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Article history: In this work, attempts were made in order to characterize the change of aroma of alcoholic and non
Received 17 March 2011 alcoholic beers during the aging process by use of a metal oxide semiconductor based electronic nose.
Received in revised form 3 June 2011 The aged beer samples were statistically characterized in several classes. Linear techniques as principal
Accepted 8 June 2011
component analysis (PCA) and Linear Discriminant Analaysis (LDA) were performed over the data that
Available online 14 June 2011
revealed non alcoholic beer classes are separated except a partial overlapping between zones correspond-
ing to two specified classes of the aged beers. A clear discrimination was not found among the alcoholic
Keywords:
beer classes showing the more stability of such type of beer compared with non alcoholic beer. In this
Beer
Aging
research, to classify the classes, two types of artificial neural networks were used: Probabilistic Neural
Electronic nose Networks (PNN) with Radial Basis Functions (RBF) and FeedForward Networks with Backpropagation (BP)
Machine olfaction learning method. The classification success was found to be 90% and 100% for alcoholic and non alcoholic
Artificial neural network beers, respectively. Application of PNN showed the classification accuracy of 83% and 100%, respectively
Metal oxide semiconductor for the aged alcoholic and non alcoholic beer classes as well. Finally, this study showed the capability of
Artificial nose the electronic nose system for the evaluation of the aroma fingerprint changes in beer during the aging
Gas sensors process.
© 2011 Elsevier B.V. All rights reserved.
0925-4005/$ – see front matter © 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.snb.2011.06.036
52 M. Ghasemi-Varnamkhasti et al. / Sensors and Actuators B 159 (2011) 51–59
Table 1
Sensor array used in the electronic nose system.
2. Materials and methods
Sensor Description
Five metal oxide semiconductor (MOS) gas sensors were sup- 1: SPMW0 Tin dioxide, monitors the changes of
plied from FIS (Osaka, Japan) and Figaro Engineering (Glenview, various gases emitted during cooking
USA) companies and the test chamber of the electronic nose sys- 2: SPAQ1 Tin dioxide semiconductor sensor, very
high sensitivity to volatile organic
tem was, therefore, fabricated (Fig. 1). The sensors included in the compounds (VOCs) and solvents
test chamber of the system and their specifications are presented 3: TGS2620 Alcohol, toluene, xylene, other volatile
in Table 1. These sensors are placed in a half bridge and are supplied organic vapors
with a 10 V circuit voltage and a 5 V heating voltage providing an 4: TGS825 Hydrogen sulfide
5: TGS880 Volatile vapors from food (alcohol)
operating temperature according to the companies operating data
M. Ghasemi-Varnamkhasti et al. / Sensors and Actuators B 159 (2011) 51–59 53
Fig. 2. The signals of the electronic nose studied: (a) one cycle of injection and
purging signal related to SPMW0 sensor and (b) stability of the instrumentation
systems in successive measurements.
Fig. 3. Fingerprints of beer headspace during the aging: (a) non alcoholic sample
(response of SPMW0) and (b) alcoholic samples (response of TGS 825).
the literature [10,31,32]. The interval time of 5 days was considered
among the experiments. The beer samples were prepared for the
experiments of electronic nose according to the literature [33]. For during the aging have been illustrated in Fig. 3a and b, respectively.
this purpose, an ultrasonic bath for 10 min was used to remove CO2 However, the features corresponding to individual sensors were
from the sample and the beers were then left to reach the ambient then extracted and the steady state of the signals was addressed in
temperature. Also, dynamic injection after static headspace sam- feature extraction [36,37]. Then, the following equation was used.
pling was considered in this study. The carrier gas was synthetic air Rsample
for preserving the beer samples. The amount of 50 ml of beer sample F= (1)
Rcalibration
was kept in a 250 ml bottle at 25 ◦ C for 45 min in order to provide a
vapor phase in equilibrium with the liquid. In this system, the syn- where Rsample is the minimum resistance of the sensor during per-
thetic air is brought into a sample container based on the bubbler forming the measurement protocol and Rcalibration is that of the
principle and then mixed with the beer headspace and the mixture sensor exposed to an ethanol solution. Autoscaling as a data pre-
portion is therefore, controlled by a mass flow controller (Brooks, processing technique was considered and the software of Matlab
Serv Instrumentation, Irigny, UK). These portions were determined 7.6 (The Mathworks Inc., Natick, MA, USA) was used to analyze the
as 100 (synthetic air) and 80 (synthetic air) + 20 (sample headspace) data collected and to perform artificial neural network as well.
ml/min in purging and injection phases, respectively. For purging In this work, Principal Components Analysis (PCA) and Linear
the sensor array, the electric valves were switched during 1300s Discriminant Analysis (LDA) as the data reduction methodologies
and dynamic injection of the beer headspace was then carried out are used to reduce the number of variables of the dataset and retain-
for 360 s (Fig. 2). This procedure was done in seven replicates for ing most of the information in the data. Score plots of the data
each beer sample. To remove the effects of sensors drift, sensor are illustrated and the PCA and LDA results are then confirmed by
array were calibrated with a blank solution (4.4% (v/v) (for alcoholic artificial neural networks.
beer samples) ethanol in deionised water). This protocol has been A probabilistic neural network (PNN) is used for classification
used and reported for wine in bibliography [34,35]. All the sensor purposes. The architecture of PNN is illustrated in Fig. 4. The PNN is
output signals were collected by use of a data acquisition board included three layers: the input one has three neurons, correspond-
(LabView, National Instruments). For instance, the sensor finger- ing to the three principal components; the hidden layer, with radial
prints of SPMW0 for alcoholic and TGS 825 for non alcoholic beers basis transfer functions, has the same number of neurons that num-
54 M. Ghasemi-Varnamkhasti et al. / Sensors and Actuators B 159 (2011) 51–59
aged beer classes (Fig. 5). The network considers the inputs and
compares its outputs in opposition to the desired outputs. Errors 0
are then propagated back through the system, causing the system
to adjust the weights that control the network. This process takes -0.5
place over and over as the weights are repeatedly tweaked. Dur-
ing the network training, the same set of data is processed many -1
times as the connection weights are always refined [42–44]. In final,
classification accuracy is computed for each method. -1.5
0.5
-0.5
-1
-1.5
-2
-4 -3 -2 -1 0 1 2 3
PC1 (58%)
(b)
Fig. 6. PCA plots of aging fingerprint characterization for (a) alcoholic beer and (b)
Fig. 5. Architecture of a backpropagation (BP) neural network. non alcoholic beer.
M. Ghasemi-Varnamkhasti et al. / Sensors and Actuators B 159 (2011) 51–59 55
in the data are known as the new axis to attain the plots of the beer 0.4
classes called as score plot (Fig. 6). The PCA score plots of PC1–PC2 4
account for 91% and 87% of variance for alcoholic and non alco- 0.2
5
holic beers, respectively. The first class seen in the left side of the
score plot is relevant to the fresh class in such a way identifica- 3
0
tion power of A0 (fresh alcoholic beer) from other classes is lesser
Loads 2 (23%)
than that of N0 (fresh non alcoholic beer) as shown in Fig. 6a and
-0.2
b, respectively. As seen in Fig. 6, the aged beer classes of alcoholic
beer are overlapped showing the more stability of alcoholic beer 1
in aging process compared with non alcoholic beer. This observa- -0.4
tion confirms the profound role of alcohol in beer to enhance the
beer stability in aging process as pointed out in literature [45–47]. -0.6
This fact is documented that ethanol has a key role in the forma-
tion of the characteristic background aroma of beer. When alcohol
-0.8
is removed from regular beer by use of different techniques of deal-
2
coholization, partial aroma loss occurred. Therefore, non alcoholic
beers do not represent the aroma components produced through -1
0.1 0.15 0.2 0.25 0.3 0.35 0.4 0.45 0.5 0.55 0.6
fermentation in a proper concentration and balance. Hence, in the Loads 1 (68%)
absence of ethanol, beer exhibits immature aroma even after pack-
ing [48]. Also, as seen in Fig. 6b, for non alcoholic beer, the speed of (a)
aroma change in early stages of the aging process is more than that
0.8
of in late stages that this phenomenon seems to be related to the
role of alcohol in beer but in contrast aroma fingerprint of alcoholic 5
beer is more stable in early stages of aging process (Fig. 6a) even 0.6
though in general, the speed of aging is dependent on many factors 1
such as storage temperature and beer composition [4]. 0.4
Besides the aged beer classes, the sensors or variables could be 2
Loads 2 (29%)
2.5 1.5
A0 A0
2
A1 A1
A2 1 A2
1.5 A3 A3
A4 A4
1 A5 A5
0.5
LDF2
DF2
0.5
0 0
-0.5
-0.5
-1
-1.5 -1
-2 -1.5 -1 -0.5 0 0.5 1 1.5 2 -2 -1.5 -1 -0.5 0 0.5 1 1.5 2
LDF1 DF1
(a) (b)
5 3
N0 2.5 N0
4 N1 N1
N2 2 N2
N3 N3
3
N4 1.5 N4
N5 N5
1
2
LDF2
DF2
0.5
1
0
0 -0.5
-1
-1
-1.5
-2 -2
-4 -3 -2 -1 0 1 2 3 -4 -3 -2 -1 0 1 2
LDF1 DF1
(c) (d)
Fig. 8. Score plots of aging treatments: (a) alcoholic beer by LDA, (b) alcoholic beer by LDA without validation, (c) non alcoholic beer by LDA and (d) non alcoholic beer by
LDA without validation.
holic beers, respectively (Tables 2 and 3). The similar results were aging process. As found in this study, the aroma fingerprint of the
obtained using PNN as 83% and 100%, respectively for aged alco- beer samples changes in aging process mimicking the long period
holic and non alcoholic beer classes. The result of the test set is storage [31]. What happens in this period is far complicated to
given in Tables 4 and 5. interpret exactly because the flavor of beer is affected by a complex
In this research effort, employment of such chemometric meth- mixture of several volatile chemical compounds as very hetero-
ods showed the capability of the electronic nose to recognize geneous groups (e.g. alcohols, esters, sulfur compounds, ketones,
alcoholic and non alcoholic beers in terms of aroma changes in aldehydes, etc.). These compounds are in very different concen-
Table 2 Table 3
Confusion matrix with 17 neurons in hidden layer for the BP classification of alco- Confusion matrix with 17 neurons in hidden layer for the BP classification of non
holic beer in aging process. alcoholic beer in aging process.
Real/predicted A0 A1 A2 A3 A4 A5 Real/predicted N0 N1 N2 N3 N4 N5
A0 6 1 0 0 0 0 N0 7 0 0 0 0 0
A1 0 7 0 0 0 0 N1 0 7 0 0 0 0
A2 0 0 6 1 0 0 N2 0 0 7 0 0 0
A3 0 1 0 6 0 0 N3 0 0 0 7 0 0
A4 0 0 0 1 6 0 N4 0 0 0 0 7 0
A5 0 0 0 0 0 7 N5 0 0 0 0 0 7
A0: fresh and A1, A2, A3, A4, A5: aged beers. N0: fresh and N1, N2, N3, N4, N5: aged beers.
M. Ghasemi-Varnamkhasti et al. / Sensors and Actuators B 159 (2011) 51–59 57
Table 4 4. Conclusion
Confusion matrix for the PNN classification of alcoholic beer in aging process.
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refrigerant gas in a humidity controlled atmosphere containing or not carbon Mahdi Ghasemi-Varnamkhasti was born in Isfahan (Iran), in 1983. He received
dioxide: application to the electronic nose, Sensors and Actuators B 98 (2004) the master in Mechanics of Agricultural Machinery Engineering in 2005 from the
46–53. University of Tehran (Iran). He is presently a Ph.D. student of the Department of
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83–89. process. At the present moment he has obtained a lecturer position at the Sharekord
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3911–3915. Seyed Saeid Mohtasebi received his B.Sc. and M.Sc. degrees in Mechanical Engineer-
[33] K. Siebert, P.Y. Lynn, Comparison of methods for degassing beer for analysis, ing from Sharif University of Technology, Tehran, Iran in 1988 and 1991, respectively.
Journal of the American Society of Brewing Chemist 65 (2007) 229–231. He received his Ph.D. in Mechanical Engineering from Concordia University, Quebec,
[34] R. Gutierrez-Osuna, Pattern analysis for machine olfaction: a review, IEEE Sen- Canada in 1997. He is currently a Professor in Department of Agricultural Machin-
sors Journal 2 (2002) 189–202. ery Engineering in University of Tehran. His current research interests are control,
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Olfaction, Wiley-VCH Velag GmbH & Co. KGaA, Weinheim, UK, 2003. Ph.D. in Biomedical Electronics engineering in 1989 from the Polytechnic Institute
[37] J. Lozano, J.P. Santos, M.C. Horrillo, Enrichment sampling methods for wine of Lorraine (ENSEM- INPL) at Nancy, France. She is an associate professor at the
discrimination with gas sensors, Journal of Food Composition and Analysis 21 University of Metz since 1991 and her research interests are in gas detection, sig-
(2008) 716–723. nal and data processing, sensor characterization and numerical electronics circuits’
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[39] B. Tudu, A. Jana, A. Metla, D. Ghosh, N. Bhattacharyya, R. Bandyopadhyay, Elec-
Jesus Lozano received the B.Sc. degree in electronic engineering in 2001 and Ph.D.
tronic nose for black tea quality evaluation by an incremental RBF network,
degree in 2005 from Universidad Complutense de Madrid, Spain. He has worked in
Sensors and Actuators B: Chemical 138 (2009) 90–95.
instrumentation systems at Electronics Department of the University Complutense
[40] C. Riverol-Canizares, V. Pilipovik, The use of radial basis function networks
of Madrid, in chemical sensors and electronic noses at the Laboratorio de Sensores,
(RBFN) to predict critical water parameters in desalination plants, Expert Sys-
Consejo Superior de Investigaciones Cientı̌ıficas (CSIC), Madrid, in control, modelling
tems with Applications 37 (2010) 7285–7287.
and simulation at Naval Engineering School of Universidad Politecnica de Madrid.
[41] K. Dutta, N. Prakash, S. Kaushik, Probabilistic neural network approach to the
Presently, he works as professor at Escuela de Ingenierıas Industriales of Universidad
classification of demonstrative pronouns for indirect anaphora in Hindi, Expert
de Extremadura, Badajoz. His research interests include pattern recognition tech-
Systems with Applications 37 (2010) 5607–5613.
niques, aroma extraction techniques applied to electronic noses, instrumentation
[42] C.M. Bishop, Neural Networks for Pattern Recognition, Oxford University Press,
and measurement systems, and chemical sensors.
Oxford, UK, 1999.
[43] H. Yu, J. Wang, C. Yao, H. Zhang, Y. Yu, Quality grade identification of green tea Hojat Ahmadi received his Ph.D. degree in agricultural machinery engineering in
using E-nose by CA and ANN, LWT 41 (2008) 1268–1273. 2001 from Tarbiat Modares University, Iran. He is currently an associate professor
[44] F. Marini, Artificial neural networks in foodstuff analyses: trends and perspec- at the University of Tehran and his research interests are condition monitoring and
tives a review, Analytica Chimica Acta 635 (2009) 121–131. nanotechnology and its application to agricultural issues.
M. Ghasemi-Varnamkhasti et al. / Sensors and Actuators B 159 (2011) 51–59 59
Seyed Hadi Razavi received his B.Sc. degree in food technology & engineering in Amadou Dicko received his Ph.D. degree in organic chemistry in 1989 from Uni-
1984 from University of Tehran and his Ph.D. degree in food process engineering & versity of Perpignan Via Domitia at Perpignan, France. He is currently a Professor
biotechnology in 2004 from the Polytechnic Institute of Lorraine (ENSAIA-INPL) at at the Laboratoire de Chimie et de Méthodologies pour l’Environnement (LCME) in
Nancy, France. He is currently an associate professor at the University of Tehran and the University Paul Verlaine-Metz. His research interests are in extraction methods,
his research interests are in food biofilms and fermented and probiotic beverages, identification and characterization of secondary metabolites applied to polyphenolic
batch, fed batch and continuous bioreactors with free of immobilized cells, dairy compounds.
and non dairy functional.