was different in the overall
odour. The triangle test was repeated on the same day. The
number of correct answers was summed up (maximum 20), and
the significance of the result (P < 0.05) was evaluated [13].

Results and discussion

Concentrations of odorants
The concentrations of 25 odorants in the Arabica coffee sample from Colombia, which was used for the
preparation of the brew as well as in the brew itself,
were determined by stable isotope dilution assays.
In the powder the concentrations of odorants 16,
8, 10, 13, 1521, 23 and 25 differed by not more than
25 % from the values reported by Semmelroch and
Grosch [3]. Only pyrazines 7, 9 and 11 (+61 %, +40 %,
98 %), furanones 12 and 14 (+29 %, +36 %) and thiols
22 and 24 (+62 % and +51 %) were higher in the
present sample.
In the coffee beverage acetaldehyde (1), 2-ethenyl3,5-dimethylpyrazine (8), 2-ethenyl-3-ethyl-5-methylpyrazine (10), 2-methyl-3-furanthiol (23) and 3-methyl2-buten-1-thiol (24) were quantified for the first time.
The amounts of the remaining odorants differed in
most cases (2, 47, 9, 1317, 19, 20, 22, 25) from those
obtained earlier [3] by not more than 25 %. Greater
deviations were only found for 2-methylbutanal (3, +
34 % in the brew presented here), pyrazine 11 (+
50 %), phenol 18 (55 %), furanone 12 (+60 %) and
methional (21, +75 %). The portions of the odorants
in the preparation of the brew were calculated.
According to the results in Table 1, diones 5 and 6,
pyrazine 7, furanones 1214, vanillin (19), 3-mercapto3-methylbutyl formate (22) and 3-methyl-2-buten1-thiol (24) were soluble in hot water quite well, leading to yields > 75 %. A group of eight odorants (14,
9, 16, 21, 25) lay in the yield range of 5075 %. The
extraction rates of pyrazines 10 and 11, b-damascenone (15) and furfurylthiol (20) amounted to 25 %. The
lower yields of odorants 10, 11 and 15 reflected their
poor solubility in hot water. The yield of furfurylthiol
(20) was reduced by reactions with components of the
coffee sample, e.g. carbonyl compounds.
In the earlier study on the composition of the coffee brew aroma [3], the yields were calculated for 15
odorants. A comparison of the results with the data in
Table 1 reveals that in the cases of pyrazines 7, 9 and
11, furanone 13, b-damascenone (15), phenols 16, 17
and 19 and thiol 22 the absolute difference was not
greater than 10 %. However, the values reported for
2,3-butanedione (5, 21 %), furanone 14 (19 %),
vinylguaiacol (18, 17 %) and furfurylthiol (20, 14 %)
were lower in the brew analysed here, and those for
2,3-pentandione (6, +12 %), furanone 12 (+18 %) and
methional (21, +29 %) were higher.

Omission experiments
An aroma model for the coffee brew was prepared on
the basis of the quantitative data listed in Table 1.
Ten assessors described its overall odour as clearly

275
Table 2 Odour profiles of the coffee brew and the aroma modela
Attribute

Coffee brew

Aroma model

Sweetish/caramel-like
Earthy
Roasty/sulfurous
Smoky
Similarityc

1.6
1.9
2.3
2.0

2.1
1.7
2.1
1.4
2.0

(0.4)
(0.2)
(0.5)
(0.6)

(0.7)b
(0.4)
(0.6)
(0.4)b
(0.3)

Intensities of the attributes were scored on a scale from 0 (not

detectable) to 3 (strong). The results of 10 assessors are given as
the mean (standard deviations in parenthesis)
b
Significant difference (P < 0.05) to the corresponding attribute
in the aroma of the coffee sample
c
Similarity of the aroma model to the coffee brew on a scale
from 0 (no similarity) to 3 (identical with coffee brew)

coffee-like. However, as shown in Table 2, the odour

profile of the model differed significantly in the intensity of the sweetish/caramel-like and smoky notes
from those of a fresh brew. Because of this difference
the similarity of the aroma of the model to that of the
original brew was only 2.0.
Table 3 Number of assessors
detecting the model in which
one or more odorants were
omitted in triangle tests

There are indications that the difference in aroma

between model and real brew is not caused by a lack
of important odorants in the former. This suggestion
was supported by a separate experiment with an
aroma model for ground roasted coffee which contained only 22 odorants in concentrations equal to
those in the headspace [14]. Odorants 2224 were
lacking but were present in both the brew aroma
model and the earlier model, which based on the concentrations of the odorants in ground roasted coffee
[4]. However, the absence of the three odorants did
not affect the aroma of the headspace model, since
the assessors agreed that its odour profile was very
close to that of the real coffee sample, and consequently gave the high similarity score of 2.6. We
suggest that the lower score of the brew aroma model
was caused by its instability. In fact during storage for
30 min, thiol 20 decreased in the model by 40 %
(Moors, personal communication). The concentrations
of the odorants were much lower in the headspace
than in the brew, hence chemical reactions of them
are unlikely.
a

Experiment
no.

Compound(s) omitted

11
12

Acetaldehyde (1)
Acetaldehyde (1), methylpropanal (2), 2-methylbutanal (3),
3-methylbutanal (4)
2,3-Butanedione (5), 2,3-pentanedione (6)
Acetaldehyde (1), methylpropanal (2), 2-methylbutanal (3),
3-methylbutanal (4), 2,3-butanedione (5), 2,3-pentanedione (6)
2-Ethyl-3,5-dimethylpyrazine (7), 2-ethenyl-3,5-dimethylpyrazine (8),
2,3-diethyl-5-methylpyrazine (9), 3-isobutyl-2-methoxypyrazine (11)
2-Ethyl-3,5-dimethylpyrazine (7), 2-ethenyl-3,5-dimethylpyrazine (8),
2,3-diethyl-5-methylpyryzine (9)
2-Ethyl-3,5-dimethylpyrazine (7)
3-Isobutyl-2-methoxypyrazine (11)
4-Hydroxy-2,5-dimethyl-3(2H)-furanone (12), 2(5)-ethyl-4-hydroxy5(2)-methyl-3(2H)-furanone (13), 3-hydroxy-4,5-dimethyl-2(5H)furanone (14)
4-Hydroxy-2,5-dimethyl-3(2H)-furanone (12), 2(5)-ethyl-4-hydroxy5(2)-methyl-3(2H)-furanone (13)
3-Hydroxy-4,5-dimethyl-2(5H)-furanone (14)
(E)-b-Damascenone (15)
Guaiacol (16), 4-ethylguaiacol (17), 4-vinylguaiacol (18), vanillin
(19)
Guaiacol (16)
4-Vinylguaiacol (18)
2-Furfurylthiol (20), methional (21), 3-mercapto-3-methylbutyl formate (22), 2-methyl-3-furanthiol (23), 3-methyl-2-buten-1-thiol (24),
methanethiol (25)
2-Furfurylthiol (20)
Methional (21), 3-mercapto-3-methylbutyl formate (22), 2-methyl3-furanthiol (23), 3-methyl-2-buten-1-thiol (24), methanethiol (25)
Methional (21)
3-Mercapto-3-methylbutyl formate (22)
2-Methyl-3-furanthiol (23)
3-Methyl-2-buten-1-thiol (24)
Methanethiol (25)
Acetaldehyde (1), methanethiol (25)

13
14
15
16
17
18
19
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
a

Number of
assessors b
6
8
4
12c
13c
12c
4
6
12c
7
8
6
12c
7
8
18c
12c
12c
14c
12c
7
6
8
13c

Models lacking in one or more components (numbering refers to Table 1) were singly compared
to two models containing the complete set of 25 odorants
b
Number of correct answers (maximum 20)
c
Significant difference (P < 0.05) in the flavour between the complete and the reduced model [14]

276

The composition of the brew aroma model was varied to identify the character impact flavour compounds. According to the results in Table 3, the omission of acetaldehyde (1) in exp. 1, the Strecker
aldehydes 14 in exp. 2 and the diones 5 and 6 in exp.
3 was not significantly perceived by the sensory panel.
This was in contrast to exp. 4 in which the lack of carbonyl compounds 16 changed the overall odour so
clearly that a significant number of answers were correct. The alkylpyrazines 79 with (exp. 5) and without
(exp. 6) methoxypyrazine 11 were clearly missed by
the assessors, but not pyrazine 7 (exp. 7) and methoxypyrazine 11 (exp. 8) alone. In case of the furanones the absence of furaneol (12) and ethylfuraneol
(13) in exp. 10 as well as of sotolon (14) in exp. 11
was not recognized. Only when the three furanones
were lacking in exp. 9 was a change in the aroma perceived by a significant number of assessors. The finding that single compounds, but not the complete class,
could be omitted without a clear effect on the aroma
was also observed for the phenolic odorants. When
omitting the whole group (exp. 13), the assessors perceived a weakening of the smoky note in the reduced
model. In contrast, guaiacol (16) in exp. 14 or 4-vinylguaiacol (18) in exp. 15 were not clearly missed.
Exp. 16 indicates that the group of sulfur compounds had the greatest effect on the aroma of the
model, as 18 of the answers were correct. The roasty/
sulfurous note was weaker in the reduced model. As
shown in exp. 17, 2-furfurylthiol (20) contributed to
the aroma. However, when it was the only sulfur compound in the reduced model (exp. 18), the odour difference to the complete model was not abolished. This
was mainly due to methional (21) and 3-mercapto3-methylbutyl formate (22) since exps. 19 and 20 indicated that 21 and 22 were further sulfur compounds
whose absence impaired the aroma. In contrast, the
odour contributions of thiols 2325 were weak (exps.
2123). According to exp. 24, the aroma of the
reduced model differed clearly from that of the complete one when methanethiol (25) together with acetaldehyde (1) were lacking.
A comparison of the results presented here with
those obtained for the model imitating the aroma of
ground roasted coffee [4] reveals major differences in
the contributions of the sulfur compounds. The effect
of 2-furfurylthiol (20), the predominating odorant of
the powder, was weaker in the brew because it its

lower extraction yield (Table 1). On the other hand,

methional (21) and formate 22 belonged to the key
odorants of the brew (Table 3) but not to those of
ground coffee [4].
A large decrease in 2-furfurylthiol (20) and also in
21 and 22 was observed in comparative aroma extract
dilution analysis (AEDA) before and after heating of
a coffee brew [15]. It was suggested that this change is
responsible for the decrease in the intensity of the
roasty aroma note after heat sterilization of the
canned coffee drinks. The results presented here support this suggestion.
Acknowledgements We thank Mrs. Laskawy for skillful technical assistance.

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