Sensors and Actuators B 120 (2006) 278–287

SPME coupled to an array of MOS sensors

Reduction of the interferences caused by water and
ethanol during the analysis of red wines
S. Villanueva a,1 , A. Vegas a,1 , J.A. Fernandez-Escudero b ,
M. Iñiguez c , M.L. Rodrı́guez-Mendez d,∗ , J.A. de Saja a,1
aDepartment of Condensed Matter Physics, Sciences Faculty, Prado de la Magdalena s/n, 47011 Valladolid,
University of Valladolid, Spain
b Oenological Centre of Castilla-Leon, Rueda, Spain
c Oenological Centre of La Rioja, Haro, Spain
d Department of Inorganic Chemistry, E.T.S. Ingenieros Industriales, Universidad de Valladolid, P◦ del Cauce s/n,

47011 Valladolid, Spain

Received 16 December 2005; received in revised form 15 February 2006; accepted 16 February 2006
Available online 17 April 2006

Abstract
A solid phase microextraction (SPME) system has been coupled to an array of metal oxide sensors. The influence of the experimental conditions
used in the injection system in the response of the sensors has been analysed. Moreover, with the help of data obtained from gas chromatog-
raphy, the system has been optimized to reduce the presence of water and ethanol in the sensors chamber while efficiently retaining and
concentrating other volatiles present in wine. The best results in terms of elimination of water and ethanol, reproducibility of the signals and
discrimination capability are obtained using a polar absorbent fiber such as the polyacrilate fiber. The performance of the sensory system is
drastically improved if the thermal desorption is carried out in two steps (a first desorption at low temperature to dry the fiber followed by a
thermal desorption at high temperature). Principal component analysis of the signals obtained using the optimized conditions has allowed the
discrimination of five red wines elaborated using the same vinification and ageing methods (vintage 2000) being the only variable modified
the variety of grape. The results agree with obtained gas chromatography. These facts demonstrate that the experimental conditions of SPME
have to be adapted to the particular requirements of the resistive sensors in order to improve the capability of discrimination of the arrays of
sensors.
© 2006 Elsevier B.V. All rights reserved.

Keywords: Electronic nose; MOS sensor; Wine; Gas chromatography; SPME

1. Introduction
In the last years, a great deal of research towards the develop-
ment of arrays of gas sensors coupled with pattern recognition
software (the so-called electronic noses) has been carried out
[1,2]. These systems have been used to analyse the headspace
of several foods or beverages [3–7]. In particular, attempts have
been made to discriminate wines [6,8–16] using a variety of
∗ Corresponding author. Tel.: +34 983 423540; fax: +34 983 423310.
E-mail address: mluz@dali.eis.uva.es (M.L. Rodrı́guez-Mendez).
1 Fax: +34 983 423572.
chemical sensors, including the use of resistive metal oxide semi-
conductor (MOS) sensors [9–12].
Unfortunately, the presence of water and ethanol in the
headspace of wines causes strong interferences in the response
of resistive sensors and conceal the responses of other compo-
nents that are present in low concentrations. As a consequence,
it is not possible to discriminate wines by analyzing directly
the headspace of the wines. The headspace of wines has to be
pre-treated to eliminate, or at least substantially diminish, the
presence of these two main components in the volatile mixture
[13]. Pretreatment methods commonly used in chromatography
such as Purge and Trap (PT) and solid phase microextraction
(SPME) can be used to inject the volatiles in the chamber where

0925-4005/$ – see front matter © 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.snb.2006.02.042
 S. Villanueva et al. / Sensors and Actuators B 120 (2006) 278–287 279

the array of sensors is housed. In these methods certain adsorbent Table 1

resins are used that show low affinity towards water or ethanol, List of the compounds of the standard solution
while are able to efficiently retain and concentrate other volatiles ID Component Concentration (ppm)
present in wine. The volatiles can be released afterwards by Major
applying a temperature program to the trap [19–23]. Both meth- 1 Ethanal 220.3
ods, PT and SPME have demonstrated to be able to concentrate 2 Ethyl acetate 225.0
volatiles efficiently. However, the capability of eliminating water 3 Methanol 236.7
and ethanol, is superior in the case of SPME [15]. 4 1-Propanol 201.0
5 2-Methyl-1-propanol 200.3
In spite of the promising results obtained connecting arrays 6 1-Butanol 101.3
of MOS sensors with a SPME thermal desorption injector 7 3-Methyl-1-butanol 404.5
[17,24–26], the adsorbing materials used in this technique, still
Minor
retain important amounts of water and ethanol, disturbing the 8 Isopenthyl acetate 0.523
measures registered by the resistive sensors. In order to improve 9 trans-2-Hexenal 0.508
the results, it is clear now that the experimental conditions of 10 Ethyl hexanoate 0.523
SPME (nature of the fiber, time and temperature of absorption 11 Hexyl acetate 0.524
12 Ethyl heptanoate 0.521
or desorption, carrier gas, etc.), need to be adapted to the partic-
13 1-Hexanol 0.492
ular requirements of the detection with MOS sensors, which are 14 Ethyl octanoate 0.520
noticeably different to those of the chromatographic analysis (in 15 1-Heptanol 0.493
the case of chromatography, the presence of mayor amounts of 16 Benzaldehyde 0.630
water and ethanol do not disturb the separation capability of the 17 Ethyl pelargonate 0.520
18 Linalool 0.517
column).
19 1-Octanol 0.494
The objective of this work is to analyse the influence of the 20 Isoamile lactate 0.517
working conditions used in the SPME, in the response of an 21 Phenil acetate 0.646
array of MOS sensors. This information will be used to optimize 22 Ethyl decanoate 0.518
the performance and capability of discrimination of the system 23 Butyrolactone 0.672
24 Diethyl succinate 4.156
towards red wines. Gas chromatography has been used as a valu-
25 Terpineol 2.239
able tool to analyse the composition of the volatiles retained by 26 Citronellol 2.062
the SPME fiber under different experimental conditions. 27 Nellol 3.508
The optimized conditions have been applied to the SPME- 28 Acetate-2-phenilethyle 2.479
MOS sensors system and its discrimination capability has been 29 Ethyl dodecanoate 0.556
30 Geraniol 3.416
evaluated by exposing repeatedly the array of sensors to five
31 Guayacol 4.516
red wines and then carrying out principal component analysis 32 Bencilic alcohol 4.200
(PCA). 33 t-Whiskylactone 4.360
34 2-Phenilethanol 4.080
2. Experimental 35 Wiskylactona 4.360
36 4-Etilguayacol 4.258
37 2-Ethylphenol 4.148
2.1. Wine samples 38 Eugenol 4.264
39 4-Ethylphenol 6.080
An “artificial wine” prepared according to reference [27], by
solving 39 organic compounds (7 major and 32 minor organic
compounds usually found in the headspace of wines) in EtOH
Table 3 collects the concentration of the volatiles of the wines
12%. The compounds selected and their concentration are listed
as analysed by GC-MS.
in Table 1.
In addition, five wine samples were purposely prepared for
this study by the oenological centre of Castilla Leon (Spain). 2.2. Chromatographic analysis
They included five Spanish red wines elaborated using the same
vinification and ageing methods (18 months of ageing in Amer- Chromatography was run in a Shimadzu GCMS QP5050 gas
ican oak barrel followed by 18 months in bottle) but using chromatographer equipped with a mass detector. A capillary
different varieties of grapes: Tempranillo (G1), Tinta del pais column phase HP-INNO-Wax (length: 30 m; inner diameter:
(G2), Tinta de toro (G3), Prieto Picudo (G4) and Mencı́a (G5). 0.32 mm) was used.
Grapes were grown in the same region (Castilla-León, Spain) When SPME sampling method was coupled to chromatogra-
and corresponded to the 2000 vintage. phy, 3 ml of wine was placed in 10 ml vial that was kept at 40 ◦ C
The Oenological Centres of Castilla y León and of Rioja during 10 min. Then the fiber was exposed to the headspace of
characterized the wines chemically and by a human panel test the vial for 5 min. The fiber was then driven to the thermal des-
following the regulations of the Office Internationale de la Vigne orption port of the gas chromatograph (250 ◦ C). The separation
et du Vin (OIV) [28]. Table 2 summarises the results of the main was reached using nitrogen as carrier gas with a flow-rate of
chemical characteristics of the wines under study. 33 ml min−1 using a specific oven temperature sequence.
280 S. Villanueva et al. / Sensors and Actuators B 120 (2006) 278–287

Table 2
Results of the chemical analysis of the wines under study
Analytic determination G1 G2 G3 G4 G5

Tartaric acid (g/l) 2.3 2.0 1.7 2.4 1.8

Glycerol (g/l) 7.8 6.7 7.8 8.7 8.4
Potassium (mg/l) 770 830 890 820 720
Antiferments (biologic test) Negative Negative Negative Negative Negative
Tannic acid (g/l) 3.4 3.1 3.6 2.9 2.5
Acquired grade 20 ◦ C (vol%) 13.7 12.8 14.3 13.6 13.5
Dry extract (g/l) 25.0 24.3 24.2 24.7 22.6
Total acidity (tartaric) (g/l) 4.9 4.9 4.8 5.3 4.9
Volatile acidity (acetic) (g/l) 0.62 0.73 0.51 0.92 0.65
Total sulphur dioxide (g/l) 37 11 29 73 43
Free sulphur dioxide (mg/l) 10 5 6 24 6
Reducers sugars (g/l) 2.0 1.6 1.9 1.6 1.8
Relative density 20/20 0.9919 0.9927 0.9909 0.9919 0.9912
pH 3.44 3.57 3.52 3.43 3.35
Malic acid (g/l) 0.1 0.1 0.1 0.1 0.1
Antocyan (mg/l) 170 133 184 209 141
Total polyphenoles 48 44 52 42 36
Colour intensity (420 + 520 + 620 nm) 8.1 8.1 11.1 8.8 7.5

Table 3
List of the compounds detected by CG-MS in the wines selected
Compound G1 (ppm) G2 (ppm) G3 (ppm) G4 (ppm) G5 (ppm)

Ethanal 16.9450 9.3327 10.9359 23.5729 19.5555

Ethyl acetate 103.8418 118.0961 91.0517 119.7693 110.0867
Methanol 150.6133 138.2185 137.1479 206.3440 151.0296
1-Propanol 25.0706 34.6019 18.3236 25.6045 31.8493
2-Methyl-1-propanol 51.2008 42.3637 53.9046 51.8071 55.4659
1-Butanol – – – – –
3-Methyl-1-butanol 246.0726 226.8117 346.7404 247.1322 394.0515
Isopenthyl acetate 0.4419 0.4926 0.5074 0.3726 0.3763
trans-2-Hexenal – – – – –
Ethyl hexanoate 0.4003 0.4863 0.4034 0.2388 0.5226
Hexyl acetate – – – – –
Ethyl heptanoate 0.0005 0.0026 0.0005 0.0013 0.0004
1-Hexanol 1.9151 1.0913 2.9009 1.3500 1.4460
Ethyl octanoate 0.4565 0.4665 0.4449 0.2274 0.4890
1-Heptanol 0.0539 0.0791 0.0705 – 0.0433
Benzaldehyde 0.0063 0.0359 0.0025 0.1011 0.1180
Ethyl pelargonate 0.0012 0.0015 0.0006 0.0006 0.0001
Linalool 0.6396 – – – –
1-Octanol 0.0157 0.0111 0.0136 0.0107 0.0171
Isoamile lactate 0.2156 0.2799 0.4326 0.3310 0.3518
Phenil acetate – – – – –
Ethyl decanoate 0.1371 0.2604 0.1117 4.1576 0.0978
Butyrolactone 0.1371 0.2604 0.1117 4.1576 0.0978
Diethyl succinate 22.6912 12.3460 95.6952 3.1164 30.0061
Terpineol – 0.5613 0.1242 16.1562 0.0517
Citronellol 0.0112 0.0080 0.0118 0.0029 0.0058
Nellol 0.0032 – 0.0090 – –
Acetate-2-phenilethyle 0.0374 0.0372 0.1017 0.0675 0.0340
Ethyl dodecanoate 0.0139 0.1282 0.0131 0.0109 0.0021
Geraniol – – 0.0206 – 0.0033
Guayacol 0.0898 – 0.0591 – 0.0621
Bencilic alcohol 0.1074 0.3531 0.2586 0.4910 0.5097
t-Whiskylactone 0.0829 – 0.0863 7.6299 0.0504
2-Phenilethanol 34.5253 17.6081 170.1036 53.8110 58.4185
Wiskylactona 0.2928 0.2608 0.5473 0.8756 0.7311
4-Etilguayacol – – – 0.0244 –
2-Ethylphenol 0.0042 – 0.0077 – –
Eugenol 0.1662 – 0.0790 – 0.0720
4-Ethylphenol 0.0300 0.0482 0.2559 1.2864 –
 S. Villanueva et al. / Sensors and Actuators B 120 (2006) 278–287 281

Table 4 the presence of oxygen in the atmosphere surrounding MOS

Array of 14 MOS sensors used in this work sensors.
ID Sensors Supplier

S1 sp31 Fis 2.4. Design of experiments

S2 sp15a Fis
S3 sbaq1a Fis Factorial experiment design (32 ) was carried out by varying
S4 sb50 Fis the temperature of the wine samples (40, 45 and 50 ◦ C) and the
S5 spmw1 Fis
time of exposure of the fiber to the headspace of the wines (5,
S6 sp11a Fis
S7 sbaq4 Fis 10 and 15 min).
S8 sb95 Fis
S9 sb31 Fis 2.5. Statistical analysis
S10 sb11a Fis
S11 spmw Fis
S12 sb30a Fis
Seven different samples were extracted from each wine, and
S13 sp19 Fis measured with the array of sensors. Principal component anal-
S14 sp12a Fis ysis was carried out using Matlab V 5.3. and The Unscrambler
v. 9.1, CAMO ASA, Norway. Seven replicates of each mea-
sure were carried out. A experimental design method has been
Several types of fibers are available in the market that has applied to evaluate the influence of various experimental param-
affinity towards molecules with different polarity, leading to eters in the performance of the system. These calculations were
retention of different types of volatiles [20–23]. In this work, carried out by means of STATGRAFICS PLUS V.5.1.
three SPME fibers were evaluated. They included a non-polar
fiber polydimethylsiloxane (PDMS), a polar fiber polyacrylate 3. Results
(PA), and a bipolar fiber of polydimethylsiloxane coated with
carbowax and divinylbenzene (PDMS/CW/DVB). The fibers The first step in this research was to evaluate the interference
were purchased from Supelco. caused by water and ethanol in the response of the MOS sensors.
For this purpose, the array of sensors was coupled to a conven-
2.3. Array of sensors tional Static Headspace device (HS) that collects the volatiles
present in the headspace of a sample, without eliminating water
The array of gas sensors was constructed using MOS sen- or ethanol. Three samples were used in this first test: water, a
sors (Table 4). The sensors were mounted in a stainless steel 12% hydroalcoholic solution and the artificial red wine. Fig. 1a,
test box with a volume of 150 ml. The test box was kept at a shows the response of the sensors (expressed as R/R0 ) towards
constant temperature (50 ◦ C) throughout the experiments. The the three samples. As observed in the figure, the similarity in the
data collection was performed through a PC-LPM-16 data acqui-
sition card from National Instruments interfaced to a personal
computer. The sensors were polarized using a constant voltage
of 5 V provided by a FAC-662B programmable power supply.
The scan rate used to measure the changes of the resistance of
the 14 sensors was 0.5 s. Data were monitored in real time and
the graphs could be followed using Visual Basic software from
Microsoft.
In preliminary experiments, a Static Headspace sampler
(Hewlett Packard Mod HP 7694E) was used for the injection of
the headspace above the sample to the sensor’s chamber without
elimination of water and ethanol. The wine samples (3 ml) were
placed in 10 ml vials that were kept at a constant temperature
(40 ◦ C) for 10 min in order to obtain a homogeneous headspace.
Each vial is pressurized for 4.68 s at 1.5 b. The pressure gradient
that builds up permits to fill a 3 ml loop in 20 s, and its content is
then injected to the charge carrier gas that drives the volatiles to
the sensor’s chamber. The carrier gas was high purity synthetic
air (N50) and the flow-rate was 100 ml min−1 . An injection of
1 min was performed every 10 min.
SPME was also used to inject the volatiles in the sen-
sors chamber. The experimental conditions were initially sim-
ilar to those used in chromatography. However, after the des-
Fig. 1. Response of the array of sensors to water, an hydroalcoholic solution
orption process the carrier gas (100 ml min−1 ) was mixed (12%) and the standard red wine using: (a) headspace and (b) SPME with a
with a flow of high purity air of 50 ml min−1 to ensure PDMS fiber.
282 S. Villanueva et al. / Sensors and Actuators B 120 (2006) 278–287

responses obtained for the three samples avoids the possibility

of discriminating red wines and justifies the need of using an
injection system able to eliminate water and ethanol (or at least
to decrease their concentration) before injecting the sample into
the test chamber.
A candidate technique to be used as the injection method is
the solid phase microextraction (SPME) [29–41]. In this work
the possibility of using SPME as the injection system coupled
to the array of sensors was explored. For this purpose, a PDMS
fiber was used to collect the headspace of water, the hydroal-
coholic solution (12%) and of the standard red wine, using the
conditions described in the experimental section and that were
taken from literature [17,18,21,29–31,33,34]. The changes in
the resistance of the array of MOS sensors exposed to the three
samples are shown in Fig. 1b. As observed in the figure, the
low affinity of the PDMS fiber towards water, reduces the level
of moisture reaching the sensor’s chamber. For this reason, the
response produced by the water sample, is lower than that of the
hydroalcoholic solution (12%) and of the red wine. Although the
differences between the responses of the hydroalcoholic solution
(12%) and the red wine increase clearly with respect to HS, the
dissimilarities observed are too low to be used to discriminate
among red wines differing only in minor volatile components.
As stated above, the experimental conditions used with
SPME, corresponded to the experimental conditions commonly
used in chromatographic analysis of wines [40,41]. However,
the needs of chromatographic analysis and of the detection using
MOS sensors are quite different. In this work a systematic study
of the influence of the experimental conditions used in SPME
in the response of the sensors has been carried out. The results
have been used to improve the capability of discrimination of
Fig. 2. Polar Plot of the electrical response (expressed as peak height) of the array
the electronic nose.
of sensors towards water (. . .), ethanol:water 12% (—) and the standard red wine
The first parameter to be optimized is the chemical nature of ( ) using three different fibers: (a) PDMS, (b) PA and (c) PDMS/CW/DVB.
the fiber used to extract the volatiles from the headspace. Fibers
of different polarities are available in the market. In this study the
performance of three fibers of different affinities was evaluated: In order to confirm this result, samples were analysed by
a non-polar polydimethylsiloxane (PDMS) fiber, a polar poly- chromatography. SPME was used under similar experimental
acrylate (PA) fiber and a bipolar fiber of polydimethylsiloxane conditions than in previous paragraphs.
coated with Carbowax and divinylbenzene (PDMS/CW/DVB). Table 5 lists the intensity of the peaks observed in the chro-
Fig. 2 shows a polar plot of the responses of the array of matograms corresponding to water, ethanol and organic com-
sensors towards the studied samples for the three different types pounds present in the headspace of the standard red wine as
of fibers. The response of the array of sensors towards water, collected using the three types of fibers. As observed in the table,
water–ethanol (12%) and the standard red wine depend on the amount of water and ethanol retained by the fibers (and hence
the chemical nature of the fiber used during the pretreatment. reaching the mass detector after thermal desorption) is high and
In all cases, the array of sensors showed an intense response of the same other of magnitude for the three absorbent materi-
towards the water sample. In addition, the response of the sen- als. Other volatiles present at low concentrations, reach the mass
sors towards ethanol:water 12% was only slightly lower of that detector in concentrations high enough to be detected whatever
of the standard red wine and only a small decrease in the inten- the type of fiber used.
sity of the responses was observed. This result indicated that These results were in good agreement with the results
although SPME was able to eliminate significant amounts of observed using the array of sensors and confirmed that using
water and ethanol, important levels of such compounds still the SPME absorbing fibers, still important amounts of water
reached the sensor chamber. Moreover, due to the different affini- and ethanol reached the sensor chamber.
ties of the fibers towards the volatile components present in the In order to improve these results, a study of the influence of
headspace of the standard wine, the composition of the gas mix- the experimental conditions used in SPME in the levels of water
ture injected in the sensor chamber was also different, and this and ethanol reaching the sensors chamber was carried out.
was the reason of the differences observed in the responses of the For instance, the results were dramatically improved by per-
sensors. forming the thermal desorption in two steps (instead of a single
 S. Villanueva et al. / Sensors and Actuators B 120 (2006) 278–287 283

Table 5
Intensity of the peaks in a standard wine detected using SPME-CG-MS
Component IntensityPDMS/CW/DVB IntensityPDMS IntensityPA

One step Two steps One Step Two steps One step Two steps

Ethanol 1.33E + 08 1.06E + 08 9.60E + 07 8.90E + 07 1.02E + 08 1.79E + 06

Water 2.31E + 06 2.96E + 05 8.61E + 05 4.24E + 05 1.30E + 06 1.34E + 05
Ethanal 4.48E + 07 1.84E + 07 7.20E + 07 5.33E + 07 7.27E + 07 2.22E + 07
Ethyl acetate 7.09E + 07 3.35E + 06 2.26E + 07 2.60E + 06 2.22E + 07 5.78E + 06
Methanol 3.92E + 06 3.35E + 06 – – 8.89E + 06 7.89E + 06
1-Propanol 5.25E + 06 2.38E + 06 1.36E + 06 1.03E + 06 1.01E + 06 5.77E + 05
2-Methyl-1-propanol 8.31E + 06 2.70E + 06 – – 1.47E + 06 1.22E + 06
1-Butanol – – – – 1.09E + 06 5.06E + 05
3-Methyl-1-butanol 1.11E + 07 1.15E + 06 6.36E + 07 3.63E + 07 5.78E + 07 1.36E + 07
Isopenthyl acetate 2.82E + 06 1.81E + 06 1.54E + 06 5.25E + 05 2.96E + 05 1.20E + 05
trans-2-Hexenal 1.58E + 06 1.12E + 06 – – 1.48E + 05 1.12E + 05
Ethyl hexanoate 1.65E + 07 1.01E + 07 9.30E + 06 3.89E + 06 9.81E + 05 7.05E + 05
Hexyl acetate 2.26E + 07 2.13E + 07 1.18E + 07 1.10E + 05 1.32E + 06 1.15E + 06
Ethyl heptanoate 4.15E + 07 2.29E + 06 2.89E + 07 5.22E + 05 1.22E + 06 9.11E + 05
1-Hexanol 1.26E + 06 1.19E + 06 4.69E + 05 4.69E + 05 9.18E + 05 8.58E + 05
Ethyl octanoate 4.68E + 07 1.12E + 07 6.65E + 07 1.03E + 07 3.63E + 06 2.39E + 06
1-Heptanol 3.79E + 06 3.25E + 06 1.57E + 06 9.48E + 05 6.30E + 05 6.11E + 05
Benzaldehyde 2.42E + 06 1.36E + 06 5.22E + 05 4.45E + 05 2.33E + 05 1.86E + 05
Ethyl pelargonate 2.66E + 07 7.95E + 05 3.07E + 07 1.86E + 07 6.37E + 05 6.04E + 05
Linalool 1.02E + 07 1.10E + 06 5.37E + 06 3.43E + 06 1.15E + 06 9.86E + 05
1-Octanol 9.07E + 06 9.00E + 06 5.52E + 06 1.40E + 06 1.61E + 06 9.42E + 05
Isoamile lactate 8.82E + 05 2.42E + 05 – – 7.81E + 04 6.37E + 04
Phenil acetate 1.42E + 06 1.02E + 06 8.15E + 05 8.46E + 04 2.88E + 05 1.89E + 05
Ethyl decanoate 8.99E + 05 7.88E + 05 8.15E + 05 9.85E + 04 2.07E + 05 1.24E + 05
Butyrolactone 1.53E + 07 1.70E + 07 2.28E + 07 2.51E + 06 8.66E + 05 7.88E + 05
Diethyl succinate 1.16E + 06 1.35E + 06 9.19E + 05 8.65E + 05 6.64E + 05 4.38E + 05
Terpineol 3.33E + 06 3.00E + 06 1.84E + 06 1.41E + 06 5.63E + 05 5.13E + 05
Citronellol 8.90E + 06 8.10E + 06 6.97E + 06 4.70E + 06 1.82E + 06 1.83E + 06
Nellol 6.15E + 06 1.05E + 06 5.36E + 06 3.02E + 06 2.19E + 06 1.60E + 06
Acetate-2-phenilethyle 3.50E + 06 1.78E + 06 5.69E + 06 5.09E + 06 1.29E + 06 1.16E + 06
Ethyl dodecanoate 2.57E + 06 2.08E + 06 1.00E + 07 9.01E + 06 1.03E + 06 9.40E + 05
Geraniol 3.12E + 06 1.85E + 06 – – 1.03E + 06 9.80E + 05
Guayacol 6.73E + 05 6.20E + 05 – – 3.76E + 05 3.51E + 05
Bencilic alcohol – – – – 1.62E + 05 1.03E + 05
t-Whiskylactone – – 6.38E + 05 2.16E + 05 2.06E + 05 1.45E + 05
2-Phenilethanol 1.11E + 06 6.10E + 05 – – 3.54E + 05 2.29E + 05
Wiskylactona 1.07E + 06 9.14E + 05 4.69E + 05 4.14E + 05 1.73E + 06 1.33E + 05
4-Etilguayacol 1.01E + 06 9.80E + 05 8.35E + 05 8.16E + 05 3.20E + 05 2.23E + 05
2-Ethylphenol 1.59E + 06 7.93E + 05 8.92E + 05 5.61E + 05 1.15E + 06 8.03E + 05
Guayacol – – 3.80E + 05 1.32E + 05 1.12E + 05 1.08E + 05
4-Ethylphenol 6.31E + 05 4.51E + 05 4.09E + 05 3.54E + 05 5.66E + 05 4.35E + 05

heating at 250 ◦ C). In a first desorption process, the fiber was
dried at 50 ◦ C during 1 min (the gases desorbed in this step were
discarded). Then, a second desorption at 250 ◦ C during 10 min
was carried out and the volatiles injected into the test chamber.
The benefits of the two-step thermal desorption in the perfor-
mance of the array of MOS sensors are illustrated in Fig. 3, where
the responses towards the standard wine, a water:ethanol solu-
tion and pure water as obtained using the three types of fibers are
represented. As observed in the figure, the drying step reduced
drastically the level of moisture reaching the sensors’s chamber.
This is specially true in the case of the PA fiber where the levels
of water detected by the sensors were almost negligible. The PA
fiber also permitted to decrease the levels of ethanol reaching
the sensor’s chamber; for this reason, the signals produced by
the water:ethanol 12% solution were clearly less intense than
those obtained for the standard red wine. This indicated that the
response of the sensors towards wines was related to the pres-
ence of other volatile components besides ethanol or water. In
contrast, both fibers containing PDMS absorbed such important
amounts of ethanol that, even using a two-step desorption pro-
cess, the responses towards the water:ethanol 12% solution were
similar to those observed for the standard red wine (notice that in
the case of PDMS/CW/DVB, the signals corresponding to wine
and water/ethanol are superimposed).
The results were confirmed with chromatography. As shown
in Table 5 using this method, the levels of water reaching the
chromatographic detector decreased whatever the type of fiber
used (one order of magnitude for PDMS/CW/DVB and PA
fibers). Moreover, the levels of ethanol decreased two orders
of magnitude when the PA fiber was used. For the three fibers,
284 S. Villanueva et al. / Sensors and Actuators B 120 (2006) 278–287

Fig. 4. Response of MOS sensors towards a red wine as collected with Poly-
acrylate fiber and using different temperatures of desorption.

The intensity of the signals could be further improved by mak-

ing adjustments in other experimental conditions, for instance,
the temperature and duration of the absorption of volatiles by the
fibers. To evaluate the influence of these parameters a series of
experiments were carried out by varying the temperature of the
wine samples (40, 45 and 50 ◦ C) and the time of exposure of the
fiber to the headspace of the wines (5, 10 and 15 min) using a fac-
torial experiment design (32 ). Fig. 5 shows the surface response
plot corresponding to the results of the nine experiments car-
ried out for each fiber. X- and Y-axes represent the time and
temperature used for the absorption, respectively, while Z-axis

Fig. 3. Polar plots of the responses (expressed as peak height) of the array of
sensors towards towards water (. . .), ethanol:water 12% (—) and the standard
red wine ( ) using a two-step desorption process (a) PDMS, (b) PA and (c)
PDMS/CW/DVB.

VOCs reached the detector in acceptable levels (in the case

of PDMS and PDMS/CW/DVB some volatiles could not be
detected).
It could be expected that the temperature at which the second
desorption is carried out, had a strong influence in the perfor-
mance of the system. In order to evaluate this influence, the
response of the array of sensors towards a red wine at desorption
temperatures ranging from 50 to 300 ◦ C was evaluated. Fig. 4
represents the intensity of the responses (expressed as the aver-
age of the intensities of the responses of the 14 sensors) obtained
using PA fiber, by carrying out the thermal desorption at differ-
ent temperatures. As observed in the figure, the intensity of the
responses of the MOS sensors increased when increasing the
temperature of desorption. This result can be explained assum-
ing that the highest the temperature, the highest the amount of
volatile components desorbed from the fiber. At temperatures
higher than 300 ◦ C, the intensity and the repeatability of the
signals decreased drastically (CV >25% for seven consecutive
measurements), making 300 ◦ C the optimal temperature. Similar
results were observed when using PDMS and PDMS/CW/DVB Fig. 5. Effect of the temperature and time of absorption in the response of MOS
fibers. sensors exposed to a red wine using (a) PDMS (b) PA (c) PDMS/CW/DVB.
 S. Villanueva et al. / Sensors and Actuators B 120 (2006) 278–287 285

Table 6
Repeatability of the measures obtained by exposure of a red wine to the MOS
sensors using the three fibers
ID C.V.PA (%) C.V.PDMS (%) C.V.PDMS/CW/DVB (%)

S1 3 3 5
S2 7 14 15
S3 1 1 1
S4 3 3 4
S5 4 12 12
S6 1 2 1
S7 10 18 25
S8 1 2 4
S9 1 1 2
S10 2 2 4
S11 1 2 1
S12 2 3 5
S13 12 15 21
S14 8 15 16

represents the response of the array of sensors (expressed as aver-
age intensity of the responses of the 14 sensors). As observed in
the figure, the amount of volatiles absorbed in the fiber and hence
the response of the sensors depends on the time and temperature
used during the exposure. For instance, when using PDMS and
PDMS/CW/DVB fibers, the intensity of the signals reached a
maximum at ca. 10 min and 45 ◦ C. In the case of PA, the oppo-
site trend was observed and a minimum of the surface appear
at medium values of temperature and time, being the optimal
conditions 40 ◦ C and 5 min of exposure.
After optimizing the experimental conditions for SPME, the
repeatability of the optimized method was evaluated. For this
purpose, experiments were carried out where the standard red
wine was exposed seven consecutive times to the array of sensors
using the three types of fibers (Table 6). In all cases a two-step
desorption process was used. The exposure of the fiber to the
wine was carried out under the optimized conditions appropriate
for each fiber.
As observed in table, the repeatability of the signals obtained
using PA fiber was higher that the obtained for data collected
with PDMS or PDMS/CW/DVB.
Taken into account the results presented in the previous para-
graphs, it can be concluded that PA fiber is able to eliminate
higher amounts of ethanol than PDMS or PDMS/CW/DVB
fibers while maintaining good levels of other minoritary
volatiles. Moreover, the results obtained using PA fiber are more
reproducible. The optimal working conditions for a SPME cou-
pled to an array of MOS sensors devoted to the analysis of
red wines can be summarized as follows: the wine sample is
immersed in a bath kept at 40 ◦ C. After equilibration, a Poly-
acrilate fiber is kept in contact with the headspace of the samples
for 5 min. The fiber is then transferred to the injection port, and
pre heated at 50 ◦ C. The desorbed volatiles are discarded. Then
a second heating was performed at 300 ◦ C using an air/nitrogen
flow, the VOCS are injected in the test box.
The capability of discrimination of the SPME coupled to an
array of MOS sensors system was evaluated by exposing the
sensors to five red wines elaborated using the same vinification
Fig. 6. PCA scores plot of the responses of the array of sensors towards five red
wines elaborated with different varieties of grape using PA fiber.
and ageing methods but differing in the different varieties of
grape used to elaborate de wine. Principal component analy-
sis (PCA) was carried out using signals corresponding to seven
repeated exposures collected in different days. The peak height
value was chosen as the input of the multivariate analysis. Fig. 6
shows the score plot of principal components. Four components
were found to be relevant. The first and second principal com-
ponents, shown in Fig. 6, capture 66.05 and 28.95% of the total
variance, respectively. Correlation loadings plot from PCA are
displayed in Fig. 7. Significant sensors are located, within cir-
cles corresponding to 50 and 100% explained variance. In this
case, the correlation loadings plot reveals that sensors S3-S5, S7-
S10 and S12 are highly correlated (correlation >0.94). Table 7
shows the explained variances for calibration and validation.
The cross-validated variances for the four principal components
were 59.16, 35.23, 4.78 and 1.02%, respectively.
The PCA clusters shown in Fig. 6 are small and well
separated, allowing an easy discrimination of wines. PCA
demonstrate that varieties that produce wines with similar
organoleptic characteristics (Tinta del Pais, Tempranillo and
Fig. 7. PCA loadings plot corresponding to the responses of the array of sensors
towards five red wines elaborated with different varieties of grape using PA fiber.
Circles correspond to 50 and 100% of explained variance.
286 S. Villanueva et al. / Sensors and Actuators B 120 (2006) 278–287
Table 7
Explained calibration and validation variance from PCA
PC’s Calibration
Explained variance
PC1 66.05
PC2 28.95
PC3 3.39
PC4 1.51
RMSEC, root mean square error of calibration; RMSEV, root mean square error of validation.
Tinta de Toro) appear close to each other in the left side of
the diagram, whereas the varieties Mencı́a and Prieto Picudo
that give rise to a different composition of the volatile fraction
appear in the right side. This result is in good agreement with
the results obtained in chromatography shown in Table 3, that
show that the composition of the headspace of wine G4 is
clearly different to that of the other wines.
These results confirm that our system is detecting the volatiles
present in the headspace of the sample and reveals the adequate
performance of the optimized SPME technique for the analysis
of red wines.
4. Conclusions
A system combining an array of MOS sensors with a SPME
preconcentration system has been optimized to increase the
discrimination capability towards red wines. The elimination
of water and ethanol is drastically improved by using a polar
absorbent material such as polyacrylate and by performing the
thermal desorption in two steps (a first desorption at low tem-
perature to dry the fiber followed by a thermal desorption at
high temperature). Other experimental parameters such as the
temperature and time used to absorb the volatiles also play an
important role in the performance of the system. Using the opti-
mized conditions the capability of discrimination of the array of
sensors is so efficient that it is possible to discriminate among
similar red wines. For instance, the principal component anal-
ysis of the obtained signals allows the discrimination of five
wines elaborated with grapes from the same geographical area
and using the same vinification and ageing methods (vintage
2000) being the only variable modified the variety of grape. The
results obtained are in good agreement with those obtained with
chromatography. As a final conclusion, it is important to high-
light that the experimental requirements of SPME coupled to an
array of sensor need to be adapted to the particular characteris-
tics of the resistive sensors. Search of the adequate experimental
conditions is crucial to improve the capability of discrimination
of the arrays of sensors.
Acknowledgments
Financial support provided by UE Project (FP6-IST-1-
508744-IP) and ITACyl Project (VA-162005) is gratefully
acknowledged.
Validation
RMSEC Explained variance RMSEV
0.331 59.16 0.420
4.653 × 10−2 35.23 6.027 × 10−2
8.625 × 10−3 4.78 1.350 × 10−2
2.753 × 10−4 1.02 1.868 × 10−4
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Biographies
Sonia Villanueva was born in Valladolid (Spain), in 1977. She received BSc in
chemistry in 2002 from the University of Valladolid (Spain). She received the
master in chemistry in 2004 from the University of Valladolid (Spain). She is
presently a PhD student of the Department of Condensed Matter Physics at the
University of Valladolid. Her current field of research interests consist of aspects
related to the use chromatography techniques and their application in electronic
noses for the characterization of different beverages.
Alberto Vegas was born in Llano de Olmedo (Spain), in 1967. He received BSc
in physics in 1991 from the University of Valladolid (Spain). He has worked
as a researcher in the development of environment sensors, photometric and
spectrophotometric instrumentation and in the development and validation of
simulation software for lighting. His current field of research consists in the
integration of sensor systems for organoleptic characterization of foods. Until
now, he has been co-author of several international publications.
Marı́a Luz Rodrı́guez-Méndez is a professor in the Department of Inorganic
Chemistry of the E.T.S. Industrial Engineers in the University of Valladolid. She
received the degree in chemistry from the University Complutense of Madrid in
1984 and her PhD in chemistry from the University of Valladolid (Spain) in 1990.
She has been working in the preparation and the structural characterization of
thin films of organic semiconductors and their potential applications. Her main
current interest is in the development of sensors based on phthalocyanines and
on conducting polymers. At the present moment, she is involved in a UE Project
devoted to the development of an electronic nose, an electronic tongue and an
electronic eye for the assessment of the organoleptic characteristics of wines
and olive oils. She is author or co-author of over 70 publications.
José Antonio de Saja was born in Miranda de Ebro (Spain), in 1940. He
is a professor and Head of the Department of condensed matter physics at
the University of Valladolid. His present research interest is at the intersec-
tion of materials science, physics, physical chemistry and device engineering
and focus on novel nanostructured materials (mainly from LB monolayers).
At the present moment he is coordinating a UE Project devoted to the devel-
opment of an electronic nose, an electronic tongue and an electronic eye for
the assessment of the organoleptic characteristics of wines and olive oils.
He is author or co-author of over 190 publications and has edited seven
books.