Food Chemistry 120 (2010) 561–571

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Food Chemistry
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Analytical Methods

Changes of volatile compounds in wine vinegars during their elaboration

in barrels made from different woods
R.M. Callejón a, M.J. Torija b, A. Mas b, M.L. Morales a,*, A.M. Troncoso a
a
Área de Nutrición y Bromatología, Facultad de Farmacia, Universidad de Sevilla, C/P, García González n°2, E-41012 Sevilla, Spain
b
Departamento de Bioquímica y Biotecnología, Facultad de Enología, Universitat Rovira i Virgili, C/Marcel
lí Domingo s/n, E-43007 Tarragona, Spain

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

Article history: Changes in the volatile components of red wine vinegars and balsamic vinegars were investigated during
Received 27 October 2008 1 year of aging in wood barrels and bottles. Barrels of four different woods (oak, chestnut, acacia and
Received in revised form 8 October 2009 cherry) were used. A total of 57 volatile compounds were analysed by Gas Chromatography–Flame
Accepted 12 October 2009
Ionization Detection (GC–FID) and Headspace Sorptive Extraction GC–Mass Spectrometry (HSSE-TD–
GC–MS). We observed significant increases in the total content of volatile compounds only for balsamic
vinegars. The concentrations of ethyl furoate, ethyl benzoate, benzaldehyde and acetophenone were
Keywords:
highest in cherry barrels. These compounds, then, seem to be characteristic of this wood. Oak lactones
Volatile compounds
Aging
presented the highest increases for vinegars aged in oak. Eugenol was only present in vinegars aged in
Wine vinegar chestnut and oak barrels. Oak and cherry seem to be the best type of wood for aging of vinegar due to
Wood their distinctive aromatic characteristics.
HSSE–GC–MS Ó 2009 Elsevier Ltd. All rights reserved.

1. Introduction phenolic profile (Tesfaye, Morales, García-Parrilla, & Troncoso,

2002) and the aroma of wine vinegars (Callejón, Morales, Silva
Barrels have been widely used to age wines and other beverages Ferreira, & Troncoso, 2008a; Morales, Tesfaye, García-Parrilla, Ca-
for centuries (Waterhouse & Towey, 1994). Most casks used for this sas, & Troncoso, 2002). It is well known that when vinegars are
purpose are made of oak wood (Pérez-Coello, Sanz, & Cabezudo, aged in barrels, the volatile compounds are enriched mainly as
1997), which comes mainly from two sources: American oak the result of two important processes: firstly, they are concen-
(Quercus alba) and French oak (Quercus robur and Quercus petraea). trated because water is lost through the wood pores; and, sec-
The chemical compositions of these types of wood have been stud- ondly, new compounds are formed, such as esters (Morales et al.,
ied and are quantitatively different (Bozalongo, Carrillo, Fernández 2002). In addition, barrel oak wood is a porous material that allows
Torroba, & Tena, 2007; Díaz-Maroto, Guchu, Castro-Vazquez, de processes to occur that are associated with the so-called ‘‘low oxi-
Torres, & Pérez-Coello, 2008; Singleton, 1995). dation conditions” (Vivas & Glories, 1993).
The production of quality wine vinegars involves a maturation Nowadays, oak is the wood that is most commonly used in the
step in wood barrels. This is the case of Jerez-Xérès-Sherry DO aging of wines or vinegars although chestnut and, more rarely, aca-
(denomination of origin), which is matured in barrels of Quercus cia, cherry or mulberry are also occasionally used. However, the
alba (American oak). The minimum time required for a vinegar to influence of the type of wood on the volatile composition of the
be considered Sherry vinegar is six months (Consejería de Agricul- aged vinegars has not been studied yet. The porosity and the chem-
tura y Pesca., 2000). Another traditional vinegar marketed all ical composition of each type of wood are different and they may
around the world is the Aceto Balsamico Tradizionale. This vinegar affect the final aroma of vinegars. Empirical data suggest that mul-
is made in Modena and Reggio Emilia with cooked grape must, berry is more porous than other woods such as acacia, cherry or
through a three-step process: conversion of sugar to ethanol by chestnut, although these last three are more porous than oak wood
yeast; oxidation of ethanol to acetic acid by acetic acid bacteria; (Vivas, Debeda, Menil, de Gaulejac, & Nonier, 2003).
and, finally, at least 12 years of aging in a set of barrels of different The goals of the present work are, first, to evaluate how the ar-
woods and volumes (Giudici, Gullo, & Solieri, 2009). oma profile changes during the elaboration of red and white wine
During vinegar aging, several processes considerably improve vinegars in barrels made from four different types of wood (chest-
sensorial complexity. Aging in wood changes the colour, the poly- nut, acacia, cherry and oak); second, to study how each type of
wood influences the aroma of the aged vinegars; and, third, to
compare the final aroma of vinegars aged in wood with that of vin-
* Corresponding author. Tel.: +34 954 556760; fax: +34 954 233765.
E-mail address: mlmorales@us.es (M.L. Morales). egars aged in glass bottles.

0308-8146/$ - see front matter Ó 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.foodchem.2009.10.026
562 R.M. Callejón et al. / Food Chemistry 120 (2010) 561–571

Table 1
Volatile compounds of red wine vinegar aged in winery 1 (Banyuls, France).

No. Compound Mean concentration (lg/L) ± SD

Acacia (A)c Cherry (C)c Oak (O)c Chestnut (N)c
Initio Final Initio Final Initio Final Initio Final
Aldehydes
1 Acetaldehydea,b 14.2 ± 0.3 34 ± 5 25 ± 4 67 ± 8 5.25 ± 0.01 70 ± 8 24.7 ± 0.2 95 ± 6
2 Hexanal 9.5 ± 1.2 84 ± 3 37.3 ± 1.6 10.8 ± 1.4 44 ± 1 13 ± 1 10 ± 1 27 ± 3
3 2-Furfuraldehyde 841 ± 81 925 ± 84 127 ± 16 104 ± 6 418 ± 54 201 ± 23 294 ± 10 396 ± 54
4 Benzaldehyde 49 ± 3 nq 69 ± 5 nq 89 ± 3 nq 52.5 ± 1.1 nq
5 5-Methyl-2- nd 184 ± 9 nd nd nd nd nd nd
furfuraldehyde
6 Vanillina nq 2.4 ± 0.3 1.17 ± 0.11 3.3 ± 0.3 nq 2.66 ± 0.02 0.88 ± 0.08 3.61 ± 0.19
Total aldehydesa 15 38 27 71 6.3 73 26 100
Acetals
7 Acetaldehyde 105.9 ± 1.5 130 ± 14 122.4 ± 1.1 176 ± 8 47.86 ± 0.17 126 ± 9 571.6 ± 1.5 194.6 ± 1.5
diethylacetala
Acetic esters
8 Methyl acetatea 11.5 ± 0.5 42 ± 3 15 ± 1 25 ± 1 10.08 ± 0.23 34 ± 3 5.99 ± 0.16 38.2 ± 2.3
9 Ethyl acetatea,b 1315 ± 170 2888 ± 369 1157 ± 75 1618 ± 216 132 ± 7 1993 ± 85 221 ± 1 3064 ± 55
10 Propyl acetate 516 ± 17 1380 ± 23 566 ± 25 948 ± 14 385 ± 3 691 ± 27 121 ± 5 1421 ± 14
11 Isobutyl acetatea 1.17 ± 0.07 2.9 ± 0.1 1.28 ± 0.04 1.80 ± 0.01 0.97 ± 0.06 1.4 ± 0.01 0.33 ± 0.04 2.8 ± 0.1
12 Butyl acetate nd nq nd nd nd nd nd nq
13 Isoamyl acetatea 3.1 ± 0.2 8.0 ± 0.4 3.6 ± 0.2 3.36 ± 0.06 2.94 ± 0.02 2.5 ± 0.3 1.2 ± 0.2 6.6 ± 0.01
15 Hexyl acetate nd nq nd nd nd nd nd nq
16 Phenylmethyl acetate nd nd nd nd nd nd nd nd
17 Benzyl acetate nd nd nd nd nd nd nd nd
18 2-Phenylethyl acetatea 0.81 ± 0.07 1.94 ± 0.04 0.92 ± 0.12 0.79 ± 0.12 1.0 ± 0.1 0.77 ± 0.09 0.69 ± 0.04 1.88 ± 0.20
Total acetic estersa,d 17 57 21 32 15 40 8 50
Ethyl esters
19 Ethyl propanoate 156 ± 7 537 ± 27 155 ± 5 480 ± 16 118 ± 3 343 ± 21 159 ± 4 628 ± 6
20 Ethyl isobutyrate 160 ± 4 803 ± 34 175 ± 3 547 ± 24 176 ± 7 465 ± 44 168 ± 12 869 ± 31
21 Ethyl butyrate nq nq nq nq nq nq 134 ± 13 nq
22 Ethyl isovalerate nd 97 ± 7 nq 155 ± 9 nd 150 ± 6 nq 178 ± 7
23 Ethyl valerate 12 ± 0.2 nq nq nq nd nq nq nq
24 Ethyl hexanoate nd 59 ± 2 nd nq nd nq 174 ± 26 68 ± 3
26 Ethyl lactatea 3.7 ± 0.3 1.33 ± 0.05 4.1 ± 0.3 2.38 ± 0.22 2.75 ± 0.09 1.23 ± 0.02 19.1 ± 1.5 2.2 ± 0.3
27 Ethyl octanoate nd nd nd nd nd nd nd nd
28 Ethyl furoate 26.5 ± 1.9 51.0 ± 0.7 72 ± 5 140 ± 1 34 ± 1 77 ± 6 21.4 ± 1.3 80 ± 4
29 Ethyl benzoate nd nd nq nq nd nd nd nd
30 Diethyl succinatea 1.65 ± 0.06 1.54 ± 0.03 2.24 ± 0.32 1.40 ± 0.01 2.16 ± 0.19 2.26 ± 0.13 1.65 ± 0.04 2.29 ± 0.25
Total ethyl estersa 5.8 4.4 6.7 5.1 5.2 4.5 21 6.3
Alcohols
31 Metanola,b 79 ± 1 84 ± 11 82 ± 5 63 ± 3 130.3 ± 0.8 70 ± 5 112 ± 13 136 ± 19
32 Ethanola,b,e 3510 ± 22 4143 ± 573 4546 ± 653 3339 ± 10 6287 ± 704 3284 ± 14 15,093 ± 227 8125 ± 1297
(0.4) (0.5) (0.6) (0.4) (0.8) (0.4) (1.9) (1.0)
33 1-Propanola,b 3.4 ± 0.2 4.0 ± 0.4 4.3 ± 0.4 3.2 ± 0.3 6.57 ± 0.24 1.19 ± 0.03 5.4 ± 0.2 8.63 ± 0.05
34 Isobutanola 6.89 ± 0.13 9.2 ± 0.7 10.9 ± 0.9 6.55 ± 0.12 11.65 ± 0.04 7.9 ± 0.5 11.4 ± 1.5 9.5 ± 0.3
35 2-Methyl-1-butanola 7.5 ± 0.8 15.0 ± 0.4 7.6 ± 0.4 13.5 ± 0.3 6.9 ± 0.5 11.26 ± 0.05 15.68 ± 0.02 15.6 ± 0.6
36 3-Methyl-1-butanola 41 ± 3 46.2 ± 0.5 42.3 ± 1.8 46.5 ± 0.8 34.9 ± 0.8 29.3 ± 1.6 75 ± 4 46.5 ± 0.8
37 1-Hexanol 194 ± 10 209 ± 3 157 ± 8 nq 167 ± 4 nq 519 ± 20 168 ± 3
38 Cis-3-hexen-1-ol 36.9 ± 1.6 43.3 ± 0.8 41 ± 4 35.0 ± 0.2 35 ± 1 31.7 ± 0.6 61 ± 9 46.2 ± 0.4
39 Benzyl alcohol 160 ± 13 441 ± 63 132 ± 8 388 ± 4 184 ± 10 787 ± 29 164 ± 5 756 ± 45
40 Furfuryl alcohol nd 758 ± 93 nq 200 ± 11 nq 393 ± 6 488 ± 19 490 ± 50
41 2-Phenylethanola 17.5 ± 1.6 18 ± 3 20 ± 3 14.67 ± 0.02 23 ± 7 30.3 ± 2.2 20.9 ± 1.3 28.7 ± 1.5
Total alcoholsa,f 157 177 168 148 214 151 242 247
Ketones
42 Diacetyla nd nd nd nd nd nd nd 1.24 ± 0.08
43 Acetoina 362 ± 39 334.2 ± 0.2 304 ± 32 498 ± 64 194 ± 16 496 ± 21 107 ± 16 501 ± 54
44 Acetophenone nd nq nq 57.2 ± 1.6 nq nq nq nq
Total ketonesa 362 334 304 498 194 496 107 502
Acids
45 Isovaleric acida 2.2 ± 0.3 2.5 ± 0.1 2.9 ± 0.3 6.4 ± 0.3 1.16 ± 0.01 11.2 ± 0.1 0.78 ± 0.09 5.0 ± 0.3
46 Hexanoic acid 553 ± 30 1905 ± 173 634 ± 35 783 ± 14 437 ± 53 2008 ± 71 602 ± 83 2096 ± 97
47 Heptanoic acid nq 267 ± 35 98 ± 7 430 ± 49 nd 133 ± 16 nq 279 ± 5
48 Octanoic acid 189 ± 7 292 ± 30 204 ± 15 274 ± 17 160 ± 14 497 ± 63 231 ± 33 296 ± 22
49 Nonanoic acid nd nq nd nq nd nq nd 53 ± 1
50 Decanoic acid nd 20.4 ± 0.6 31 ± 2 35.5 ± 1.5 27.0 ± 1.1 46 ± 1 38 ± 3 15 ± 1
Total acidsa 2.9 5.0 3.9 7.8 1.8 14 1.7 7.7
Terpenes
51 Limonene 91.3 ± 2.4 nd 93 ± 7 nd 89.4 ± 2.3 nd nq nd
Lactones
52 c-Butyrolactonea 0.6 ± 0.1 2.6 ± 0.3 1.05 ± 0.06 1.77 ± 0.15 1.15 ± 0.01 1.46 ± 0.04 1.58 ± 0.14 2.58 ± 0.02
53 Trans-b-methyl-c- nd nd nd nd 102 ± 6 313 ± 15 nd nd
octalactone
 R.M. Callejón et al. / Food Chemistry 120 (2010) 561–571 563

Table 1 (continued)

No. Compound Mean concentration (lg/L) ± SD

Acacia (A)c Cherry (C)c Oak (O)c Chestnut (N)c
Initio Final Initio Final Initio Final Initio Final
54 Cis- b -methyl-c- nd nd nd nd 363 ± 35 1534 ± 197 nd nd
octalactone
Total lactonesa 0.6 2.6 1.05 1.77 1.15 1.6 3.3 2.58
Phenols
55 Guaiacol 14.4 ± 1.7 22 ± 2 6.2 ± 0.6 6.27 ± 0.02 8.4 ± 1.1 23.0 ± 0.3 5.2 ± 0.5 8.7 ± 0.1
56 Eugenol nd nd nd nd nq 118 ± 16 nd 87 ± 10
57 4-Ethylphenol 49 ± 6 52.1 ± 0.5 88 ± 10 65 ± 2 94 ± 5 102 ± 8 149 ± 16 162 ± 22
Total phenols 63 74 94 71 103 243 154 258
Total amountsa 5491 7779 6357 5896 6905 6185 16,293 12,299
Total amountsa,d,e 666 748 654 939 486 908 979 1110
Acetic acid degreeg 6.6 6.8 6.3 6.9 6.3 6.6 6.7 7.3
Dry extractg,h 8.8 10.2 9.1 10.9 9.0 10.2 9.1 10.6
pH 2.9 2.9 2.9 2.9 2.8 2.9 2.9

nd: not detected.

nq: below quantification limit.
a
Concentration in mg/L.
b
GC-FID.
c
Kind of wood of aging barrels.
d
Without considering ethyl acetate.
e
Value in brackets is alcoholic degree.
f
Without considering ethanol.
g
g/100 mL.
h
Data transfer by Cerezo et al. (2009).

2. Experimental Headspace Sorptive Extraction (HSSE) and then determined by

Gas Chomatography–Mass Spectrometry (HSSE–GC–MS).
2.1. Samples
2.3.1. GC-FID analysis
Twelve wine vinegars produced from three wines, two red Ethyl acetate, acetaldehyde, methanol, ethanol and propanol
wines (Grenache variety) and one white wine (Trebbiano variety), were quantified by GC-FID using the method proposed by Morales,
were aged in four types of 60 L wood barrels (oak, chestnut, acacia González, Casas, and Troncoso (2001). A 1 mL sample was filtered
and cherry). Each of the three series was aged in different wineries through 0.22 lm Millex-GV13 filters and 10 lL of 4-methyl-2-pent-
located in Banyuls, France (winery 1), Priorat, Spain (winery 2) and anol at 102.14 mg/L was added as the internal standard (IS). The
Reggio Emilia, Italy (winery 3). The balsamic vinegar was produced filtered samples were analysed using a Hewlett–Packard 6890
by mixing cooked grape must and white wine vinegar. The acetic gas chromatograph equipped with a flame ionization detector
degree of the vinegars at the beginning of the aging was: 6.5°, (FID). 1 lL was injected in the split mode (1:60) into a CP-Wax
6.4° and 5.7° for vinegars of winery 1, 2 and 3, respectively. Vine- 57 CB column, 50 m  0.25 mm ID  0.2 lm film thickness (Varian,
gars were aged for one year in the same type of barrels in which Middelburg, Netherlands). The carrier gas was H2 at 1 mL/min. The
they had been acetified. The 60 L barrels were manufactured by program temperature was: 35 °C for 5 min, ramped at 4 °C/min to
the barrel-maker Torner (Vilafranca del Penedes, Spain). In addi- 150 °C held for 17.5 min. The injector was set at 220 °C and the
tion, winery 2 (Priorat) carried out four simultaneous aging con- detector at 250 °C. The data acquisition software was the HPChem-
trols in 8 L glass bottles closed by cork stoppers. Hence, a total of station data processing system (Agilent Technologies).
16 aging processes were studied by taking samples at the begin-
ning and at the end of aging (0 and 12 months, respectively). 2.3.3. HSSE–GC–MS analysis
The HSSE sampling conditions were as follows (Callejón, Tronc-
2.2. Reagents and chemicals oso, & Morales, 2008b): 5 mL of sample (wine vinegar) and 10 lL of
4-methyl-2-pentanol (IS) at 1045 mg/L was placed into a 20-mL
The standards of 57 aroma compounds (see Tables 1–4) were headspace vial with 1.67 g of NaCl. A 10 mm long stir bar coated
obtained from commercial sources as follows: 2, 3, 14, 15, 19–21, with a 0.5 mm polydimethylsiloxane (PDMS) layer (Twister, Ger-
23–27, 29–32, 40–42, 45–51, 53–57 (Sigma–Aldrich, Madrid, stel, Müllheim an der Ruhr, Germany) was put in an open glass in-
Spain); 1, 4, 6–10, 13, 17, 18, 28, 34–39, 44, 52 (Merck, Darmstadt, sert and placed in the vial to carry out the extraction in the
Germany); 5, 11, 12, 16, 22, 33, 43 (Fluka, Madrid, Spain). 4- headspace. Then, the vial was tightly capped and heated for
methyl-2-pentanol (Merck) was used as internal standard (IS). 60 min at 62 °C in a thermostatic bath. The stir bar was removed
Water was obtained from a Milli-Q purification system (Millipore, with tweezers, rinsed with Milli-Q water and dried with lint-free
USA). tissue paper. Finally, for the thermal desorption (TD), the stir bar
was placed in a glass tube 60 mm long, 6 mm OD and 4 mm ID.
2.3. Volatile compound analysis This tube was then placed on the autosampler tray of the thermo
desorption unit for GC–MS analysis.
We used two methods of analysis because we expected to find Gas Chromatography analysis was carried out with a 6890 Agi-
volatile compounds with different volatilities and a wide range of lent GC system coupled to a Agilent 5975 inert quadrupole mass
concentrations. So, the major volatile compounds were determined spectrometer equipped with a Thermo Desorption System (TDS2)
by direct injection using Gas Chromatography–Flame Ionization and a cryo-focusing CIS-4 PTV injector (Gerstel). The thermal
Detection (GC–FID). The minor compounds were extracted by desorption was performed in splitless mode and with a flow rate
564 R.M. Callejón et al. / Food Chemistry 120 (2010) 561–571

Table 2
Volatile compounds of red wine vinegars from winery 2 (Priorat, Spain) aged in wood (acacia and cherry) and bottle.

No. Compound Mean concentration (lg/L) ± SD

Acaciab Cherryb
c
Initio Final Bottle Initio Final Bottled
Aldehydes
1 Acetaldehydee,a 35.5 ± 0.5 60 ± 5 116 ± 6 66 ± 4 40 ± 2 134 ± 15
2 Hexanal nq 11.8 ± 1.5 19.6 ± 2.3 15.9 ± 1.6 11 ± 1 18.7 ± 0.3
3 2-Furfuraldehyde 426 ± 57 495 ± 26 584 ± 59 nd 198 ± 20 740 ± 83
4 Benzaldehyde nq nq nq 89.0 ± 1.8 295 ± ± 31 387 ± 14
5 5-Methyl-2-furfuraldehyde nd nq 43 ± 5 nd nd 35 ± 4
6 Vanilline nq 1.83 ± 0.13 nq nq 1.69 ± 0.18 nq
Total aldehydese 36 63 123 66 42 138
Acetals
7 Acetaldehyde diethylacetale 154 ± 5 133 ± 5 208 ± 9 270 ± 7 272 ± 24 266 ± 12
Acetic esters
8 Methyl acetatee 17.7 ± ± 0.3 45.62 ± 0.16 30.5 ± 3.4 10.28 ± 0.15 26.9 ± 2.6 28.2 ± 3.6
9 Ethyl acetatee,a 4476 ± 378 3276 ± 125 3348 ± 517 3892 ± 572 918 ± 27 2472 ± 347
10 Propyl acetate 3227 ± 17 2760 ± 188 3603 ± 264 2141 ± 143 2898 ± 44 4440 ± 263
11 Isobutyl acetatee 3.12 ± 0.13 2.9 ± 0.3 3.2 ± 0.2 2.05 ± 0.06 2.79 ± 0.08 3.7 ± 0.3
12 Butyl acetate 131 ± 7 71 ± 10 170 ± 19 88.3 ± 0.1 133 ± 12 363 ± 43
13 Isoamyl acetatee 10.2 ± 0.4 5.6 ± 0.3 8.64 ± 0.08 7.07 ± 0.23 9.3 ± 0.5 14 ± 2
14 Amyl acetate nd nd nq nd nd 63 ± 8
15 Hexyl acetate 69 ± 9 nd nq 63 ± 5 61 ± 8 159 ± 23
16 Phenylmethyl acetate 187 ± 19 nq 115 ± 4 nq nq 198 ± 29
17 Benzyl acetate nd nd nq nd nq nq
18 2-Phenylethyl acetatee 1.89 ± 0.23 0.80 ± 0.03 1.61 ± 0.14 1.10 ± 0.16 2.7 ± 0.3 3.8 ± 0.4
Total acetic esterse,f 37 57 48 23 44 55
Ethyl esters
19 Ethyl propanoate 661 ± 16 1343 ± 118 1352 ± 120.8 539 ± 16 1278 ± 16 1921 ± 228
20 Ethyl isobutyrate 458 ± 56 1267 ± 173 1107 ± 126 268 ± 10 793 ± 49 1552 ± 197
21 Ethyl butyrate nq nq 137 ± 11 nq 99 ± 1 2045 ± 21
22 Ethyl isovalerate nq 397 ± 33 288 ± 37 nq 145 ± 11 288 ± 33
23 Ethyl valerate nq 9.8 ± 0.9 10.0 ± 0.5 nq 10 ± 1 13.9 ± 1.6
24 Ethyl hexanoate 52 ± 6 142 ± 20 107 ± 16 43 ± 4 104 ± 9 217 ± 28
25 Ethyl heptanoate nd nd 8±1 nd nd 8±1
26 Ethyl lactatee 17.6 ± 0.4 2.0 ± 0.3 2.5 ± 0.3 14.2 ± 1.7 5.0 ± 0.4 5.5 ± 0.3
27 Ethyl octanoate nd nd nd nd nd 169 ± 25
28 Ethyl furoate 97 ± 9 99 ± 6 148 ± 17 191 ± 13 426 ± 30 412 ± 56
29 Ethyl benzoate nd nd nd 113 ± 7 245 ± 15 233 ± 4
30 Diethyl succinatee 22.5 ± 1.6 5.3 ± 0.7 15 ± 10 8.6 ± 1.2 16.6 ± 2.3 15 ± 2
Total ethyl esterse 41 11 21 24 25 26
Alcohols
31 Metanole,a 118 ± 18 107 ± 7 187 ± 4 170 ± 26 119 ± 9 213 ± 3
32 Ethanole,a,g 6522 ± 826 (0.8) 4240 ± 281 (0.5) 9223 ± 114 (1.2) 10784 ± 116 (1.3) 5863 ± 379 (0.7) 9421 ± 544 (1.2)
33 1-Propanole,a 22 ± 3 16.77 ± 0.02 37.0 ± 0.3 36 ± 1 27 ± 3 54 ± 3
34 Isobutanole 7.87 ± 0.17 13 ± 0.5 73.5 ± 0.2 8.43 ± 0.13 10.34 ± 0.08 10.3 ± 0.8
35 2-Methyl-1-butanole 13.62 ± 0.25 17.8 ± 0.6 13.9 ± 1.6 8.7 ± 0.4 12.0 ± 0.6 13.5 ± 1.8
36 3-Methyl-1-butanole 89 ± 6 67 ± 7 75 ± 3 75 ± 5 74 ± 4 80 ± 7
37 1-Hexanol 569 ± 20 nq 369 ± 42 438 ± 26 462 ± 23 732 ± 28
38 Cis-3-hexen-1-ol 58.9 ± 0.4 51.2 ± 2.5 60 ± 1 44 ± 1 55 ± 4 81 ± 3
39 Benzyl alcohol 5670 ± 608 518 ± 33 1402 ± 187 1657 ± 381 1022 ± 114 865 ± 109
40 Furfuryl alcohol 604 ± 66 589 ± 76 1492 ± 73 54 ± 4 519 ± 70 1401 ± 190
41 2-Phenylethanole 47 ± 6 20 ± 2 30 ± 5 14.8 ± 1.1 39 ± 5 33 ± 5
Total alcoholse,h 304 243 353 315 283 407
Ketones
42 Diacetyle nd nd 4.6 ± 0.5 nd 2.9 ± 0.3 14 ± 1
43 Acetoine 1437 ± 148 821 ± 116 699 ± 1 743 ± 53 1022 ± 115 713 ± 421
44 Acetophenone nd nd nq nq 139 ± 15 79 ± 10
Total ketonese 1437 821 704 743 1025 727
Acids
45 Isovaleric acide 3.1 ± 0.2 18.5 ± 0.3 8.0 ± 0.7 2.0 ± 0.1 5.5 ± 0.6 3.9 ± 0.3
46 Hexanoic acid 1636 ± 127 2152 ± 260 4129 ± 214 647 ± 10 3029 ± 289 2813 ± 383
47 Heptanoic acid nq 100 ± 1 227 ± 12 nq 166 ± 15 301 ± 42
48 Octanoic acid 975 ± 127 454 ± 44 1274 ± 41 222 ± 14 912 ± 130 935 ± 136
49 Nonanoic acid nd 62 ± 7 119 ± 5 nd 81 ± 10 nq
50 Decanoic acid 163 ± 21 37 ± 5 nq 222 ± 14 101 ± 13 nq
Total acidse 5.9 21 14 3.1 9.8 8
Terpenes
51 Limonene 112 ± 4 nd 79 ± 9 80 ± 3 nd 234 ± 15
Lactones
52 c-Butyrolactonee 3.9 ± 0.3 1.92 ± 0.08 4.7 ± 0.3 2.2 ± 0.1 2.3 ± 0.3 2.97 ± 0.21
53 Trans-b-methyl-c-octalactone nd nd nd nd nd nd
54 Cis-b-methyl-c-octalactone nd nd nd nd nd nd
Total lactonese 3.9 1.92 4.7 2.2 2.29 2.97
Phenols
55 Guaiacol 22.3 ± 0.1 22.5 ± 2.0 47 ± 6 8.0 ± 0.6 25.2 ± 0.6 36 ± 4
 R.M. Callejón et al. / Food Chemistry 120 (2010) 561–571 565

Table 2 (continued)

No. Compound Mean concentration (lg/L) ± SD

Acaciab Cherryb
c
Initio Final Bottle Initio Final Bottled
56 Eugenol nd nd nd nd nd nd
57 4-Ethylphenol 871 ± 37 329 ± 37 1583 364 ± 47 1101 ± 148 967
Total phenols 893 351 1630 372 1126 1003
Total amountse 13,018 8867 14,048 16,123 8487 13,523
Total amountse,f,h 2020 1351 1477 1447 1706 1630
Acetic acid degreei 6.4 8.4 6.9 6.0 8.7 6.1
Dry extracti,j 2.4 3.1 2.9 2.7 3.5 2.9
pH 3.0 2.8 2.9 3.0 2.9 3.0

nd: not detected.

nq: below quantification limit.
a
GC-FID.
b
Kind of wood of aging barrels.
c
Vinegars acetified in Acacia barrel and aging 1 year in bottle.
d
Vinegars acetified in Cherry barrel and aging 1 year in bottle.
e
Concentration in mg/L.
f
Without considering ethyl acetate.
g
Value in brackets is alcoholic degree.
h
Without considering ethanol.
i
g/100 mL.
j
Data transfer by Cerezo et al. (2009).

of 90 mL/min. The desorption temperature program was the fol- The main phenomenon that takes place during aging is the
lowing: 35 °C for 1 min, ramped at 60 °C/min to 250 °C held for enrichment of the aroma due to the loss of water through wood
5 min. The CIS-4 PTV injector, with a Tenax TA inlet liner, was held pores (Singleton, 1995). In this experiment, we only observed sig-
at –35 °C with liquid nitrogen for the total desorption time and nificant increases in the total volatile concentration during the
then raised at 10 °C/s to 290 °C and held for 4 min. The solvent vent aging of samples from winery 3. This concentration phenomenon
mode was used to transfer the sample to the analytical column. A is supported by the marked increase in dry extract observed in this
CPWax-57CB column, 50 m  0.25 mm, 0.20 lm film thickness winery (Table 4). However, vinegars aged in the other two wineries
(Varian, Middelburg, Netherlands) was used and the carrier gas (1 and 2) underwent decreases in most of the cases, being these
was He at a flow rate of 1 mL/min. The oven temperature program changes statistically significant for winery 2. These last results
was 35 °C for 5 min, which was then raised to 220 °C at 2.5 °C/min are not in agreement with Morales et al., 2002 who observed an
(held for 5 min). The quadrupole, source and transfer line temper- important enrichment of the volatile composition during the aging
atures were maintained at 150, 230 and 280 °C, respectively. Elec- of vinegar in wood barrels. This can be due to acetification pro-
tron ionization mass spectra in the full-scan mode were recorded cesses may be taking place at the same time as aging. Samples from
at 70 eV electron energy in the range 35–350 amu. wineries 1 and 2 showed increases in acetic acid content, being
All data were recorded using a MS ChemStation. The identity of considerable in winery 2 (average increases in acetic acid degree
peaks was assigned using the NIST 98 library and confirmed by ranging from 1.8 to 2.5) and a corresponding decrease in ethanol
standard retention indices when they were available. Quantifica- concentration. Vinegars from wineries 1 and 2 were filtered before
tion was performed by using the relative area to internal standard they were aged in wood barrels, but they were not sterilized.
of the target ion of each compound. The samples were analysed in Hence, the microbiological activity during aging (10e5 10e6 cells/
triplicate and blank runs were made with empty glass tubes before mL) was enough to continue transforming the ethanol into acetic
and after each analysis. RIs were calculated from the retention acid. Therefore, vinegars are suffering losses of ethanol due to
times of n-alkanes by linear interpolation, in accordance with the the simultaneous acetification and aging process. If we do not con-
literature (Silva Ferreira, Hogg, & Guedes de Pinho, 2003). sider the ethanol content we observed increases in the total vola-
tile concentration of vinegars of winery 1. This fact points out
that in the both wineries, 1 and 3, take place concentration phe-
2.4. Statistical analysis
nomena. These two wineries had environmental conditions that
provide higher average temperature and lower relative humidity,
One-way analysis of variance (ANOVA) and linear discriminant
favouring concentration processes (Singleton, 1995).
analysis (LDA) were performed using Statistica, version 7.0 soft-
As far as the evolution of the various groups was concerned, vol-
ware (Statsoft, Tulsa, USA).
atile acids were the only compounds to increase significantly in all
the aging processes. In wines fermented in wood, these compounds
3. Results and discussion also increase, so they seem to be extracted from the wood and par-
ticularly so in new barrels (González-Marco, Jiménez-Moreno, &
A total of 28 samples of wine vinegars aged in wood and in bot- Ancín-Azpilicueta, 2008). However, we observed that acids also in-
tles were analysed for 57 volatile compounds. Their respective con- creased in the samples stored in bottles. The average increase was
centrations are shown in Tables 1–4. Data are collected in chemical similar to that observed in vinegars from wineries 1 and 3. Hexa-
families. noic and heptanoic acids increased significantly in all aging exper-
Alcohols is the major group of compounds in finished vinegars iments. Octanoic and isovaleric acid increased in most of them. As
(3.4–12.6 g/L) due to the high amounts of residual ethanol. The has been previously found in wine vinegar, this last acid was the
next most abundant group of volatile compounds is acetic esters most abundant (Guerrero, Natera, Castro, & Barroso, 2007). Isova-
and the principal compound of this fraction is ethyl acetate. leric acid has an odor that has been described as cheese or foot (Az-
566 R.M. Callejón et al. / Food Chemistry 120 (2010) 561–571

Table 3
Volatile compounds of red wine vinegars from winery 2 (Priorat, Spain) aged in wood (oak and chesnut) and bottle.

No. Compound Mean concentration (lg/L) ± SD

Oakb Chestnutb
c
Initio Final Bottle Initio Final Bottled
Aldehydes
1 Acetaldehydee,a 52 ± 6 44 ± 5 71 ± 7 32 ± 4 41 ± 4 49 ± 5
2 Hexanal 24 ± 1 47 ± 6 16.2 ± 1.4 39 ± 2 38 ± 4 24.4 ± 3.4
3 2-Furfuraldehyde nq 598 ± 87 195 ± 15 nd 66 ± 3 76 ± 1
4 Benzaldehyde nq nq nq nq nq nq
5 5-Methyl-2-furfuraldehyde nd nd nd nd nd nd
6 Vanilline nd 3.6 ± 0.5 0.90 ± 0.08 nq 2.250 ± 0.00 3 nd
Total aldehydese 52 49 72 32 43 49
Acetals
7 Acetaldehyde diethylacetale 193 ± 7 90.7 ± 0.7 116 ± 13 184 ± 8 141.5 ± 0.3 101 ± 5
Acetic esters
8 Methyl acetatee 16.9 ± 0.5 40.1 ± 0.6 24.7 ± 0.5 14.1 ± 0.3 25.2 ± 0.6 21.8 ± 1.6
9 Ethyl acetatee,a 3955 ± 266 1739 ± 1 1614 ± 227 2905 ± 363 2660 ± 326 2089 ± 281
10 Propyl acetate 2207 ± 118 2078 ± 72 2584 ± 26 2681 ± 41 2466 ± 135 2876 ± 79
11 Isobutyl acetatee 2.17 ± 0.08 2.28 ± 0.02 2.15 ± 0.04 2.16 ± 0.13 2.57 ± 0.22 2.21 ± 0.19
12 Butyl acetate 83.8 ± 0.6 nq 106 ± 1 93 ± 2 89 ± 12 135 ± 8
13 Isoamyl acetatee 7.26 ± 0.05 5.87 ± 0.08 5.51 ± 0.13 7.61 ± 0.22 6.1 ± 0.5 6.5 ± 0.3
14 Amyl acetate nd nd nq nd nd nq
15 Hexyl acetate 62 ± 2 82 ± 3 nq nd nd nq
16 Phenylmethyl acetate 142 ± 6 nq 122 ± 18 137 ± 6 nq nq
17 Benzyl acetate nd nq nq nd nq nq
18 2-Phenylethyl acetatee 2.05 ± 0.28 1.03 ± 0.11 1.6 ± 0.2 1.49 ± 0.09 1.62 ± 0.22 1.6 ± 0.22
Total acetic esterse,f 31 51 37 28 38 35
Ethyl esters
19 Ethyl propanoate 527 ± 20 1142 ± 38 1166 ± 19 644 ± 20 1143 ± 123 1248 ± 41
20 Ethyl isobutyrate 284 ± 7 1033 ± 31 798 ± 8 394 ± 11 940 ± 42 1006 ± 67
21 Ethyl butyrate nq 143 ± 1 174 ± 4 nq 87 ± 7 131 ± 6
22 Ethyl isovalerate nq 491 ± 21 200 ± 7 nq 462 ± 25 203 ± 19
23 Ethyl valerate nq 11.4 ± 0.5 11.4 ±0.2 nq 9.5 ± 0.7 10.3 ± 0.4
24 Ethyl hexanoate nq 121 ± 9 121 ± 7 48.6 ± 1.4 122 ± 3 132 ± 9
25 Ethyl heptanoate nd nd nq nd nd nq
26 Ethyl lactatee 10.9 ± 0.1 2.09 ± 0.05 1.5 ± 0.2 14.3 ± 0.2 1.99 ± 0.13 1.7 ± 0.1
27 Ethyl octanoate nd nd nd nd nd 103 ± 11
28 Ethyl furoate 101 ± 5 122 ± 8 140 ± 16 94 ± 5 130 ± 1 141 ± 20
29 Ethyl benzoate nd nd nd nd nd nd
30 Diethyl succinatee 22 ± 3 6.5 ± 0.5 8.5 ± 1.3 15.3 ± 1.3 12.1 ± 1.6 7.5 ± 0.8
Total ethyl esterse 34 12 13 31 17 12
31 Metanole,a 193 ± 25 126 ± 19 155 ± 9 145 ± 20 111 ± 2 168 ± 22
32 Ethanole,a,g 9480 ± 1450 (1.2) 4204 ± 623 (0.5) 5553 ± 242 (0.7) 9471 ± 959 (1.2) 4927 ± 570 (0.6) 7673 ± 71 (1.0)
33 1-Propanole,a 35 ± 4 16.1 ± 1.7 22.6 ± 0.7 33 ± 3 18.4 ± 1.2 40 ± 6
34 Isobutanole 9.2 ± 0.6 12.9 ± 0.3 7.2 ± 0.2 9.2 ± 0.6 9.3 ± 0.6 7.1 ± 0.3
35 2-Methyl-1-butanole 10.6 ± 0.4 14 ± 1 9.1 ± 0.3 8.9 ± 0.4 14.00 ± 0.09 9.2 ± 0.6
36 3-Methyl-1-butanole 78.3 ± 0.3 53.7 ± 0.6 51 ± 1 82 ± 3 55.9 ± 1.7 56 ± 2
37 1-Hexanol 449.1 ± 0.6 nq 282 ± 13 503 ± 15 nq 469 ± 23
38 Cis-3-hexen-1-ol 55.0 ± 1.2 45.2 ± 0.4 54 ± 2 58 ± 1 45 ± 4 59 ± 3
39 Benzyl alcohol 4407 ± 466 630 ± 37 721 ± 102 3869 ± 421 868 ± 114 545 ± 61
40 Furfuryl alcohol nd 1044 ± 58 304 ± 43 nq 342 ± 20 157 ± 24
41 2-Phenylethanole 29 ± 5 24.7 ± 0.7 32 ± 1 24 ± 3 33 ± 4 21 ± 3
Total alcoholse,h 360 249 278 306 244 303
Ketones
42 Diacetyle nd nd 5.0 ± 0.6 nd nd 3.49 ± 0.07
43 Acetoine 488 ± 43 740 ± 33 809 ± 96 499 ± 6 686 ± 51 594 ± 49
44 Acetophenone nd nq nd nq nq nq
Total ketonese 488 740 814 499 686 598
Acids
45 Isovaleric acide 2.0 ± 0.2 16.3 ± 1.2 8.89 ± 0.04 1.78 ± 0.05 17.6 ± 0.2 3.37 ± 0.03
46 Hexanoic acid 1077 ± 45 3322 ± 164 2433 ± 198 1067 ± 55 3790 ± 505 1844 ± 199
47 Heptanoic acid nq 153 ± 8 103 ± 4 114 ± 5 242 ± 28 103 ± 2
48 Octanoic acid 284 ± 14 732 ± 70 1098 ± 28 301 ± 29 994 ± 118 434 ± 62
49 Nonanoic acid nd 86.3 ± 0.7 57 ± 3 nd 89 ± 12 nd
50 Decanoic acid 48 ± 6 136 ± 18 157 ± 4 17 ± 2 141 ± 19 nq
Total acidse 3.4 21 13 3.3 23 6
Terpenes
51 Limonene 76.6 ± 1.2 nd 104.3 ± 1.8 91.1 ± 1.7 nd 104.4 ± 0.9
Lactones
52 c-Butyrolactonee 1.23 ± 0.17 2.24 ± 0.06 1.75 ± 0.16 1.56 ± 0.19 2.1 ± 0.3 1.74 ± 0.15
53 Trans-b-methyl-c-octalactone 126 ± 13 161 ± 21 nd nd nd nd
54 Cis-b-methyl-c-octalactone 422 ± 54 1424 ± 198 nd nd nd nd
Total lactonese 1.8 3.8 1.75 1.56 2.1 1.74
Phenols
55 Guaiacol 13.9 ± 1.2 30.6 ± 0.8 22 ± 3 10.2 ± 0.1 10.7 ± 1.3 nq
 R.M. Callejón et al. / Food Chemistry 120 (2010) 561–571 567

Table 3 (continued)

No. Compound Mean concentration (lg/L) ± SD

Oakb Chestnutb
c
Initio Final Bottle Initio Final Bottled
56 Eugenol nq nq nq nq 162 ± 17 nd
57 4-Ethylphenol 427 ± 54 395 ± 55 1002 518 ± 49 932 ± 125 577
Total phenols 441 426 1024 528 1105 577
Total amountse 14,598 7159 8512 13461 8783 10,868
Total amountse,f,h 1604 1216 1345 1085 1196 1106
Acetic acid degreei 6.7 8.5 7.4 6.5 9.0 7.0
Dry extracti,j 2.6 3.2 2.6 2.7 3.2 2.9
pH 2.9 2.8 2.9 3.0 2.8 2.9

nd: not detected.

nq: below quantification limit.
a
GC-FID.
b
Kind of wood of aging barrels.
c
Vinegars acetified in Acacia barrel and aging 1 year in bottle.
d
Vinegars acetified in Cherry barrel and aging 1 year in bottle.
e
Concentration in mg/L.
f
Without considering ethyl acetate.
g
Value in brackets is alcoholic degree.
h
Without considering ethanol.
i
g/100 mL.
j
Data transfer by Cerezo et al. (2009).

nar, Lopez, Cacho, & Ferreira, 2001), its threshold for vinegar is Aldehydes and lactones reached higher concentrations at the
150 lg/L (Callejón, Morales, Silva Ferreira, & Troncoso, 2008a) end of aging in all cases, and in the samples from winery 2 the
and in high concentrations it can result in an off-flavour. changes were statistically significant.
Esters are continuously formed and hydrolysed and their oscil-
lations are independent of wood contact. Equilibrium is governed 3.1. Aging in barrels versus bottles
by the relative abundance of acids and alcohols, pH and tempera-
ture, among other factors. A comparative study of two kinds of aging, in wood barrels and
Acetic esters (mainly ethyl acetate) are formed during the aging glass bottles, was carried out in the winery 2.
of vinegars in outstanding quantities (Morales et al., 2001; Morales The overall content of volatile compounds was higher in vine-
et al., 2002). As can be seen in Tables 1–4, ethyl acetate was the gars aged in bottles, and the differences with respect to the vine-
most abundant acetic ester followed by methyl acetate. Both com- gars from wood barrels at the end of one year aging were
pounds make a different contribution to vinegar aroma because statistically significant. The amounts of aldehydes and alcohols
they do not present fruity aromas as the other acetic esters do. are significantly higher in vinegars from bottles. As mentioned
Ethyl acetate underwent significant changes in all the aging pro- above, the samples aged in wood barrels showed considerable in-
cesses: it increased in vinegars from wineries 1 and 3 and de- creases in acetic acid content, a corresponding decrease in ethanol
creased in samples from winery 2 (bottle and wood aging). On concentration and a microbiological activity during aging
the contrary, methyl acetate increased significantly in all aging (10e5 10e6 cells/mL). This suggests that acetification is taking
processes. The formation of methyl acetate is favoured by the place at the same time as aging. The degree of acetic acid of the
acidic environment (Morales et al., 2002) as it is the case of our samples stored in bottles also increased although to a lesser extent
samples (Tables 1–4), and high amounts of methanol. Red wines (from 0.1 to 0.7). This shows that there may have been microbio-
have a higher concentration of this alcohol (152 mg/L) than white logical activity in all samples except for vinegar from acacia wood
wines (63 mg/L) because the methoxyl group of the grape-skin aged in bottle, in which ethanol content did not decrease (Tables 2
pectins hydrolyzes (Ribéreau-Gayon, Glories, Maujean, & Dubour- and 3). Lack of air exchange in the bottle could limit the oxygen
dieu, 2006). Thus, the initial concentrations of methanol in red vin- available to microorganisms and thus reduce their activity. In both
egars ranged from 79 to 193 mg/L while white vinegars ranged aging experiments (wood and bottle), ethyl acetate decreased sig-
from 20 to 23 mg/L. Consequently, methyl acetate reached higher nificantly in most cases as a consequence of the ethanol require-
concentrations in red vinegars (22–46 mg/L) than in white vine- ment of acetic acid bacteria, which shifted the chemical
gars (13–23 mg/L). For the remaining acetic esters, significant in- equilibrium.
creases are observed for white wine vinegar (group 3) during Tesfaye, Morales, Benitez, Garcia-Parrilla, and Troncoso (2004)
aging. Possibly, this leads to a higher fruity character as a result reported increases in acetaldehyde during the experimental aging
of wood aging. of wine vinegar in bottles due to the oxidation of ethanol. In our
Regarding fatty acid ethyl ester we observed a phenomenon aging bottle assay, we observed increases in acetaldehyde in all
contrary to what happens in wine. These compounds are produced cases (Tables 2 and 3).
during yeast fermentation and they decrease during aging to reach Diacetyl is a compound formed from the oxidation of acetoin
a chemical equilibrium in wines. On the contrary, in vinegars, fatty and it is related to the aging of sherry vinegars in oak barrels (Mor-
acid ethyl esters decrease during the surface acetification process ales et al., 2002; Callejón, Morales, Troncoso, & Silva Ferreira,
because ethanol is consumed by acetic bacteria (Callejón et al., 2008c). Nevertheless, although we found this compound in all
2009) and they increased during aging (Tables 1–4), probably to our bottle experiments we found it in wood only when the increase
reach chemical equilibrium. These increases were statistically sig- in acetoin was considerable.
nificant for ethyl isobutyrate and ethyl isovalerate in all the pro- Limonene tends to increase in bottle aging whilst in wood it dis-
cesses and for ethyl propanoate and ethyl hexanoate in most of appears. These facts could be explained by the sorption phenome-
them. non in wood already hypothesized for other terpenes (linalool) in
568 R.M. Callejón et al. / Food Chemistry 120 (2010) 561–571

Table 4
Volatile compounds of white wine vinegars aged in winery 3 (Reggio Emilia, Italy).

No. Compound Mean concentration (lg/L) ± SD

Acacia (A)c Cherry (C)c Oak (O)c Chestnut (N)c
Initio Final Initio Final Initio Final Initio Final
Aldehydes
1 Acetaldehydea,b 38 ± 3 80 ± 12 27.9 ± 0.5 203 ± 26 35 ± 2 56 ± 4 33 ± 3 38 ± 5
2 Hexanal 5.0 ± 0.2 28 ±4 11.5 ± 0.6 43 ± 5 10.7 ± 0.8 61 ± 4 15.8 ± 1.9 49 ± 6
3 2-Furfuraldehyde 1096 ± 130 1330 ± 178 1286 ± 48 4527 ± 583 1056 ± 106 3703 ± 469 1338 ± 163 2494 ± 309
4 Benzaldehyde nd 58.3 ± 1.1 36 ± 4 988 ± 48 nq 115 ± 3 30 ± 2 145 ± 19
5 5-Methyl-2- 615 ± 49 1451 ± 198 953 ± 56 2979 ± 455 729 ± 42 2282 ± 47 685 ± 99 2160 ± 141
furfuraldehyde
6 Vanillina 1.50 ± 0.02 2.6 ± 0.4 0.59 ± 0.03 1.75 ± 0.24 2.9 ± 0.5 2.27 ± 0.08 0.74 ± 0.05 5.3 ± 0.8
Total aldehydesa 42 85 31 213 41 64 36 48
Acetals
7 Acetaldehyde 164 ± 10 183 ± 15 198 ± 2 545 ± 32 193 ± 5 223 ± 6 204 ± 8 291 ± 3
diethylacetala
Acetic esters
8 Methyl acetatea 8.6 ± 0.4 13.1 ± 1.1 13.0 ± 1.8 23 ± 3 10.2 ± 1.2 16.6 ± 1.4 11.7 ± 1.2 20 ± 2
9 Ethyl acetatea,b 2893 ± 20 5141 ± 273 2256 ± 281 4857 ± 239 1929 ± 34 3751 ± 170 2193 ± 236 1714 ± 106
10 Propyl acetate 3473 ± 380 3928 ± 281 3949 ± 145 4816 ± 614 3923 ± 517 4605 ± 456 4230 ± 295 5154 ± 593
11 Isobutyl acetatea 2.14 ± 0.15 2.81 ± 0.02 2.42 ± 0.12 3.2 ± 0.3 2.4 ± 0.3 3.1 ± 0.4 2.8 ± 0.3 3.4 ± 0.3
12 Butyl acetate 61 ± 5 68 ± 3 78 ± 7 136 ± 16 77 ± 6 108 ± 13 85 ± 8 123 ± 15
13 Isoamyl acetatea 3.6 ± 0.5 5.1 ± 0.3 3.87 ± 0.13 5.9 ± 0.8 4.0 ± 0.4 5.3 ± 0.7 4.5 ± 0.5 5.9 ± 0.8
15 Hexyl acetate nd nd nd nd nd nd nd nd
16 Phenylmethyl acetate nd nq nq nq nq nq nq nq
17 Benzyl acetate 239 ± 15 373 ± 31 264 ± 3 442 ± 25 328 ± 20 512 ± 54 387 ± 25 597 ± 50
18 2-Phenylethyl acetatea 0.68 ± 0.06 1.52 ± 0.16 0.91 ± 0.01 1.93 ± 0.14 1.04 ± ± 0.09 2.2 ± 0.2 1.13 ± 0.11 2.4 ± 0.1
Total acetic estersa,d 19 27 25 40 22 32 25 37
Ethyl esters
19 Ethyl propanoate 3531 ± 327 3839 ± 306 3831 ± 95 4397 ± 534 3969 ± 268 4547 ± 636 4311 ± 404 4857 ± 415
20 Ethyl isobutyrate 1022 ± 109 1339 ± 91 1161 ± 54 1531 ± 65 1202 ± 116 1653 ± 120 1388 ± 106 1826 ± 151
21 Ethyl butyrate 324 ± 22 366 ± 3 367 ± 12 501 ± 69 387 ± 22 770 ± 88 426 ± 26 510 ± 53
22 Ethyl isovalerate 831 ± 74 1318 ± 76 883 ± 49 1427 ± 179 969 ± 81 1492 ± 171 1139 ± 112 1663 ± ± ± 212
23 Ethyl valerate 13.8 ± 1.5 16.6 ± 0.1 19.6 ± 0.9 33 ± 4 18.1 ± 0.8 26 ± 4 19.1 ± 1.2 24 ± 3
24 Ethyl hexanoate 84 ± 10 109 ± 7 90 ± 4 131.9 ± 0.1 98 ± 8 143 ± 2 115 ± 12 166 ± 20
26 Ethyl lactatea 50 ± 5 55 ± 7 44.2 ± 2.2 60 ± 4 41.4 ± 1.5 49 ± 6 43 ± 5 47.7 ± 2.5
27 Ethyl octanoate nd nd nd nd nd nd nd nd
28 Ethyl furoate 174 ± 10 247 ± 7 228 ± 32 522 ± 61 220 ± 3 313 ± 4 243 ± 20 348 ± 23
29 Ethyl benzoate nd nd nd nq nd nd nd nd
30 Diethyl succinatea 3.48 ± 0.23 5.9 ± 0.7 4.3 ± 0.3 5.52 ± 0.19 4.9 ± 0.4 8.2 ± 0.3 5.8 ± 0.9 10.3 ± 1.0
Total ethyl estersa 60 69 55 75 53 66 57 68
Alcohols
31 Metanola,b 20 ± 1 69 ± 10 23 ± 1 98 ± 12 22 ± 2 79 ± 13 20.1 ± 0.7 48 ± 7
32 Ethanola,b,e 5302 ± 99 7620 ± 15 4841 ± 131 11,283 ± 468 4616 ± 140 12,387 ± 106 5189 ± 468 10,839 ± 108
(0.7) (1.0) (0.6) (1.4) (0.6) (1.5) (0.6) (1.4)
33 1-Propanola,b 18.0 ± 0.5 39.5 ± 0.8 23.5 ± 0.8 60 ± 2 19.6 ± 1.8 63 ± 9 26 ± 2 52 ± 7
34 Isobutanola 8.7 ± 0.3 8.7 ± 1.2 8.79 ± 0.07 10.1 ± 1.4 9.9 ± 0.8 10.8 ± 1.3 10.6 ± 1.2 13.1 ± 1.6
35 2-Methyl-1-butanola 7.66 ± 0.19 8.9 ± 0.3 8.15 ± 0.18 9.3 ± 0.4 8.6 ± 0.4 9.7 ± 0.8 9.5 ± 1 11 ± 1
36 3-Methyl-1-butanola 28.9 ± 1.9 33.7 ± 1.6 30.5 ± 0.4 34.4 ± 0.4 32 ± 2 35.7 ± 0.8 35 ± 3 39 ± 3
37 1-Hexanol nq nq nq nq nq nq nq nq
38 Cis-3-hexen-1-ol 16 ± 1 19.4 ± 1.6 18.7 ± 0.3 21.4 ± 0.4 18.3 ± 0.4 20.4 ± 1.6 18.9 ± 0.2 23.7 ± 1.6
39 Benzyl alcohol 319 ± 43 437 ± 25 380 ± 2 432 ± 11 529 ± 45 563 ± 79 407 ± 58 610 ± 11
40 Furfuryl alcohol 907 ± 68 460 ± 53 448 ± 52 1217 ± 55 635 ± 69 1147 ± 59 1088 ± 148 625 ± 65
41 2-Phenylethanola 12.6 ± 1.6 18.2 ± 0.5 14.9 ± 0.1 17.9 ± 0.8 21 ± 3 22.9 ± ± 0.1 16 ± 2 23.1 ± 0.7
Total alcoholsa,f 97 179 110 232 109 222 119 188
Ketones
42 Diacetyla 21.1 ± 0.7 50 ± 5 29 ± 1 50 ± 6 19 ± 2 56 ± 3 22 ± 2 49 ± 4
43 Acetoina 1432 ± 197 696 ± 94 1117 ± 94 1427 ± 87 931 ± 16 1020 ± 132 924 ± 128 899 ± 68
44 Acetophenone nq nq nq 118.6 ± 0.6 nq nq nq nq
Total ketonesa 1453 747 1146 1477 949 1076 946 949
Acids
45 Isovaleric acida 24.7 ± 0.4 28 ± 2 22.7 ± 0.3 23.7 ± 1.4 24.4 ± 0.2 33.2 ± 0.8 22.1 ± 0.3 24.8 ± 1.6
46 Hexanoic acid 974 ± 112 3861 ± 532 1231 ± 113 1861 ± 258 1424 ± 164 2296 ± 214 1594 ± 38 3811 ± 209
47 Heptanoic acid nq 451 ± 65 nq 83 ± 10 nq 237 ± 29 77 ± 8 422 ± 35
48 Octanoic acid 194 ± 17 717 ± 108 223 ± 8 446 ± 55 299 ± 42 546 ± 24 314 ± 27 751 ± 51
49 Nonanoic acid nq 124 ± 14 nd nq 152 ± 20 52.8 ± 0.3 34 ± 4 149 ± 20
50 Decanoic acid 44 ± 4 128 ± 4 45 ± 5 86 ± 13 66 ± 7 81 ± 6 52 ± 6 151 ± 8
Total acidsa 26 33 24 26 26 36 24 30
Terpenes
51 Limonene nd nd nd nd nd nd nd nd
Lactones
52 c-Butyrolactonea 2.6 ± 0.4 3.07 ± 0.05 2.5 ± 0.3 2.8 ± 0.4 1.67 ± 0.12 3.34 ± 0.02 2.2 ± 0.3 2.28 ± 0.02
53 Trans-b-methyl-c- 65.3 ± 0.9 73 ± 3 66.0 ± 0.5 66.7 ± 0.8 85 ± 6 237 ± 30 74.4 ± 2.8 87 ± 9
octalactone
 R.M. Callejón et al. / Food Chemistry 120 (2010) 561–571 569

Table 4 (continued)

No. Compound Mean concentration (lg/L) ± SD

Acacia (A)c Cherry (C)c Oak (O)c Chestnut (N)c
Initio Final Initio Final Initio Final Initio Final
54 Cis-b-methyl-c- 77.8 ± 1.7 109 ± 11 82.1 ± 1.7 82.2 ± 0.6 204 ± 25 1179 ± 167 123 ± 14 191 ± 13
octalactone
Total lactonesa 2.8 3.3 2.8 3.0 2.0 4.8 2.3 2.5
Phenols
55 Guaiacol 120 ± 12 232 ± 7 152 ± 4 224 ± 16 149 ± 16 301 ± 43 157 ± 13 286 ± 7
56 Eugenol nd nd nd nd nd 81 ± 10 nd 108 ± 9
57 4-Ethylphenol 286 ± 16 509 ± 64 352 ± 14 428 ± 18 405 ± 52 509 ± 51 420 ± 61 641 ± 60
Total phenols 406 741 504 652 554 891 578 982
Total amountsa 10,058 14,088 8689 19,149 7942 17,863 8794 14,168
Total amountsa,d,f 1863 1327 1592 3009 1397 1725 1412 1615
Acetic acid degreeg 5.8 6.2 5.7 5.9 5.7 5.9 5.8 6.3
Dry extractg,h 14.0 16.6 14.0 19.4 14.4 17.0 14.4 18.6
pH 2.9 2.8 2.9 2.8 2.9 2.8 2.9 2.8
a
Concentration in mg/L.
b
GC-FID.
c
Kind of wood of aging barrels.
d
Without considering ethyl acetate.
e
Value in brackets is alcoholic degree.
f
Without considering ethanol.
g
g/100 mL.
h
Data transfer by Cerezo et al. (2009).

wine aging experiments (Garde-Cerdán & Ancín-Azpilicueta, tions were lower than those observed in our vinegars aged in cher-
2006). This phenomenon is more likely to occur when new barrels ry (Tables 1–4). These compounds, then, may be characteristic of
are used as is our case. Other possible reason could be oxidation this specific type of wood. In fact, the results of sensory analysis
reactions, since the porosity of wood provides ‘‘low oxidation con- realized by other authors showed high scores for ‘‘red fruit”
ditions” (Vivas & Glories, 1993). descriptor in vinegars aged in cherry wood (Cerezo et al., in press).
When vinegar previously acetified in cherry wood was aged in
3.2. Influence of the different woods on the aromatic profile of aged bottles, we also observed an increase in ethyl benzoate, ethyl furo-
vinegars ate and benzaldehyde. Cherry wood probably releases a number of
precursors that are transformed into the abovementioned com-
In this study, we have acetified and subsequently matured wine pounds during aging.
vinegars in four types of wood to ascertain whether the wood has As expected, oak-lactone isomers presented higher concentra-
any influence on the final quality of aroma. We found significant tions in vinegars aged in oak wood, and it was the cis isomer which
differences in the total volatile content of final samples (1 year underwent the highest increases. The cis/trans ratios obtained (be-
aging). If we remove ethanol and ethyl acetate (because they are tween 5 and 8), are in accordance with the values found in wines
the major aroma compounds and their concentrations are too high aged in American oak barrels (Towey & Waterhouse, 1996). These
for any differences among samples to be analysed), we find that the compounds reached concentrations ca. 20 times higher than their
total amount of the remaining volatile compounds is similar in all detection threshold in vinegar (78 lg/L) (Callejón et al., 2008a).
the aged vinegars independently of the kind of wood used. Vinegars aged in oak wood presented the typical ‘‘wood” aroma,
Some of these aroma compounds showed differences which de- reaching high values for ‘‘wood” descriptors in sensory analysis
pended on the kind of wood, as follows. (Cerezo et al., in press).
Ethyl benzoate was only detected in initial samples acetified in In samples from winery 3 (balsamic vinegars, Italy), small
cherry wood and it increased during aging. Ethyl furoate reached amounts of oak lactones appear in all vinegars at the beginning
its highest concentrations during aging in cherry barrels. Aceto- of aging due to the fact that the raw material (cooked grape musts
phenone, which presented concentrations under its quantification and white wine vinegar) was stored in oak wood barrels. Important
limit (LOQ) at the beginning of aging of all the vinegars, could be increases in both isomers were only found for samples aged in oak
only quantified in those vinegars aged in cherry wood. According wood.
to the results of Flamini, Dalla Vedova, Cancian, Panighel, and De Besides oak lactones, other oak-wood extractable compounds
Rosso (2007), benzaldehyde content also seems to be related to have been extensively studied in wines and contribute to wine fla-
cherry wood. These compounds were described as fruit, red fruit vour (Jarauta, Cacho, & Ferreira, 2005).
or sweet odors in gas chromatography–olfactometry studies (Bail- Hundreds of volatile compounds have been identified in untoa-
ly, Jerkovic, Marchand-Brynaert, & Collin, 2006; Callejon et al., sted oak wood (Chatonnet, 1991; Díaz-Maroto et al., 2008; Maga,
2008c; Fan & Qian, 2005). They have been determined in different 1984; Nishimura, Ohnishi, Masuda, Koga, & Matsuyama, 1983):
types of wine, some of which are aged in oak barrels, such as Sher- for example, vanillin, eugenol, guaiacyl derivatives and whisky lac-
ry (Moreno, Zea, Moyano, & Medina, 2005; Zea, Moyano, Moreno, tones (Sefton, Francis, Pocock, & Williams, 1993). Toasting in-
Cortes, & Medina, 2001), red (Escudero, Campo, Fariña, Cacho, & creases the levels of those compounds found in untoasted oak
Ferreira, 2007; Zhang, Xu, Duan, Qu, & Wu, 2007), sweet Fiano (Chatonnet, Boidron, Dubourdieu, & Pons, 1989; Díaz-Maroto
(Genovese, Gambuti, Piombino, & Moio, 2007), Madeira (Campo, et al., 2008), such as guaiacyl derivates, vanillin or eugenol and it
Ferreira, Escudero, Marqués, & Cacho, 2006), Albillo (Sánchez-Palo- also leads to the formation of other new compounds like furanic
mo, González-Viñas, Díaz-Maroto, Soriano-Pérez, & Pérez-Coello, aldehydes (Guchu, Díaz-Maroto, Pérez-Coello, González-Viñas, &
2007) and Sauternes (Bailly et al., 2006). However their concentra- Cabezudo Ibáñez, 2006).
570 R.M. Callejón et al. / Food Chemistry 120 (2010) 561–571

Eugenol was not detected in vinegar aged in acacia or cherry are the best wood for the aging of vinegars due to the distinctive
barrels. However, it was present in all vinegars aged in chestnut aromatic characteristics that they provide.
and in most of oak barrels (mean concentration of ca. 111 lg/L).
These results were similar to those of Flamini et al. (2007), who 4. Multivariate statistical analysis
analysed extracts from acacia, cherry, mulberry, chestnut and oak
wood, and found that only the latter two woods presented a note- Linear Discriminant Analysis (LDA) is a supervised chemometric
worthy concentration of eugenol. method widely used for classification purposes. Hence, LDA was
Vanillin is a compound whose aroma is related to oak barrels. carried out to check if the changes produced in the volatile profile
In general, as the time of contact between wine and oak wood in- due to the aging could classify the samples according to the aging
creases, the levels of vanillin increase (Ortega-Heras, González- time. Therefore, LDA was performed considering two groups of
Sanjosé, & González-Huerta, 2007). However, Flamini et al. samples: vinegars that had not been subject to aging and vinegars
(2007) pointed out that chestnut wood provides higher concen- that had been subject to one year of aging. To perform multivariate
trations of this aromatic aldehyde than oak wood. In our case, statistical analysis, we made a substantial reduction of variables.
we observed the highest increases in concentration in the sample First, those compounds accounting for a high number of non de-
aged in chestnut from winery 3. In the other two wineries, vanil- tected or non quantified concentrations in the samples were elim-
lin showed the highest increases in samples aged in oak and inated. Then, redundant variables with high correlation coefficients
chestnut wood. (r > 0.7) were eliminated, choosing those ones which represented a
Guaiacol also presented high concentrations in the initial sam- higher number of compounds. Finally, we used the following 17
ples from winery 3. They were much higher than those found in variables: ethyl acetate, ethanol, methyl acetate, propyl acetate,
wines (Escudero et al., 2007; Ortega-Heras et al., 2007), which sup- hexanal, isobutanol, 3-methyl-1-butanol, ethyl hexanoate, 2-fur-
ports the idea mentioned above that the cooked grape musts were furaldehyde, benzaldehyde, furfuryl alcohol, diethyl succinate, 2-
probably stored in oak wood barrels. In these cases, the content of phenylethyl acetate, vanillin, hexanoic, heptanoic and decanoic
this compound underwent statistically significant increases. acids.
Furanic compounds such as 2-furfuraldehyde and 5-methyl-2- We correctly classified 100% of samples in the cross-validation
furfuraldehyde are originated by the thermal degradation of hemi- analysis by the leave one out method. The leave one out method
cellulose and cellulose, respectively (Bozalongo et al., 2007). (Lachembruch & Michey, 1968) consists of dividing the whole set
In initial samples, 5-methyl-2-furfuraldehyde was only quanti- of samples into two groups; a training set containing all the sam-
fied in samples from winery 3 between 615 and 953 lg/L. On the ples except one which is used as a test set. LDA, then, was applied
other hand, although 2-furfuraldehyde appears in most initial sam- as many times as the number of samples.
ples, it presented the highest concentrations in samples from win-
ery 3 (Table 4). This may be due to the fact that must cooking
5. Conclusions
generates a considerable amount of furanic compounds as a conse-
quence of sugar degradation (Antonelli, Chinnici, & Masino, 2004).
There was no common pattern for changes in volatile composi-
5-methyl-2-furfuraldehyde and 2-furfuraldehyde increased in
tion during aging. We observed that the only group of volatile com-
these samples during aging, and changes for both compounds were
pounds that increased during the 16 aging experiments was acids.
statistically significant. The threshold perception of furanic com-
When we compared aging in bottles with aging in wood, we found
pounds is high. For 2-furfuladehyde it is 6.2 mg/L (Tesfaye et al.,
that the overall increase in volatile compounds was higher in vin-
2008), so its concentration in final vinegars (1.33–4.53 mg/L) did
egars aged in bottles. In general, the final quantitative volatile
not surpass its threshold. It is believed that furanic compounds
composition of vinegars was not affected by the type of wood used,
do not have an important role in the aroma of products aged in
although some compounds may be related to the kind of wood
oak wood, although they enhance the perception of oak lactones
used. Hence, oak lactones reached the highest concentrations in
(Reazin, 1981).
vinegars aged in oak wood. Ethyl benzoate, ethyl furoate, aceto-
In this study, the barrels were toasted for the minimum amount
phenone and benzaldehyde seem to be related to cherry wood
of time required for manufacture. For this reason, the content of
since, except for ethyl furoate, they were only quantified in this
furanic aldehyde compounds was lower than expected (Tesfaye
kind of wood. Lastly, eugenol was only present in all vinegars aged
et al., 2002). 2-Furfuraldehyde tends to increase even during aging
in chestnut and in most vinegars aged in oak barrels. According to
in bottles, and this was also observed in wine aged in oak barrels
the results, oak and cherry seem to be the best type of wood for
for nine months and then in bottles for one year (Pérez-Prieto,
aging of vinegar due to their distinctive aromatic characteristics.
López-Roca, Martínez-Cutillas, Pardo-Mínguez, & Gómez-Plaza,
2003).
Acknowledgements
4-Ethylphenol is produced by non-Saccharomyces yeasts and it
is undesirable for aroma because it introduces an organoleptic de-
This work was supported by Grant AGL2004-07494-C02/ALI
fect (Martorell, Martí, Mestres, Busto, & Guasch, 2002). Initial vin-
from the Ministerio de Educación y Ciencia, Spain, and the WINE-
egars from winery 2 and 3 yielded concentrations above 200 lg/L.
GAR Project; UE, Cooperative Research Project number 017269.
In both cases the final concentrations were higher than those found
in wine aged in oak wood (Jarauta et al., 2005). The formation of
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