E. T. Contis et al.

(Editors)
Food Flavors: Formation, Analysis and Packaging Influences
© 1998 Elsevier Science B.V. All rights reserved 69

Aroma analysis of coffee brew by gas chromatography-olfactometry

K. D. Deibler, T. E. Acree, E. H. Lavin

Depart, of Food Science & Technology, Cornell University, Geneva, NY 14456

Abstract
During the study of coffee flavor, the processes of brewing, extraction and
sampling cause losses of the aroma compounds present in coffee grounds. In
this study, coffees from two brewing methods were extracted, serially diluted and
each dilution sniffed twice using the gas chromatography-olfactometry (GCO)
technique called CharmAnalysis . Among the hundreds of volatile chemicals
present, 18 of the thirty most potent odorants were identified by comparing the
mass spectra, odor activity and Kovat's retention indices with those of authentic
standards. Our studies have verified the presence of previously identified
aroma compounds among the most potent odorants in coffee and show the
differences between the two brewing methods tested.

1. INTRODUCTION

According to legend, coffee was discovered by an Arab goat herder named

Kaidi. He noticed that his goats became frisky and danced around the fields after
chewing on the berries from coffee bushes. After watching this, an abbot gave
some of the berries to neighboring monks, who prayed all night without falling
asleep. The first coffee drink, a steeped water broth, was consumed around the
year 1000 AD. Arabs from the port of Al Mukkah (Mocha) on the Red Sea
became the sole source for the world's coffee controlling the lucrative coffee
market by only permitting the export of boiled or roasted beans. In the 1600's,
smugglers broke the Arabian monopoly in coffee growing. They took seven
seeds of unroasted coffee beans from the port of Mocha to the western Ghats of
southern India. In the early 1700's, the Dutch began cultivating descendants of
the original plants in Java [1, 2].
Today coffee is the second most important trade commodity, second to oil
[3]. Coffee shops grew 20% annually from 1991 to 1995 with an expected four fold
increase by 1999 making coffee shops the fastest-growing type of food and drink
outlet in the United States [4]. However, coffee houses or bars are not a new
phenomenon. New York colonists first brought coffee to their breakfast table in
about 1668 to replace beer. Coffeehouses became the centers of cities' business.
70

political and social life during colonial times. Court trials and city council
meetings were held in early coffee houses. Paul Revere plotted the American
Revolution at the Green Dragon Coffee House in Boston [2].
Breakfast remains the most popular time of day for coffee consumption in
the US [5]. Coffee sales in the United States reached $7.4 billion in 1995 with a 2
cup per person daily consumption [4]. Consumer tests show that the taste of
coffee is the most important factor in purchasing coffee, thus understanding the
aroma profile of coffee is imperative [6].
The two commercially consumed varieties of coffee come from Coffea
arabica and Coffea canephora var. robust a. Most supermarket coffees are a blend
of the two and most instant coffees are made from Robusta beans. Robusta beans
are generally considered inferior to the more expensive Arabica beans.
Coffee grows in the regions between the Tropic of Cancer and the Tropic
of Capricorn. Many countries' economy depends on its sales of coffee beans.
Beans grown at lower altitudes are believed to be of lower quality with less
flavor. Where the coffee is grown is very important to the quality. Table 1
shows commonly accepted characteristics of beans grown in various regions [7].

Table 1
Characteristics of coffees from different regions of the world.

GENERAL AREA COUNTRY OR TYPE CHARACTERISTICS

African Tanzanian, Kenya, Heavy body; bright and floral;
Ethiopian excellent for blending
Arabian Yemen (Mocha) Heavy body but more aroma
Peninsula than African coffees.
Hawaii Kona No body; some aroma
Caribbean Jamaica Blue Mountain Balance of body and aroma
Indonesian Java, Sumatra, Celebes Balance of body and aroma;
spicy
Central American Nicaraguan, Mexican, Some body, lots of aroma;
Costa Rican, Guatemalan hints of cocoa
South American Colombian, Brazilian Some body; lots of aroma;
nutty

The coffee bean is actually half of a bean found inside a fruit called the
coffee cherry. The coffee cherry is ripe when the skin is red and has two green
beans inside. The fruit is picked by hand since the fruits ripen at different times
on the same bush. The fruit is fermented to loosen the beans, which are then
removed, washed and dried. There are two methods of extracting the green seed
from the fruit: the wet method and the dry method. The wet method produces
a higher acidity and cleaner flavor than the dry method which produces an
increased body and earthy flavors [3]. The green bean is the commodity
primarily traded. It is roasted by a roastmaster at 180 °C which is primarily w h e n
 71

the characteristic aromas are formed. Formation pathways of many coffee

odorants at roasting conditions have been discussed by Holscher [8], Baltes [9],
and Tressl [10]. During roasting the composition of the beans dramatically
changes; sucrose content drops from 7.3% to 0.3%, chlorogenic acid drops from
7.6% to 3.5% and protein content goes from 11.6% to 3.1%. Free amino acid
levels also change greatly [11]. The length of time for roasting affects the amount
of caffeine in the beans; the darker the roast the less the caffeine. Roastmasters
use both smell and sight to determine when the type of roast they desire has
been achieved. The roast is differentiated based on color from a Light city roast,
city roast, Brazilian to Viennese, French roast, Spanish -Cuban and espresso
being the longest roast time and darkest bean [7].
Due to the high quantity of unsaturated oils (13%), coffee beans are highly
vulnerable to autoxidation. Different brewing methods call for different sizes of
grinds. Grinds for espresso are much finer than those used for the long slow
method of percolation which use a course grind. Contact with light and
moisture affect the composition of the coffee bean while stored. All of these
factors make coffee flavor highly variable.

1.1. Coffee Aroma and Brewing Method

The enticing aroma of coffee cannot be characterized by a single chemical
component but is a combined response to many different chemical components.
More than 800 volatile compounds have been found in roasted coffee [12, 13].
Only a small number of these volatile compounds contribute to the aroma.
Aroma profiles of the green beans, roasted beans, brewed coffee, Coffea arabica,
and Coffea canephora var. Robusta have been evaluated [8,14-21]. The Werner
Grosch group has quantitated 22 important odorants in coffee brews by stable
isotope dilution assay and identified 32 of the 38 odorants detected. Stable
isotope dilution assay, aroma extraction dilution analysis (AEDA), odor active
value (OAV) analysis, and gas liquid chromatographic analysis have been
conducted on coffee [22, 23].
Extraction temperature, time and particle size are among the ways
brewing methods profoundly affect coffee flavor. In the US market filtered
coffee (extracted between 2 and 10 min) falls in between the extremes of espresso
(extracted in seconds) to percolator coffee (extracted between 15 to 30 min) and it
is used widely around the world. In this study a laboratory method for brewing
filtered coffee was developed to allow both controlled brewing time followed by
rapid cooling and solvent extraction. Because the technique involved cooling
under reduced pressure, the potential for aroma loss was examined by
comparing the gas chromatography-olfactometry (GCO) data from solvent
extracts of rapidly cooled coffee with coffee cooled in an ice bath. This quick brew
method produces an extractable brew ideal for GCO analysis. Using the
experimental brew method, shorter brew times (down to seconds); immediate
and rapid cooling; controlled contact time of water and grinds; and controlled
brew time are easy to achieve. This quick brew method uses apparatus available
in most modern chemistry laboratories. It allows for the extraction into water of
the coffee aromas with a minimized loss of aroma with the water vapor.
72

The aroma profile of a cup of coffee is variable and can be influenced by

bean origin, annual weather conditions, roasting method and time, grind size,
freshness, and brewing procedures. By using this experimental brewing method,
brewing time and temperature can be easily controlled and comparisons may
easily be made between experiments while producing an extractable simulation
of a typical cup of coffee.

2. MATERIALS AND METHODS

2.1. Brewing Methods

2.1.1. Quick Brew
The coffee grind to water ratio most commonly reported in the literature
(0.035, [24, 25]) was used. Approximately 50 g of a blend of Brazilian,
Guatemalan, and Colombian roasted Arabica coffee beans were ground in a
Krups Type 203 for 8 sec to achieve a particle size range of 300-500 jim. The
apparatus used for the experimental brew is shown in Figure 1. Distilled de-
ionized water (1250 mL, 95 °C) was filtered over the roasted and ground coffee
(45.0 g) on a UF-50 filter (Mr. Coffee., Inc., Bedford Heights, OH) in a 10 cm
diameter Buchner funnel attached to a 20 cm water cooled condenser collected in
a 2000 mL ice bath cooled vacuum flask. The condenser and exposed glassware
other than the funnel were insulated and chilled with frozen chill packs. A
minimal vacuum was pulled (0.13 atm) to achieve an increased flow rate (3.5
mL/sec) and reduced brewing time (6 min).

2.1.2. Conventional Brew

Water temperature, grind size, water volume, filter paper, and grind
quantity were held constant for the conventional brew method. The
conventional brew had a flow rate of 1.0 mL/sec. After brewing, the coffee was
chilled in an ice bath to 35 °C.

2.2. Aroma Extraction and Dilution Analysis

The aroma extraction procedures are summarized in Figure 2. The brew
(1.0 L) was successively extracted with a nonpolar solvent, Freon 113^^ (666 mL)
and a polar solvent, ethyl acetate (666 mL). This successive extraction with two
solvents (non-polar and polar) produces a greater volatile recovery than would
have been achieved using a single solvent. Each solvent extraction was first
stirred gently with a magnetic stirrer for 30 minutes, then separated in a
separatory funnel, and dried by filtering over MgS04. The extracts were
concentrated 243 times at 0.5 atm for freon and at 0.8 atm for ethyl acetate in a
rotary evaporator. The concentrates were then diluted in increments of 3-fold.

Gas chromatography-olfactometry (GCO) using CharmAnalysis was

conducted on the dilutions down to the concentration in which no aroma could
be detected [26]. A GCO run consisted of a 1 vil injection into a 0.25 mm x 10 m
column coated with 0.52 micron OVIOI methyl silicone in an HP5890 gas
 73

Water at 95X

Coffee Grinds
45.0 g Coffee Filter

Cold Packs
Water

Vacuum
4 in Hg
Coffee

Ice Bath

Figure 1. Diagram of quick brewing method.

chromatograph modified by DATU, Inc. The temperature was held at 35 °C for 3

min, programmed at 6 °C/min to 225 °C. The injector temperature was 200 °C
and the detector was held at 225 °C. Retention times of all odor active
compounds were recorded on a Macintosh^^^ computer and converted to
retention indices by linear interpolation of the retention times of a series of 7-18
carbon paraffin standards run under identical conditions and detected with a
flame ionization detector (FID) [27]. The retention times of the n-paraffins were
measured before each series of analyses and periodically between GCO analyses
to account for any changes in the column. The OVIOI column was used because
it elutes most odorants at the lowest possible temperature and can be
temperature-programmed at high rates to minimize sniffer fatigue [26]. The
same human subject was used for all GCO analyses. Multiple measures of each
GCO analysis were conducted on 2 replicates of the brewing methods and
extraction procedure, comprising a total of sixteen sets of dilutions. The
corresponding data from the two solvents were grouped together to total all the
aromatic components of the coffee brew.
The resulting dilution analyses were converted into Charm units (the
areas of the peak in the Charm chromatogram) a unitless ratio proportional to
74

the amount of eluting stimulus divided by its odor-detection threshold [27].

Odor spectra were generated from the Charm data using an exponent of 0.5 and
normalizing to the most potent odorant.
Chemical identification of odor ants in the coffee samples was based on an
exact match of odor character and retention index with that of an authentic
standard [27] [28]. Gas chromatography-mass spectrometry (GC-MS) correlation
of authentic standards verified the chemical identification. The GC-MS was
conducted at 70 electron volts on a mass range of 33-300 M / Z in an HP5970. The
HP5890 GC was programmed to heat isothermally at 35 °C for 3 min and then
increase at 4 °C/min to 240 °C. The same column type used for GCO except twice
the length (20m) was used for GC/MS. The injector temperature was 200 °C and
the detector was held at 250 °C.

1 Liter Coffee Sample

added 666 mL Freon 1 13TM
stirred gently 30 min
separated and dried over MgS04
Freon 113TM

- added 666 mL ethyl acetate

- stirred gently 30 min
- separated and dried over MgS04

Water Ethyl Acetate

Discan ^Concentrate 243X ^ Concentrate 243X^

3 by rotovap by rotovap

f Serial Dilutions Serial Dilutions^

by factor of 3X by factor of 3X

f CharmAnalysisTM ^ r CharmAnalysisTM ]

(Ethyl Acetate CHARM] (Freon 113 CHARM)

CHARM GROUP TOTAL i

Figure 2. Flow summary of solvent extraction of the coffee brews.
 75

3. RESULTS AND DISCUSSION

The thirty most potent aroma chemicals detected in the coffee extracts
(spectral values greater than 1.0%) are listed in Table 2. The 18 odorants
identified were also among the most potent odorants detected in coffee by
Aroma Extraction Dilution Analysis (AEDA) in three other studies [22-24, 29]. In
all three studies 2-furfurylthiol and P-damascenone were among the top three
most potent odorants found in coffee.
As shown in Table 2, the odorants were the same in both brews although
they were ranked somewhat differently. Table 3 shows that quantitative GCO
data is very noisy since the ranking variation in spectral values contributed by
multiple measures (Al, A2) is almost as great as the variation contributed by the
replicate samples (Al, Bl). Therefore, the ranking data should be accepted as
approximations and perhaps listed as "most potent groups," not individual
compounds. These errors partially result from using a human subject as a GC
detector.
To compare the yield of the two methods, total Charm (sum of the peak
areas in the Charm chromatogram) for each grouped chromatogram was
logarithmicly transformed (for normalization) and compared using analysis of
variance (ANOVA). A significant difference between the extracted aromas from
the two methods was detected at p=0.03. The experimental brew produced 100%
greater total Charm than the conventional brewing method. The challenge with
comparison of individual chemical responses is that the system is over defined;
there are more variables (intensity measurements) than there are cases (brewing
methods and replications). It would not be reasonable to increase the number of
cases due to cost and time of each experiment. Spectral data was used since
cluster analysis strongly indicated an increase in charm values between the
duplicate. Zero charm values were replaced with a calculated upper limit equal
to 3 s where s was the standard deviation in the blank. For this data s was taken
as the median standard deviation, 2.3. Any charm value below 6.9 was thus
replaced with 6.9 [27]. The spectral data was arcsine square-root transformed.
Six chemicals (methional, E-2-nonenal, sotolon, guaiacol, 5-methyl-6,7-
dihydrocyclopyrazine, and Furaneol) were selected because they all varied in the
same direction. The selection was required to reduce the number of variables. A
factor analysis using Statistica resulted in three factors with an eigenvalue
greater than 1.0 and also exhibited an apparent cut off on a Scree plot. The
resulting factors explaining 86% of the variation were varimax rotated (Table 4).
Multivariate analysis of variance (MANOVA) was conducted considering
brewing method and duplication with factor 2 and 3. There was an overall
intensity increase in the data from the first run to the duplicate. Based on the
MANOVA and the factor analysis, it can be concluded that there is a 280%
(p=0.03) increase in concentration of methional comparing the conventional
brewing method to the quick brewing method. Sotolon demonstrated a 167%
increase and cis-2-nonenal demonstrated a 100% decrease at a significance level
of 15%. Using discriminate analysis, methional and cis-2-nonenal showed a
significant change (p=0.5).
76

Table 2
Aroma occurrences resulting from CharmAnalysis of two brewing methods of
coffee. Retention times were converted to retention indices (RI) by linear
interpolation of the retention times of the series of 7-18 carbon paraffin.

CHEMICAL RI EXPERIMENTAL CONVENTIONAL DESCRIPT CAS

STIMULANT CHARM OSV CHARM OSV NUMBER
sotolon 1057 46200 100 13937 81 toast 28664-35-9
P-damascenone 1349 41123 94 20266 98 fruit 23726-93-4
2-furfurylthiol 881 37226 90 21092 100 toast 98-02-2
4-vinylguaiacol 1279 22327 70 7998 62 cloves 7786-61-0
2-methyl-3- 844 19701 65 16740 89 nuts 28588-74-1
furanthiol
vanillin 1335 18899 64 10773 71 vanilla 121-33-5
guaiacol 1066 16159 59 12641 plastic 90-05-1
furaneol 1033 15152 57 7064
n
58 caramel. 3658-77-3
methional 863 14221 55 3950 43 potato 3268-49-3
3-methoxy-2- 1160 8378 43 2989 38 plants 24683-00-9
isobutyl pyrazine
unknown 1502 5331 34 2016 31 burnt
unknown 1252 5285 34 1117 23 floral
2,4,5- 965 4973 33 3035 38 plastic 13623-11-5
trimethylthiazole
Abhexon 1156 2977 25 4086 44 honey 698-10-2
unknown 990 2493 23 1118 23 plastic
unknown 1403 2059 21 2006 31 spice
unknown 1222 2001 21 856 20 honey
4-ethyl guaiacol 1250 1692 19 2027 31 spice 2785-89-9
5-methyl-6,7- 1110 1613 19 983 22 cotton 23747-48-0
dihydrocyclo- candy
pentapyrazine
unknown 1285 1507 18 808 20 cloves
unknown 850 1280 17 1107 23 stinky
2-ethyl-3,5-di- 1045 907 14 1295 25 burnt 18138-04-0
n\ethylpyrazine
cis-2-nonenal 1132 866 14 1585 27 toast 18829-56-6
unknown 1206 865 14 576 17 licorice
unknown 1142 656 12 495 15 cereal
unknown 908 589 11 392 14 nutty
unknown 984 547 11 357 13 plastic
unknown 803 480 10 351 13 skunk
2-isopropyl-3- 1076 464 10 403 14 green 25773-40-4
methoxypyrazine
2,3,5- 971 461 10 449 15 toast 14667-55-1
trimethylpyrazine
 77

Table 3
Comparison of spectral results from GCO multiple measures (1 and 2) and
brewing replicates (A and B) for the experin\ental brewing method extracts for
the ten most potent components. Data are combined results from ethyl acetate
and Freon 113^^ fractions.
AROMA CHEMICAL A l A2 Bl B2 STDev STDev STDev
multiple replicates All
measures
2-furfurylthiol 100 71 66 100 34 32 18
p-damascenone 19 31 34 35 12 9 7
2-methyl-3-furanthiol 56 20 50 13 7 39 21
sotolon lb 67 100 31 30 30 29
guaiacol 6 29 23 11 18 21 11
vanillin 32 75 33 40 13 33 20
4-vinylguaiacol 62 100 57 7 36 45 38
furaneol 5 28 27 14 21 21 11
methional 37 35 23 11 18 6 12
3-methoxy-2-isobutyl 19 19 15 10 6 2 4
pyrazine

Table 4
Factor loading (variance maximized rotated) from factor analysis of selected
chemicals' arcsine square-root transformed spectral data.
AROMA CHEMICAL FACTOR 1 FACTOR 2 FACTOR 3
methional -0.8 0.0 0.96
furaneol 0.9 -0.2 0.1
sotolon -0.1 0.7 0.5
guaiacol 0.9 0.2 -0.3
5-methyl-6,7- 0.6 0.6 -0.2
dihydrocyclopyrazine
E-2-nonenal 0.0 0.8 0.0

4. CONCLUSIONS

CharmAnalysis and AEDA detect the same important aroma chemicals in

coffee but variability in the data makes it difficult to obtain exact orders of
importance. The experimental brewing method described here should
minimize errors by providing better control of time and temperature. Although
quantitative GCO is more error prone than other chemical measurements, it is
useful for understanding the affects of various treatments on coffee aroma and
provides direction for more precise chemical analysis such as isotope dilution
analysis.

5. ACKNOWLEDGMENTS

We are grateful for the financial and sample support from Nihon Tetra Pak.
78

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