Food Research International 89 (2016) 982–988

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Food Research International

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Volatile thiols in coffee: A review on their formation, degradation,

a r t i c l e i n f o a b s t r a c t

Article history: Thiols are among the compounds that have the greatest impact on the flavor of coffee. Due to their extremely low
Received 30 November 2015 odor thresholds, they have a significant sensory impact even at very low concentrations. Thiols are formed during
Received in revised form 11 February 2016 coffee roasting and are described as the key odorants responsible for the typical “coffee” and “roasty” odor notes,
Accepted 12 February 2016
greatly influencing the sensory characteristics of coffee. They are particularly reactive and prone to oxidation;
Available online 13 February 2016
their rapid depletion after preparation of a coffee brew and during storage of roasted coffee has been associated
Keywords:
with sensory quality decrease and coffee going stale. For these reasons, their determination and insight into their
Coffee formation and degradation mechanisms could help us to preserve the sensory quality of coffee and to modulate
Thiol its sensory features. Coffee aroma has been widely studied in recent decades, and it has become evident that the
Aroma role of certain volatile thiols is paramount. Nevertheless, a limited number of studies have specifically addressed
Quality this class of compounds, and several aspects have not yet been satisfactorily elucidated. The aim of this review is
Sensory to provide an overview of the current state on knowledge about coffee thiols, focusing on their occurrence,
Review determination, sensory impact, formation and evolution in roasted and brewed coffee.
© 2016 Elsevier Ltd. All rights reserved.

1. Introduction of coffee are formed during the roasting of beans through the Maillard
reaction, Strecker degradation and autooxidation, among other process-
Coffee has a series of peculiar characteristics that make it a unique es (Buffo & Cardelli-Freire, 2004; Baggenstoss, Poisson, Kaegi, Perren, &
beverage and consequently it is one of the most commonly consumed Escher, 2008; Cerny, 2008; Sunarharum et al., 2014). Some sulfur-
and appreciated products around the world. In addition to the stimulant containing compounds are among the most significant for coffee flavor.
properties of caffeine and its capability to promote beneficial health ef- In particular, certain volatile thiols are extremely influential on the sen-
fects (Higdon & Frei, 2006; Hall, Desbrow, Anoopkumar-Dukie, Arora, & sory profile of coffee. Despite their low concentrations, their extremely
McDermott, 2015), the popularity of brewed coffee stems mainly from low odor thresholds mean that they have a great olfactory impact
its pleasant and attractive aroma: determined by its volatile fraction. (Holscher & Steinhart, 1992; Semmelroch & Grosch, 1995; Cerny,
Around 800 compounds have been identified to date in the volatile 2008; McGorrin, 2011).
fraction of coffee (Sunarharum, Williams, & Smyth, 2014), including Coffee flavor has been reviewed by various authors in recent
ketones, aldehydes, furans, pyrroles, pyridines, pyrazines, phenols, years (Grosch, 1998; Buffo & Cardelli-Freire, 2004; Kumazawa,
alcohols, esters, hydrocarbons oxazoles, carboxylic acids, lactones, ter- 2006; Sunarharum et al., 2014). This review aims to outline the cur-
penes, amines and sulfur compounds. Their concentrations range from rent state of scientific knowledge of coffee thiols, some of the flavor
a few ng/L to hundreds of mg/L. Despite this complexity, only a small compounds that have the greatest impact on the product. Research
number of compounds are responsible for the majority of the olfactory from the last three decades is summarized, focusing on the occur-
sensation coffee provokes (Tressl, 1989; Holscher, Vitzum, & Steinhart, rence, assessment, sensory impact, formation and evolution of thiols
1990; Blank, Sen, & Grosch, 1992; Semmelroch, Laskawy, Blank, & in roasted and brewed coffee.
Grosch, 1995; Semmelroch & Grosch, 1995, 1996; Czerny, Mayer, &
Grosch, 1999; Mayer & Grosch, 2001), although sensory studies indicate 2. Thiols in coffee: occurrence and sensory impact
that synergies among stimuli, oral processing, and dynamic evolution of
the sensory stimulus, could play a major role in the aroma perception Thiols or mercaptans, are organic compounds containing an SH
(Ferreira, 2011; Foster et al., 2011). Most of the impact odor compounds group. They are sulfur analogs of alcohols, where the SH group replaces
the OH group, and are highly susceptible to oxidative degradation. Their
⁎ Corresponding author. boiling points are lower than those of the corresponding alcohols and
E-mail address: [email protected] (S. Vichi). some of them are characterized by a very strong odor. Due to the

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 N. Dulsat-Serra et al. / Food Research International 89 (2016) 982–988 983

extremely low odor thresholds of certain thiols, they have a significant concentrations are similar to reference coffee samples (Czerny
sensory impact even at very low concentrations, and their identification et al., 1999; Mayer et al., 2000; Mayer & Grosch, 2001) some authors
and quantification is crucial for the assessment and improvement of reported that while concentrations of 2-furfurylthiol below 0.5–1 μg/L
food sensory quality. Many studies report the relevance of volatile thiols provide a freshly brewed coffee aroma, higher concentrations are per-
as aroma components in foodstuffs such as wine (Roland, Schneider, ceived as sulfury, stale or rancid coffee (Tressl & Silwar, 1981;
Razungles, & Cavelier, 2011), beer (Vermeulen, Lejeune, Tran, & Collin, McGorrin, 2011). Likewise, 2-methyl-3-furanthiol below 0.5–1 μg/L
2006), cheese (Sourabié, Spinnler, Bonnarme, Saint-Eve, & Landaud, provides a meat-like note, while at higher concentrations it is described
2008) and food products that have undergone the Maillard reaction as sulfurous or mercaptan-like (Tressl & Silwar, 1981; McGorrin, 2011).
(Schieberle, 1991; Hofmann, Schieberle, & Grosch, 1996; Kerscher & 3-methyl-2-buten-1-thiol is characterized by a skunky, fox-like note
Grosch, 1998), including roasted coffee (Cerny, 2008; McGorrin, 2011). and although is generally present in lower concentrations than other
The major thiols reported in roasted and brewed coffee are summa- thiols, in particular in brewed coffee, it possesses one of the lowest
rized in Table 1, and their molecular structures are shown in Fig. 1. The odor thresholds (Table 1).
concentrations of thiols in roasted and brewed coffee, as reported by 3-Mercapto-3-methyl-1-butanol has been related to broth, cooked
different authors over the last two decades, vary from a few ng/kg to meat, spicy and sweat notes (Holscher, Vitzum, & Steinhardt, 1992;
several mg/kg (Table 1). Several factors such as the degree of roasting McGorrin, 2011); while the corresponding formic and acetic acid esters
and the coffee species, variety and origin, can have an effect on the have been described as contributors to the blackcurrant-like and roasty
thiol content of coffee, but the use of different analytical methods for notes in coffee (Czerny et al., 1999; Mayer et al., 2000; Kumazawa &
their determination could be a cause of certain differences between re- Masuda, 2003a). Although 3-mercapto-3-methyl-1-butanol in coffee is
sults. The principles and the performance of the methods used for thiol much more abundant than the corresponding esters (Table 1), its con-
analysis are discussed in the next section. An overall diminution of thiol tribution to the aroma is less important because of its higher odor
concentration is noticeable when passing from roasted to brewed coffee threshold. According to Holscher et al. (1992), the free polar hydroxyl
(Table 1), due to the low extraction rate of brewing coffee (Semmelroch group interferes with the tertiary mercaptan group, which is responsi-
& Grosch, 1996; Mayer, Czerny, & Grosch, 2000). ble for the “catty” notes of the esters and among the most potent odor-
2-Furfurylthiol is a key odorant reported as the main compound ants known to date, causing loss of the odorant potency and conversion
responsible for the “coffee” odor (Mayer et al., 2000; McGorrin, 2011) of the odor note.
and its influence on coffee sensory characteristics is highly dependent Methanethiol is the most abundant thiol in both roasted and brewed
on its concentration. Although sensory models prepared at higher coffee (Table 1), and although as a pure compound it is described as

Table 1
Thiols described in coffee, their concentrations in roasted and brewed coffee, and thiol odor characteristics.

Compounds Concentration Odor descriptor Odor threshold

1 2-Furfurylthiol 1080–1730a; 1680b; 1050–2910c; 1700d; 1350–1650e; 17d; 19–39i; Roaste,k,l; fresh coffeem 0.01k; 0.00004n
2600–3400f; 2800–5080g; 0.06–0.18h 0.002–0.004j
2 2-Methyl-3-furanthiol 68b; nd-104c; 60d 1.1d Boiled meat-likek,m,o; nutsl 0.05p; 0.004n;
0.007q
3 3-Methyl-2-butene-1-thiol 8b; 8.6–27.7c; 13d; 0.08–0.86h; 8.2i; 31.8p 0.6d; 0.12r Foxy, skunkyk; amine-likeo 0.0002–0.0004s
4 Methanethiol 4700b; nd-5300c; 4400d; 4500e; 3500–6400f 170d; 210–600i Putrid, cabbage-like, sulfurousk, 0.2t; 0.02q
fresh coffeem
5 3-Mercapto-3-methyl-1-butyl 120–130a; 77b; 5.6–304c; 130d; 130–240f; 0.005–0.083h; 5.7d; 4.3–5.5i; Roastya,k; blackcurrant-likee; 0.0035k;
formate ≤8.8u 0.011–0.032j Cattyk,m 0.002–0.005s
6 3-Mercapto-3-methyl-1-butyl ≤7.5u; 0.006–0.087h 0.017–0.058j Roastyu –
acetate
7 3-Mercapto-3-methyl-1-butanol 0.167–1.3h 0.11–0.22j Broth, sulfur, sweet, sweat, 2–6s; 1.5v
onionm; cooked leeksv
8 4-mercapto-1-butanol 0.002–0.013h 0.001–0.002j – –
9 2-Methyl-3-tetrahydrofuranthiol 0.014–0.047h 0.001–0.002j Meatyw –
a
Semmelroch et al., 1995.
b
Czerny et al., 1999.
c
Mayer et al., 1999.
d
Mayer et al., 2000.
e
Mayer & Grosch, 2001.
f
Baggenstoss et al., 2008.
g
Cheong et al., 2013.
h
Vichi et al., 2014.
i
Semmelroch & Grosch, 1996.
j
Quintanilla-Casas et al., 2015.
k
Semmelroch & Grosch, 1995.
l
Buffo & Cardelli-Freire, 2004.
m
McGorrin, 2011.
n
Tominaga et al., 2000.
o
Blank et al., 1992.
p
Tressl, 1989.
q
Belitz, Grosch, & Schieberle, 2009.
r
Poisson, Hug, Baggenstoss, Blank, & Kerler, 2011.
s
Holscher et al., 1992.
t
Guth & Grosch, 1994.
u
Extrapolated from Kumazawa & Masuda, 2003a.
v
Tominaga et al., 1998.
w
Batemburg & van der Velden, 2011.
984 N. Dulsat-Serra et al. / Food Research International 89 (2016) 982–988

Fig. 1. Molecular structures of coffee thiols reported in Table 1. (1) 2-Furfurylthiol; (2) 2-methyl-3-furanthiol; (3) 3-methyl-2-butene-1-thiol; (4) methanethiol; (5) 3-mercapto-3-
methyl-1-butyl formate; (6) 3-mercapto-3-methyl-1-butyl acetate; (7) 3-mercapto-3-methyl-1-butanol; (8) 4-mercapto-1-butanol; (9) 2-methyl-3-tetrahydrofuranthiol.

putrid and cabbage-like (Semmelroch & Grosch, 1995), its presence 3. Analytical determination of thiols in coffee
in coffee has been related to the pleasant “fresh coffee” perception
(Holscher & Steinhart, 1992; McGorrin, 2011). Analytical assaying of volatile thiols in food is mainly hindered
The sensory impact of thiols in coffee is usually determined by sensory by their low concentrations and their susceptibility to oxidative
analysis, by aroma extract dilution assay (AEDA) and CharmAnalysis™, or degradation reactions, which causes rapid conversion of thiols to
by the calculation of the odor activity values (OAVs; ratio of concentration disulfides via auto-oxidation or their degradation at high temperatures.
to odor threshold) (Acree, Barnard, & Cunningham, 1984; Grosch, 2001). In recent years, different methods have been applied to the determina-
Sensory studies based on the evaluation of the overall odor after the tion of thiols in coffee, including non-specific techniques, suitable for a
omission of one or more odorants indicated that 2-furfurylthiol is the wide range of volatile compounds, and methods that are selective for
thiol with the highest impact on ground coffee aroma whereas thiol compounds.
2-furfurylthiol and 3-mercapto-3-methyl-1-butyl formate are
among the main odorants in brewed coffee (Czerny et al., 1999; 3.1. Non-specific techniques
Mayer et al., 2000). These results are in agreement with the OAVs
of these thiols in powdered and brewed coffee, as reported in other Gas chromatography coupled to mass spectrometry (GC–MS) is the
studies (Semmelroch et al., 1995; Semmelroch & Grosch, 1996). most frequently used technique for the analysis of coffee thiols.
According to the same omission tests, the absence of 2-methyl-3- On-column injection at low temperature has been applied by some
furanthiol, 3-methyl-2-butene-1-thiol and methanethiol does not authors in order to prevent thermal degradation of the thiols
affect the aroma of the model. (Semmelroch et al., 1995; Semmelroch & Grosch, 1996; Czerny
In contrast, the flavor dilution factors (FDs) obtained by AEDA et al., 1999).
indicated that all the abovementioned components have an impact on Simultaneous distillation/extraction (SDE) and vacuum distillation
the odor of coffee powder (Blank et al., 1992; Semmelroch & Grosch, (Tressl & Silwar, 1981; Holscher et al., 1992; Schenker et al., 2002),
1995). In particular, 3-mercapto-3-methyl-1-butyl formate appeared as well as static headspace analysis (Holscher & Steinhart, 1992;
comparable or even almost 10-fold more potent than 2-furfurylthiol Mayer, Czerny, & Grosch, 1999; Bröhan, Huybrighs, Wouter, & Van
(Blank et al., 1992; Semmelroch & Grosch, 1995) and methanethiol der Bruggen, 2009), have been reported to pre-concentrate thiols
was described as the major contributor to the freshly roasted coffee from coffee powder or brewed coffee prior to analysis. Other authors
aroma (Holscher & Steinhart, 1992). In brewed coffee, some AEDA have used organic solvents for the extraction of thiols from coffee
results confirmed the higher sensory impact of 3-mercapto-3-methyl- powder or brewed coffee, and have concentrated them by combining
1-butyl formate over the other thiols (Blank et al., 1992; Sanz, Czerny, this with either vacuum distillation, preparative column chromatog-
Cid, & Schieberle, 2002; Kumazawa & Masuda, 2003a); while others raphy, microdistillation, covalent chromatography (Semmelroch
indicated 2-furfurylthiol as the most relevant thiol (Semmelroch & et al., 1995; Semmelroch & Grosch, 1996; Mayer et al., 1999, 2000;
Grosch, 1995; Kumazawa & Masuda, 2003b). Meanwhile, 3-mercapto- Sanz et al., 2002; Kumazawa & Masuda, 2003a) or solvent assisted
3-methyl-1-butyl formate and 2-furfurylthiol were defined as potent flavor evaporation (SAFE) (Hofmann, Czerny, Calligaris, & Schieberle,
odorants in coffee brews by CharmAnalysis™; but their impact was 2001; Hofmann & Schieberle, 2002; Sanz et al., 2002). Extraction
often lower than that of 3-methyl-buten-1-thiol (Akiyama et al., 2008). times ranged from a few minutes to more than 18 h, and different
 N. Dulsat-Serra et al. / Food Research International 89 (2016) 982–988 985

procedures were often necessary for the determination of each thiol. formation of H2 S, methanethiol, ethanethiol, 3-mercapto-2-
More recently, solid-phase microextraction (SPME) has been intro- butanone and 3-mercapto-2-pentanone. 5-Methyl-2-furfurylthiol
duced for the analysis of thiols in coffee brews (Charles-Bernard, (responsible for the roasty, coffee-like notes) was predominant in
Kraehenbuehl, Rytz, & Roberts, 2005a; Charles-Bernard, Roberts, & the rhamnose/cys model; while 2-methyl-3-furanthiol was charac-
Kraehenbuehl, 2005b; Baggenstoss et al., 2008; Akiyama et al., 2008; teristic of the ribose/cysteine model (Hofmann & Schieberle, 1997).
Genovese, Caporaso, Civitella, & Sacchi, 2014; Caporaso, Genovese, Methanethiol is believed to result from the pyrolysis of methionine
Canela, Civitella, & Sacchi, 2014). (Baggenstoss et al., 2008).
In order to compensate for the losses of thiols caused by the isolation Another important pathway for the formation of coffee thiols
procedures and to reduce quantification errors, a stable isotope dilution during roasting involves sulfur-containing amino acids and prenyl
assay (SIDA) has been applied by some authors when using solvent alcohol (3-methyl-2-buten-1-ol); a volatile constituent of green coffee
extraction and concentration (Semmelroch et al., 1995; Semmelroch & beans. Under roasting conditions, H2S liberated from cysteine or
Grosch, 1996; Czerny et al., 1999; Mayer et al., 1999, 2000) or SPME methionine may react with the double bond of prenyl alcohol to form
(Baggenstoss et al., 2008). Using this procedure, thiols in the sample 3-mercapto-3-methyl-1-butanol (Holscher et al., 1992). Prenyl alcohol
are quantified by means of internal standards labeled with stable was also identified as the precursor of 3-methyl-2-butene-1-thiol,
isotopes, which in many cases need to be synthesized. which could be formed in the presence of H2S by substitution of the
hydroxyl group by a thiol group (Holscher et al., 1992). Although the
3.2. Selective methods addition of formic acid to model reactions could not confirm the
formation of the corresponding ester (Holscher et al., 1992), it is gen-
To overcome thiol degradation during analytical procedures, erally assumed that under real coffee roasting conditions, the ester-
selective derivatization could stabilize the free thiol group. For this ification of 3-mercapto-3-methyl-1-butanol with short-chain fatty
reason, the analysis of thiols in foodstuff frequently implies the use of acids generated by carbohydrate degradation during the process
thiol-specific derivatization agents, such as p-hydroxymercury benzo- (Ginz, Balzer, Bradbury, & Maier, 2000) leads to the formation of 3-
ate (Tominaga, Murat, & Dubordieu, 1998; Tominaga, Blanchard, mercapto-3-methyl-1-butyl formate and acetate (Holscher et al.,
Darriet, & Dubourdieu, 2000; Vermeulen et al., 2006) or 2,3,4,5,6- 1992; Kumazawa & Masuda, 2003a).
pentafluorobenzyl bromide (Mateo-Vivaracho, Cacho, & Ferreira,
2007, 2008; Rodríguez-Bencomo, Schneider, Lepoutre, & Rigou, 4.2. Influence of roasting conditions on thiol formation
2009), among others.
In coffee, derivatization of 3-methyl-2-butene-1-thiol with Roasting plays a primary role in thiol formation, which is highly
p-hydroxymercury benzoate has been reported by Mayer et al. influenced by the process conditions; in particular, by roasting time
(1999). After derivatization, glutathione was added to liberate the and temperature. The distinct thiol species follow different generation
thiols which underwent solvent extraction and concentration. and degradation kinetics, according to their mechanism of formation,
Recently, simultaneous derivatization/extraction followed by high- molecular stability and the availability of their precursors (Kumazawa
performance liquid chromatography and electrospray-high resolution & Masuda, 2003a; Baggenstoss et al., 2008). In general, thiols increase
mass spectrometry (HPLC-ESI-HRMS) was developed for the analysis in amount throughout the roasting process, reaching a maximum at
of coffee thiols (Vichi, Jerí, Cortés-Francisco, Palacios, & Caixach, 2014; the “dark roast” point (Holscher, & Steinhart, 1992; Mayer et al., 1999;
Quintanilla-Casas, Dulsat-Serra, Cortés-Francisco, Caixach, & Vichi, Kumazawa & Masuda, 2003a; Baggenstoss et al., 2008); while at more
2015; Vichi, Dalmau, & Caixach, 2015). This procedure is based on the advanced roasting stages, degradation reactions can induce a slowdown
selective and efficient reaction between thiols and a reagent in their formation or even a decrease in the amount of them in the coffee
containing selenium: ebselen, which enables the derivatization and iso- (Baggenstoss et al., 2008).
lation of the thiols in minimum time and with minimal sample manip- Methanethiol content increases greatly during the first stages
ulation. Moreover, HRMS provides information on molecular structure of roasting; while 2-furfurylthiol and 3-mercapto-3-methyl-1-butyl
and composition, and is crucial in food analysis to avoid interference formate require higher temperatures than methanethiol does for their
from isobaric compounds and thus false positives (Kaufmann, 2012). formation reactions, so their formation starts later. Nevertheless, the
This method provided thiol concentrations in coffee below those content of 2-furfurylthiol in coffee is mainly determined by the time of
previously reported (Table 1); although the results achieved in other roasting (Baggenstoss et al., 2008). The stability of the molecular struc-
matrices such as wine and beer were in line with those obtained ture or the existence of a considerable pool of precursors allows the con-
using other derivatization reagents (Vichi, Cortés-Francisco, & Caixach, centration of 2-furfurylthiol to increase over longer roasting times than
2015). those of other thiols, such as 3-mercapto-3-methyl-1-butyl formate,
even after excessive roasting (Schenker et al., 2002; Baggenstoss et al.,
4. Formation of thiols in coffee 2008). By comparing the behavior during roasting of 3-mercapto-3-
methyl-1-butanol and the corresponding esters, different kinetics have
4.1. Mechanisms of formation been reported. 3-Mercapto-3-methyl-1-butanol and 3-mercapto-3-
methyl-1-butyl formate increase linearly with the degree of roasting;
The mechanism of formation of volatile thiols in roasted coffee is still while mercapto-3-methyl-1-butyl acetate sharply increases only at ad-
not completely understood. However, it is generally accepted that vanced degrees of roasting (Kumazawa & Masuda, 2003a). As the acetic
sulfur-containing amino acids are the key precursors and the sulfur acid content in coffee beans is always slightly more than that of formic
source for reactions with sugars and other minor compounds that acid, this behavior has been explained by different and temperature-
occur during coffee bean roasting. Maillard-type reactions play a dependent reactivity of these acids, rather than the differences in their
major role in coffee thiol formation. The formation of 2-furfurylthiol amounts (Kumazawa & Masuda, 2003a).
and 2-methyl-3-furanthiol from the reaction between pentoses or Moreover, the rate of heat transfer during roasting is reported
hexoses and cysteine, through the formation of furaldehyde and H2S, to have an effect on the volatile profile and the evolution of thiols in
has been reported in model systems (Hofmann & Schieberle, 1997, coffee beans. In fact, to an equal degree of roasting, different time–
1998a, 1998b; Cerny & Davidek, 2003; Cerny, 2008) and confirmed temperature combinations lead to distinct volatile compositions,
by biomimetic in-bean experiments (Poisson, Schmalzried, Davidek, including thiol profiles (Schenker et al., 2002; Baggenstoss et al.,
Blank, & Kerler, 2009). In addition to 2-furfurylthiol, thermally 2008). Methanethiol, 3-methyl-2-butene-1-thiol and 3-mercapto-3-
treated solutions of glucose/cysteine or rhamnose/cysteine led to the methyl-1-butyl formate seem to be favored by higher temperatures,
986 N. Dulsat-Serra et al. / Food Research International 89 (2016) 982–988

since significantly higher concentrations are reached using high- methanethiol was observed in either American coffee (Genovese et al.,
temperature-short roasting time processes; while 2-furfurylthiol has 2014) or in Neapolitan coffee (Caporaso et al., 2014). These varying re-
been reported to be more abundant when a low-temperature long- sults hinder the drawing of clear conclusions regarding the influence of
time process is adopted (Schenker et al., 2002; Baggenstoss et al., 2008). these methods on coffee thiol extraction.

4.3. Influence of coffee species, variety and geographical origin on 5. Degradation of thiols and coffee going stale
thiol profile
5.1. Thiol depletion in brewed coffee
Although the roasting process is the main determinant of coffee
thiol formation, other factors intrinsic to the coffee bean have been The main problem with storing or processing brewed coffee is the
shown to play a significant role in the development of the thiol instability of its typical aroma; in particular of the roasty-sulfury note,
fraction. To similar degrees of roasting, both genetic and geographical which decreases in intensity shortly after coffee is brewed (Hofmann
factors produce differences in coffee thiol profiles. By comparing et al., 2001; Hofmann & Schieberle, 2002). The modification of coffee
coffee species, 2-furfurylthiol and methanethiol show significantly aroma quality, also known as going stale or staling, is caused by a
higher concentrations or sensory impact in robusta (Coffea canephora decrease of some potent odorants; in particular volatile thiols. Several
var. robusta) than arabica (Coffea arabica) coffee powders (Tressl & studies have sought to clarify the mechanisms of thiol degradation in
Silwar, 1981; Holscher & Steinhardt, 1992; Semmelroch et al., 1995; brewed coffee. In addition to thiol volatility, their sensitivity to oxidative
Semmelroch & Grosch, 1995); while the amounts or the sensory impact processes and their reactivity toward the matrix compounds are
of 3-methyl-2-buten-1-thiol and 3-methyl-1-butyl formate reported in considered the principal causes of thiol loss.
arabica and robusta coffee were comparable (Semmelroch & Grosch, Thiols in an organic model solution were observed to oxidize rapidly
1995, 1996; Semmelroch et al., 1995). The reports of the abundance of to disulfides even at low temperatures (Hofmann et al., 1996).
2-methyl-3-furanthiol in the species are equivocal, indicating that this Oxidation of thiols under Fenton type reactions has also been studied
is not the main factor affecting its content. It was found to be more (Blank et al., 2002), indicating that hydroxyl radicals (•OH), generated
abundant in some arabica coffee powders (Tressl & Silwar, 1981); in brewing coffee from hydrogen peroxide and transition metals, can in-
but its sensory impact was higher in other robusta coffee samples duce the formation of dimers as oxidation products. Model studies with
(Semmelroch & Grosch, 1995). 2-furfurylthiol revealed the formation of difurfuryl disulfide as the
In brewed coffee, Semmelroch and Grosch (1995) reported in an major component.
initial study that the contribution to the aroma of several thiols did Regarding flavor binding phenomena, Maillard reaction products,
not differ with the coffee species; while in a later study they observed melanoidins, phenols and their quinones have been indicated as
that the concentration and the OAV of 2-furfurylthiol and methanethiol, being mainly responsible for thiol depletion in brewed coffee
but not that of 3-mercapto-3-methyl-1-butyl formate, were notably (Hofmann et al., 2001; Hofmann & Schieberle, 2002; Charles-Bernard
higher in brewed robusta coffee (Semmelroch & Grosch, 1996). et al., 2005a; Charles-Bernard et al., 2005b; Müller & Hofmann, 2005;
The variety and geographical origin of coffee have also been reported Müller, Hemmersbach, Van't Slot, & Hoffmann, 2006; Müller &
to influence the volatile thiol profile (Mayer et al., 1999; Akiyama et al., Hofmann, 2007). Thiols have been demonstrated to covalently bind
2008; Vichi et al., 2014; Quintanilla-Casas et al., 2015). Nevertheless, the (excluding disulfide bonds) to coffee melanoidins by the results of
same studies do not allow us to clearly distinguish the effects of the two Hofmann et al. (2001; 2002). The proposed reaction pathway involved
factors, as samples of different geographical origin often also belong to diquaternary pyrazinium ions derived from the CROSSPY radical; an
different varieties. intermediate of melanoidin formation in roasted coffee (Hofmann &
Schieberle, 2002). Thioether derivatives from pyrazinium intermedi-
4.4. Influence of extraction conditions on thiols in brewed coffee ates, and 2-furfurylthiol, 3-mercapto-3-methyl-1-butyl formate and
2-methyl-3-furanthiol have been identified in model solutions, thus
The amount of thiols in brewed coffee is not only related to the initial corroborating the proposed mechanism (Hofmann & Schieberle, 2002).
concentration in the powder, but it also depends on the efficiency of the Although the effect of chlorogenic acids on the decrease of free
solid–liquid extraction during the brewing process. This efficiency thiols was not clear in model system (Hofmann & Schieberle, 2002),
should be proportional to the polarity of the thiols, although the extrac- biomimetic “in-bean” experiments demonstrated that chlorogenic
tion yields are not always correlated to thiol polarity (Mayer et al., 2000; acids and their thermal degradation phenolics, catalyzed by transition
Semmelroch & Grosch, 1996) but to physical parameters related to the metals, are relevant thiol-binding site precursors in raw coffee
brewing method. These parameters are: the proportions between coffee (Müller & Hofmann, 2005). Thiol conjugates with phenols and with
and water; the water temperature and pressure; and the extraction quinones formed by chlorogenic acid degradation, such as catechol,
time. The influence of the extraction method on coffee aroma has 4-ethylcatechol and hydroxyhydroquinone, were shown to be present
been assessed by some authors (Andueza et al., 2003; Caporaso et al., in both model studies and real coffee brews, and the oxidative coupling
2014; Genovese et al., 2014), but information on the behavior of thiols of 2-furfurylthiol and hydroxyhydroquinone was stated as one of the
under different coffee brewing methods is extremely scarce. In fact, principal causes of thiol losses during storage of brewed coffee
for volatile sulfur compounds, only methanethiol data are available. (Müller et al., 2006; Müller & Hofmann, 2007).
This thiol, quantified as percentage of peak areas, is always more abun- Finally, the degradation of 3-mercapto-3-methyl-1-butyl formate
dant in espresso coffee than in other types of brewed coffee. The ratio and acetate observed in thermally-treated coffee drinks has been
between coffee powder and water, as well as the extraction pressure, attributed to the hydrolysis of the esters with the production of
could justify this higher content. In addition, the water temperature is 3-mercapto-3-methyl-1-butanol (Kumazawa & Masuda, 2003b).
crucial to the final quality of the espresso coffee and the extraction The molecular structure of thiols plays a primary role in their
efficiency of methanethiol; its effect varied according to the type of reactivity and in their depletion during storage of brewed coffee. First,
coffee: arabica, robusta natural blend and robusta torrefacto blend. The although all thiols decrease in the presence of melanoidins, the most
highest amount of methanethiol was achieved at 96 °C, 88 °C–92 °C pronounced effects have been observed for 2-furfurylthiol (Hofmann
and 92 °C–98 °C, respectively (Andueza et al., 2003). & Schieberle, 2002). Likewise, the formic acid ester of 3-mercapto-3-
Meanwhile, coffee brewed using the Moka method showed slightly methyl-1-butanol showed a lower thermal stability and a higher pH
lower contents of methanethiol than espresso coffee did (Genovese dependence than the corresponding acetic acid ester, which was
et al., 2014; Caporaso et al., 2014); while the lowest content of ascribed to its molecular structure (Kumazawa & Masuda, 2003b).
 N. Dulsat-Serra et al. / Food Research International 89 (2016) 982–988 987

In addition, tertiary thiols were found to be more stable in brewed cof- important part in modulating coffee thiol profiles. Nevertheless,
fee, followed by secondary and primary thiols, and a correlation be- although much progress has been made, thiol chemistry under real
tween thiol hydrophobicity and their interaction with coffee matrix roasting conditions should be further elucidated, and only fragmentary
components was shown (Charles-Bernard et al., 2005b). It was also sug- information is available on the effect of brewing conditions. Moreover,
gested that the molecular structure determines the mechanism of thiol while extensive knowledge has been acquired regarding thiol degrada-
degradation in coffee brew models (Charles-Bernard et al., 2005b); tion in brewed coffee, little information is available on the modifications
while aliphatic thiols, such as methanethiol and ethanethiol seem to volatile thiols undergo during roasted coffee storage or the mechanisms
react mainly by nucleophilic addition on quinones or pyrazinium driving thiol degradation during roasted coffee storage. In-depth
cations in the coffee matrix, an additional radical mechanism has been information on coffee thiol chemistry, occurrence and dependence
hypothesized for furanic and benzylic thiols. on technological factors would be useful to enhance coffee quality
The characteristics and storage conditions of brewed coffee also management.
influenced the depletion of free thiols. Thiol-binding activity of non-
volatile components of brewed coffee was shown to be proportional
Acknowledgments
to the roasting degree (Charles-Bernard et al., 2005a; Müller &
Hofmann, 2005; Müller & Hofmann, 2007). Moreover, thiol degradation
This study was supported by the Spanish Ministerio de Economia y
and the resulting staling of the coffee brew are accentuated by Competitividad through the Ramón y Cajal program (RYC-2010-07228).
heating or by keeping the coffee warm during storage or processing,
and by pH N 4 (Hofmann & Schieberle, 2002; Kumazawa & Masuda,
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