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Coffee Avour: An Overview: January 2004
Coffee Avour: An Overview: January 2004
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ABSTRACT: This paper is a concise review of the research on coffee flavour to serve as a rapid reference on the
subject. It covers the process of roasting coffee beans, the volatile and non-volatile components generated by the
process and the chemical reactions responsible for their formation. Volatile compounds significant on the determin-
ation of coffee aroma are given according to the most recent research. Finally, the paper discusses the chemical
indexes used over the years to characterize coffee flavour deterioration and estimation of shelf-life. Copyright © 2004
John Wiley & Sons, Ltd.
KEY WORDS: coffee flavour; volatiles; non-volatiles; chemical indexes
Copyright © 2004 John Wiley & Sons, Ltd. Flavour Fragr. J. 2004; 19: 99–104
100 R. A. BUFFO ET AL.
all pyrolytic reactions, resulting in coffee with under- that impart to roasted coffee its characteristic colour.
developed organoleptic characteristics.2 6. Carboxylic acids, mainly citric, malic and acetic, re-
sponsible for sourness.
7. Chlorogenic acids, mainly cinnamic, caffeic, ferulic,
Chemical Composition of Roasted Coffee isoferulic and sinapic, and their main degradation
product, quinic acid, all responsible for astringency.
The chemical reactions that take place during roasting 8. Lipids, including triglycerides, terpenes, tocopherols
have not been completely elucidated. This results from and sterols, that contribute to brew viscosity.
the extreme difficulty of reproducing or simulating in the 9. Minerals, with potassium being the most abundant
laboratory all the reactions that take place inside a bean, (around 40% w/w). Metals such as manganese (10–
since: 50 ppm), iron (15– 40 ppm) and copper (2–5 ppm)
may catalyse reactions occurring during roasting and
1. Not all the active precursors of aroma, colour and storage.
taste present in green coffee have been identified.
2. The very large number of precursors give rise to com-
plex reactions, difficult to isolate, since intermediate Carbon Dioxide
products react further.
3. Most reactions take place within intact bean cells, Carbon dioxide is quantitatively the most important non-
which have very thick walls. These walls are com- aroma-contributing volatile compound in roasted coffee.
parable to autoclaves, where the pressure can only be It is generated by pyrolysis and the Strecker degradation
guessed.2 reaction.6 The amount is dependent on the degree of roast
and can be up to 10 ml/g coffee.7 This gas is released
Roasting produces a net loss of dry matter, primarily slowly in whole beans but rapidly after grinding. Because
as gaseous carbon dioxide, water and volatiles products it has a zero dielectric constant, carbon dioxide is very
of pyrolysis. There is a considerable degradation of poly- soluble in the coffee matrix. Its loss from the bean is
saccharides, sugars, amino acids and chlorogenic acids, most likely due to relationships between temperature and
and a moderate relative increase in organic acids and the glass transition state in the system, although this later
lipid content. Roasting also produces high levels of physical effect has not been explored.
caramelization and condensation products. Caffeine and After coffee grinding, much of the carbon dioxide pro-
trigonelline (N-methyl nicotinic acid) concentrations duced during roasting is released. A suitable degassing
remain almost unchanged.5 time (2–8 h) must be applied before packaging using her-
metic containers. Efficient degassing of roasted ground
coffee is critical when it is packaged in flexible bags
Non-volatile Components without vacuum. If the time for degassing is too short,
the package can swell, losing appearance and even burst-
As aforementioned, chemical components of roasted ing. To solve this, gas valves can be placed in the wall
coffee can be grouped into volatile and non-volatile sub- of plastic bags to allow the release of carbon dioxide.8
stances, some of the former being responsible for the It has been reported that 45% of the carbon dioxide is
aroma and the latter for the basic taste sensations of sour- released during the first 5 min after grinding.9 One work
ness, bitterness and astringency. The non-volatile com- in the literature states that 1.21 ml/g carbon dioxide and
pounds in roasted coffee are:2,5,11 0.002 ml oxygen/g roasted ground coffee (Arabica) were
released during the first hour after grinding.10 As particle
1. Caffeine, which contributes to the strength, body and size decreases, the release of carbon dioxide is facilitated
bitterness of brewed coffee. because of greater surface-to-volume ratios. A decrease
2. Trigonelline and its two non-volatile derivatives: of particle size from 1000 to 500 µm has been reported
nicotinic acid (of nutritional value) and N- to double the release of the gas.7 Pressurization with
methylnicotinamide. nitrogen and carbon dioxide itself helps to prolong the
3. Proteins and peptides that did not undergo Maillard shelf-life of espresso coffee, because it maintains carbon
reaction. dioxide inside the coffee cells, avoiding cell wall damage
4. Polysaccharides, namely cellulose, hemicellulose, and further flavour release.11
arabinogalactan and pectins, that play an import-
ant role in the retention of volatiles and contribute to
coffee brew viscosity. Volatiles
5. Humic acids or melanoidins, as final products of the
Maillard reaction between amino acids and mono- The mechanisms of formation of coffee aroma are
saccharides; they are the brown-coloured substances extremely complex and there is clearly a wide range of
Copyright © 2004 John Wiley & Sons, Ltd. Flavour Fragr. J. 2004; 19: 99–104
COFFEE FLAVOUR: AN OVERVIEW 101
interactions between all the routes involved. The major Table 1. Classes of volatile compounds identified in
mechanisms include:2,12,13 roasted coffee
Sulphur compounds
1. Maillard reaction (non-enzymatic browning): a reac- Thiols14
tion between nitrogen-containing substances on the Hydrogen sulphide15
Thiophenes (esters, aldehydes, ketones)16
one hand (proteins, peptides, amino acids, seroto-
Thiazoles (alkyl, alcoxy and acetal derivatives)17
nine and trigonelline) and reducing carbohydrates, Pyrazines
hydroxy-acids and phenols on the other, to form Pyrazine itself 18
aminoaldoses and aminoketones by condensation. Thiol and furfuryl derivatives19
Alkyl derivatives (primarily methyl and dimethyl)20
2. Strecker degradation: a reaction between an amino
acid and an α-dicarbonyl with the formation of an Pyridines
Methyl, ethyl, acetyl and vinyl derivatives14
aminoketone that condenses to form nitrogen hetero-
Pyrroles
cyclic compounds or reacts with formaldehyde to Alkyl, acyl and furfuryl derivatives14,21,22
form oxazoles. Oxazoles23
3. Breakdown of sulphur amino acids, viz. cystine, Furans
cysteine and methionine, that are transformed into Aldehydes, ketones, esters, alcohols, acids, thiols, sulfides and in
combination with pyrazines and pyrroles24
mercaptans, as well as thiophenes and thiazoles,
Aldehydes and ketones
after reacting with reducing sugars or intermediate
Aliphatic and aromatic species25
products of the Maillard reaction. Phenols26
4. Breakdown of hydroxy-amino acids, viz. serine and
threonine, able to react with sucrose to form mostly
alkylpyrazines. Semmelroch et al.,13 using AEDA, selected only 14
5. Breakdown of proline and hydroxyproline, that react compounds to reproduce coffee aroma based on odour
with intermediate Maillard products; the former gives activity values (OAV), i.e. the ratio of concentration to
pyridines, pyrroles and pyrrolyzines, whereas the odour threshold (Table 2). Deibler, Acree and Lavin27
latter forms alkyl-, acyl- and furfurylpyrroles. used CharmAnalysis™ to signal 30 potent odorants in
6. Degradation of trigonelline, forming alkyl-pyridines brewed coffee, of which 18 compounds were identified
and pyrroles. by comparing their mass spectra, odour activity and
7. Degradation of the quinic acid moiety, forming Kovát’s retention indices with those of authentic stand-
phenols. ards (Table 3).
8. Degradation of pigments, mostly carotenoids. Semmelroch and Grosch28 quantified these potent
9. Minor lipid degradation, primarily diterpenes. odorants in ground roasted Arabica and Robusta coffee
10. Interaction between intermediate decomposition pro- and in the corresponding brews, finding that a change in
ducts (mostly unknown). aroma takes place from roasted to brewed coffee due to
a shift in the concentration of the odorants. The polar
odorants, e.g. 4-hydroxy-2,5-dimethyl-3(2H)-furanone,
Aroma Volatiles in Roasted Ground Coffee were preferentially extracted, whereas the yield of the
unpolar ones, e.g. 3-isobutyl-2-methoxy pyrazine, (E)-β -
Active research on the volatile composition of coffee has damascenone and 2-furfurylthiol, was low. On the basis
taken place in the last 25 years with the advent of gas of the quantitative data obtained, these authors formulated
chromatography–mass spectrometry. The principal classes synthetic mixtures (aroma models) for the Arabica and
of aroma compounds in roasted ground coffee are listed Robusta brews. The models smelled clearly coffee-like
in Table 1. and reproduced the differences in the odour profile of the
original brews.
For roasted Arabica coffee, Czerny, Mayer and
Significant Contributors to Aroma Grosch29 carried out sensory assessments of model
systems of 27 odorants in an oil/water mixture. An
The identification of new volatiles in roasted coffee may expert sensory panel evaluated the changes in the
well become an exercise in futility because the central overall odour after omission of one or more odorants.
issue is to determine the chemicals effectively respons- These omission experiments indicated that 2-furfurylthiol,
ible for coffee aroma.12 Gas chromatography–olfactometry 4-vinylguaiacol, several alkylpyrazines, furanones,
(GCO) techniques, such as AEDA (aroma dilution extrac- acetaldehyde, propanal, methyl propanal and 2- and 3-
tion analysis) and CharmAnalysis™ have allowed the menthylbutanal had the greatest impact on the flavour
individualization of those key odorants by directly sniff- of ground coffee. In contrast, the absence of 2,3-
ing the chromatographic eluent. From the list of around butanedione, 2,3-pentanedione, β -damascenone and vanil-
80 compounds proposed by Holscher and Steinhart,26 lin in the aroma model according to the corresponding
Copyright © 2004 John Wiley & Sons, Ltd. Flavour Fragr. J. 2004; 19: 99–104
102 R. A. BUFFO ET AL.
Table 2. Odour activity values (by AEDA) and formation mechanisms of volatiles in
the aroma of roasted ground Arabica coffee13
Sotolon 81 Toast
β -Damascenone 98 Fruit
2-Furfurylthiol 100 Toast
4-Vinylguaiacol 62 Cloves
2-Methyl-3-furanthiol 89 Nuts
Vanillin 71 Vanilla
Guaiacol 77 Plastic
Furaneol 58 Caramel
Methional 43 Potato
3-Methoxy-2 isobutyl pyrazine 38 Plants
2,4,5-Trimethylthiazole 38 Plastic
Abhexon 44 Honey
4-Ethyl guaiacol 31 Spice
5-Methyl-6,7-dihydrocyclopentapirazine 22 Cotton candy
2-Ethyl-3,5,-dimethylpyrazine 25 Burnt
cis-2-Nonenal 27 Toast
2-Isopropyl-3-methoxypyrazine 14 Green
2,3,5-Trimethylpyrazine 15 Toast
omissions was not noticed by the assessors. This study formate. The higher impact of methional and formate and
confirmed for the most part the compounds previously the lower aroma activity of 4-vinylguaiacol were in con-
identified by Semmelroch et al.13 with the exception of trast to the results previously obtained for ground coffee
(E)-β -damascenone, the compound with the highest odour of the same provenance and roast degree.
activity value. Although the degradation of carotenoids Finally, Mayer and Grosch32 quantified 22 potent
that generates β -damascenone has been regarded as odorants in the headspace of roasted Arabica coffee pow-
having a major importance on tea flavour and is even der, and a model mixture was prepared accordingly.
suggested to play an important role in coffee aroma as When evaporated, the similarity of the aroma of the
well,30 sensory studies did not validate this possibility. model to that of the roasted coffee headspace was scored
In a follow-up study, Mayer, Czerny and Grosch31 2.6 on a scale of 0 (no similarity) to 3.0 (identical). The
quantified the most potent odorants in brewed medium- model included odorants such as acetadehyde, methyl-
roasted Arabica coffee. In accordance with previous re- propanal, 2- and 3-methylbutanal, 2,3-butadione, 2,3-
sults,28 the more polar compounds yielded much larger pentadione, 2-furfurylthiol, 2-ethyl-3,5-dimethylpyrazine
amounts than the unpolar ones (>75% vs. < 25%, respect- and 2,3-diethyl-5-methylpyrazine.
ively). An aroma model was prepared based on these
results for the brew. In triangle tests, the model contain-
ing all 24 odorants was compared with a set of models Chemical Indicators of Sensory
missing one or more compounds using the afore- Deterioration
mentioned omission tests. These experiments indicated
that the aroma of the brew was mainly caused by The onset of sensory staleness is used to determine the
some alkylpyrazines, furanones and phenols, and by end of shelf-life of roasted ground coffee.9 Staleness
2-furfurylthiol, methional, and 3-mercapto-3-methylbutyl in coffee is defined as ‘a sweet but unpleasant flavour
Copyright © 2004 John Wiley & Sons, Ltd. Flavour Fragr. J. 2004; 19: 99–104
COFFEE FLAVOUR: AN OVERVIEW 103
and aroma of roasted coffee which reflects the oxidiza- key volatiles, viz. hexanal, vinylpyrazine, pyrrol, furfuryl-
tion of many of the pleasant volatiles and the loss of methylketone and pyridine, with a good fit of their sen-
others; a change in the flavour and the acid constituents sory data (r 2 = 0.87).
causing a partial bland tone’.33 Since the late 1950s
when the gas chromatographic work on coffee aroma was FQI = 6.53 + 0.027 [hexanal] − 0.08 [vinylpyrazine]
initiated, a great evolution in analytic and data pro- − 0.04 [pyrrol] − 0.022 [furfurylmethylketone]
cessing techniques has occurred, and different staling − 0.001 [pyridine]
indexes have been developed and correlated to sensory
deterioration. Nevertheless, the equation was only an experimental fit
and did not have a theoretical basis.
Copyright © 2004 John Wiley & Sons, Ltd. Flavour Fragr. J. 2004; 19: 99–104
104 R. A. BUFFO ET AL.
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Copyright © 2004 John Wiley & Sons, Ltd. Flavour Fragr. J. 2004; 19: 99–104