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Sensors and Actuators B 119 (2006) 538546

Characterization of Chinese vinegars by electronic nose


Qinyi Zhang a,b , Shunping Zhang a , Changsheng Xie a, , Dawen Zeng a ,
Chaoqun Fan a , Dengfeng Li a , Zikui Bai a
a

Department of Material Science and Engineering, Huazhong University of Science and Technology, Wuhan 430074, China
b Department of Material Science and Engineering, Wuhan University of Technology, Wuhan 430070, China
Received 31 August 2005; received in revised form 30 December 2005; accepted 4 January 2006
Available online 8 February 2006

Abstract
In this paper, 17 commercial Chinese vinegars, acetic acid and 5% diluted acetic acid were analyzed by an electronic nose containing nine nano
ZnO thick film gas sensors, which are doped by 5 wt.% and 10 wt.% TiO2 , 5 and 10 wt.% MnO2 , 1 wt.% V2 O5 , 5 wt.% Bi2 O3 , 0.6 and 2.4 wt.% Ag,
and 5 wt.% W, respectively. Principal component analysis (PCA) and cluster analysis (CA) were employed to investigate the presence of classes
inside the sample population. It was shown that characterizing the Chinese vinegars by the electronic nose was highly related to their type, raw
materials, total acidity, fermentation method and production area and all these influencing factors were not independent. The CA results indicated
that the type and fermentation method were more effective than the other influencing factors when the vinegars were analyzed by the electronic
nose. Finally, the data colleted by the electronic nose were applied to the learning vector quantization (LVQ) neural network performing the role of
recognition and classification of the vinegars. The accuracy in terms of predicting tested vinegar measurements was 72.1%, 76.5%, 77.9%, 94.1%
and 82.4% according to their type, raw materials, total acidity, fermentation method and production area, respectively. This work was the first
step to establish a gas-sensing fingerprint database of Chinese vinegars and develop a commercial electronic nose on the Chinese vinegars quality
control.
2006 Elsevier B.V. All rights reserved.
Keywords: Electronic nose; Chinese vinegar; PCA; CA; LVQ

1. Introduction
Vinegar is defined as a liquid fit for human consumption
and contains a specified amount of acetic acid. China has more
than 5000 years history of producing vinegar. Every year over
26 million hectoliters of vinegar is produced in China. Chinese
people treat the vinegars as favorite condiments, health products
and even medicines. More than 3.2 million liters of vinegar is
consumed every day in China. Because the quality of vinegar
directly affects the peoples health, Chinese governments have
paid more and more attention on the quality control of vinegar.
The China State Bureau of Quality and Technical Supervision
had issued the market allowance policy on vinegar quality and
safety in 2002 in China. From then on, the vinegar enterprises
must take out the vinegar producing license and pass the onthe-spot check of the producing necessary conditions. At the

Corresponding author. Tel.: +86 27 8755 6544; fax: +86 27 8754 3776.
E-mail address: csxie@mail.hust.edu.cn (C. Xie).

0925-4005/$ see front matter 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.snb.2006.01.007

same time, the China State Bureau of Standards has issued the
related standards to specify the classification, requirement, labeling, packaging, storage, transport and inspecting of vinegar to
ensure the quality of vinegar and the peoples health.
In China, studies on Chinese vinegar quality evaluation are
scarce, but in Europe, the quality control of vinegar is widely
investigated by using sensory analysis for the concession of
manufacturers seals of guarantee over the last decade [1,2].
Sensory analysis requires a well trained testing panel and limited vinegar samples are examined at each tasting session, in
order not to excessively tire the assessors [2]. At the same time,
the accuracy and objectivity cannot always be ensured because
the assessors are influenced by their healthy conditions, emotions and environment. So, various chemical analysis methods,
such as ion-selective electrodes [3], atomic absorption spectrum
[4], gas chromatography [58] and pyrolysis-mass spectrometry [9,10], are developed to measure the vinegar compounds and
control the vinegar quality. Since vinegars contain more than
100 compounds, chemical analysis methods are complicated and
expensive. Also, they are not convenient for real-time, on-line

Q. Zhang et al. / Sensors and Actuators B 119 (2006) 538546

and in situ detection. Therefore, there is a need for new reliable


methods for the assessment of characteristics of Chinese vinegar
products.
The electronic nose is a very promising technique for overcoming the aforementioned disadvantages for vinegar characterization. Recently, electronic noses have been extensively used
to test the food quality, and good results have been reported in
the characterization of foodstuffs, such as wine [11,12], beverage [13], coffee [14], milk [15], orange and apple [16], and
vegetable oils [17]. Unfortunately, only a few incomplete studies
concentrate on the vinegar characterization with electronic noses
[10,18]. These studies are far from the need of the application
of electronic noses on the vinegar characterization.
In this paper, we presented an approach to the application of
an electronic nose in the characterization of the 17 commercial
Chinese vinegars. The electronic nose contained nine thick-film
gas sensors prepared from ZnO nanoparticles doped with MnO2 ,
TiO2 , V2 O5 , Bi2 O3 , W and Ag. Acetic acid and diluted acetic
acid were also measured by the electronic nose for comparison.
The responses of the array of nine ZnO thick film sensors to 17
vinegars were studied by principal component analysis (PCA)
and cluster analysis (CA) to investigate the presence of classes
inside the sample population. Finally, the data colleted by the
electronic nose were applied to the learning vector quantization

539

(LVQ) neural network performing the role of recognition and


classification of the vinegars. This work was the first step to
develop a commercial electronic nose on the Chinese vinegar
characterization.
2. Experimental
2.1. Vinegar samples
Seventeen commercial Chinese vinegars purchased in a local
supermarket were used as testing samples. The name, type, raw
materials, total acidity, fermentation method and production area
were copied from the vinegar bottle labels and are listed in
Table 1. The main difference between Chinese vinegars and
European vinegars is the raw materials. Chinese vinegars are
mainly produced from rice, sticky rice and wheat bran, while
European vinegars are usually fermented from wine, cider, fruit
juices, malted barley, honey or pure alcohol [7,9]. As shown
in Table 1, 17 commercial Chinese vinegars are divided into 5
groups, namely, aromatic vinegar (7 samples), mature vinegar
(5 samples), rice vinegar (2 samples), white vinegar (2 samples)
and fruit vinegar (1 sample), according to their type. Although
China has a long history for brewing vinegar, there is no specific standard of the Chinese vinegar type at present. The type of

Table 1
The details of the vinegar samples utilized in the experiment
No.

Sample name

Type

Raw materials

Total acidity
(g/100 ml)a

Fermentation method

Production area

Hengshun Xiangcu

Aromatic vinegar

4.0

Solid fermentation

Jiangsu province

Beigushan Xiangcu

Aromatic vinegar

5.0

Solid fermentation

Jiangsu province

Yanhui Xiangcu

Aromatic vinegar

5.5

Solid fermentation

Jiangsu province

4
5

Jinyou Xiangcu
Zhengjiang Xiangcu

Aromatic vinegar
Aromatic vinegar

6.0
6.0

Solid fermentation
Solid fermentation

Jiangsu province
Jiangsu province

Longmen Xiangcu

Aromatic vinegar

4.4

Solid fermentation

Beijing

Weichunyuan Xiangcu

Aromatic vinegar

5.0

Solid fermentation

Guizhou province

Shuita Chencu

Mature vinegar

4.5

Solid fermentation

Shanxi province

Donghu Chencu

Mature vinegar

6.0

Solid fermentation

Shanxi province

10

Beigushan Chencu

Mature vinegar

4.5

Solid fermentation

Jiangsu province

11

Zhengjiang Chencu

Mature vinegar

5.0

Solid fermentation

Jiangsu province

12

Weichunyuan Chencu

Mature vinegar

5.0

Solid fermentation

Guizhou province

13
14

Jinbiao Micu
Longmen Micu

Rice vinegar
Rice vinegar

5.0
4.4

Liquid fermentation
Solid fermentation

Guangdong province
Beijing

15
16
17

Meiweixian Baicu
Longmen Baicu
Haitian Pingguocu

White vinegar
White vinegar
Fruit vinegar

Water, sticky rice, sugar, salt,


sodium benzoate
Water, sticky rice, wheat bran,
sugar, salt
Water, sticky rice, wheat bran,
sugar, salt
Water, sticky rice, sugar, salt
Water, sticky rice, wheat bran,
sugar, salt
Water, rice, wheat bran, sugar,
salt, potassium sorbate
Water, rice, wheat bran, sodium
benzoate
Water, sorghum, barley, pea,
wheat bran, sodium benzoate
Water, sorghum, barley, pea,
sodium benzoate
Water, sticky rice, wheat bran,
sugar, salt
Water, sticky rice, wheat bran,
sugar, salt
Water, rice, wheat bran, sodium
benzoate
Water, rice, salt, alcohol
Water, rice, wheat bran, salt,
potassium sorbate
Water, rice, alcohol
Water, rice, alcohol
Water, rice, apple, glucose,
fructose

3.5
3.95
2.5

Liquid fermentation
Liquid fermentation
Liquid fermentation

Guangdong province
Beijing
Guangdong province

As total acidity expressed in % acetic acid.

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Table 2
Specification of the sensors utilized in the array

2.3. Data analysis

Sensor no.

Dopants (wt.%)

1
2
3
4
5
6
7
8
9

TiO2 (5)
MnO2 (5)
V2 O5 (1)
W (5)
TiO2 (10)
Ag (2.4)
Ag (0.6)
Bi2 O3 (5)
MnO2 (10)

The responses of the electronic nose were first analyzed by


PCA to investigate the presence of classes inside the samples
population. The PCA results were discussed in detail according
to the type, raw materials, total acidity, fermentation method and
production area of the samples to characterize the vinegars by
the electronic nose. CA was employed to examine the sensorial
data and test the relationships of various vinegars. Finally, LVQ
was used to perform the classification of all vinegar samples.
All calculations were performed in matlab 6.5 software.

Chinese vinegars mainly rely on their raw materials, traditional


technologies and production areas.
Considering the main component in vinegar is acetic acid,
acetic acid (analytical purity, 99.7%) was tested by the electronic
nose for comparison. Also, 5% diluted acetic acid was tested by
the electronic nose in order to distinguish the forged vinegar from
the commercial vinegars, since the total acidity in the Chinese
vinegars is about 5%.
2.2. Electronic nose and measurement
The electronic nose contained nine nano ZnO thick-film gas
sensors. ZnO nanoparticles were prepared by thermal evaporation of metallic zinc as raw material in a gas mixture of Ar + O2
under a pressure of 1.0 104 Pa, where the oxygen partial pressure was kept at about 2 103 Pa by controlling the oxygen flux.
The sensors were doped with some commercial oxides and metals to improve their sensitivity and selectivity. The details of the
preparation are described elsewhere [19,20]. The compositions
of the array are shown in Table 2.
All nine thick-film gas sensors were mounted in a printed circuit board to constitute the gas sensor array. Gas-sensing studies
were carried out on a HW-30 gas sensor detection system made
in Hanwei Electronics Co., Ltd., under laboratory conditions
(27 C, 78% relative humidity). In this measurement system,
the signals of nine sensors, the temperature and humidity of the
air can be detected at the same time, and the resistances of all
sensors were observed in real-time by a personal computer. The
measurements were carried out as follows: (1) the sensors were
operated at 320 C and exposed to air in a measurement chamber
with 30 l in volume for 5 min at a constant operating temperature; (2) 20 l vinegar samples were injected by a liquid syringe,
then vaporized by a heater, and the vaporized vinegar vapor was
dispersed throughout the air in the chamber by two fans; (3) the
resistances of sensors reached new stable values after the fans
were shut down to keep the air static in the chamber; (4) fresh air
was fed into the chamber for the recovery before next measurement. The gas response, S is calculated by S = Rair /Rgas , where
Rair and Rgas express the resistance of a sensor in air and in a
detecting gas, respectively.
Each measurement was repeated eight times. Half of the 136
vinegar measurements were used as the training data set (calibration data set) and the other vinegar measurements (68) were
used as the testing data set in LVQ analysis.

3. Results and discussion


3.1. PCA analysis
PCA is a well-known statistical method for reducing the
dimensionality of numerical data sets and widely used for analyzing gas-sensing data [1115,17]. The experimental data were
examined with PCA in order to visualize response patterns in
the feature space of principal components. The data were not
be normalized. The first two principal components were kept
because they accounted for 98.56% of the variance in the data
set (PC1 and PC2 accounted for 97.59, 0.97% of the variance,
respectively). Fig. 1 shows the PCA results of acetic acid, 5%
diluted acetic acid and the vinegars data projected onto their first
two PCs.
It is evident that acetic acid and 5% diluted acetic acid
obviously differed from the vinegars. Vinegars contain a large
amount of trace components, such as esters, alcohols, aldehydes, phenol, glucose and aminophenol, though main ingredients
are water and acetic acid. All the trace components contribute
to smell, taste and the responses of the electronic nose. That is
the reason why the gas-sensing properties to acetic acid and 5%
diluted acetic acid varied from the responses of the vinegars.
Thus, the electronic nose is powerful to distinguish the forged
vinegars from the commercial vinegars.
Fig. 2 shows the PCA results of the all commercial Chinese
vinegars utilized in the experiment. Good reproducibility can

Fig. 1. PCA results of acetic acid, 5% diluted acetic acid and the vinegars data
obtained from sensor array.

Q. Zhang et al. / Sensors and Actuators B 119 (2006) 538546

Fig. 2. PCA results of the vinegars data obtained from sensor array.

be seen in Fig. 2. Most of the samples could be congregated


together by their trademarks. Only a few slight overlaps occurred
at the edges in Fig. 2, for example, the Weichunyuan Chencu
and the Donghu Chencu, and the Zhenjiang Chencu and the
Baigushan Chencu. To character the vinegars and investigate the
relationships between the responses and the type, raw materials,
total acidity, fermentation method and production area of the
vinegars, the same data were plotted with different markings in
Figs. 37. Figs. 37 show the PCA results of the vinegars making
for type, total acidity, fermentation method, raw materials and
production area, respectively.
As shown in Fig. 3, the different type vinegars formed the different groups of points except that a few overlaps occurred in the
aromatic vinegars and the mature vinegars. The aromatic vinegars and the mature vinegars are the most favorite vinegars in
China. Traditionally, the aromatic vinegars are fermented from
stick rice and mainly produced in Jiangsu province, while the
mature vinegars are fermented from sorghum and mainly produced in Shanxi province in China. In Table 1, both the raw
materials and the production areas of the aromatic and mature
vinegars have been changed recently. So the differences between
the aromatic vinegars and the mature vinegars become more and

Fig. 3. PCA results of the vinegars data obtained from sensor array; making for
vinegar type.

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Fig. 4. PCA results of the vinegars data obtained from sensor array; making for
total acidity.

Fig. 5. PCA results of the vinegars data obtained from sensor array; making for
fermentation method.

more ambiguous now. That is the reason why there is no specific


standard of the Chinese vinegar types yet. However, it can be
observed that all the vinegars were well associated to their types
in Fig. 3, except the Shuita Chencu. Meanwhile, we noticed
that the seven aromatic vinegars were divided into two isolated

Fig. 6. PCA results of the vinegars data obtained from sensor array; making for
raw materials.

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Q. Zhang et al. / Sensors and Actuators B 119 (2006) 538546

Fig. 7. PCA results of the vinegars data obtained from sensor array; making for
production area.

areas by the rice vinegars in the PCA plane. The reason will be
discussed later.
Considering acetic acid is the main ingredient in the vinegars,
the PCA data were redrawn according to the total acidity of the
vinegars in Fig. 4. The graph in Fig. 4 shows a sufficient but not
so good separation among clusters. Only the Longmen Baicu,
Meiweixian Baicu, Hengshun Xiangcu and Haitian Pingguocu,
which contain less than or equal to 4.0 g/100 ml total acidity,
can ideally come together in a group. The other groups, which
contain 4.44.5, 5.05.5 and 6.0 g/100 ml total acidity, highly
overlapped either at their edges or inside their groups. It is clearly
evident that acetic acid is an important but not critical factor to
character the Chinese vinegars.
It is indicated that two distinct groups of points, which correspond to solid fermentation and liquid fermentation vinegar,
respectively, are well distinguished in Fig. 5. The vinegars used
in our experiment can be perfectly divided into two classes,
i.e. solid fermentation vinegar and liquid fermentation vinegar,
according to their fermentation methods. We also noticed that
the fermentation method was highly related to the vinegar raw
materials, as will be discussed below. Furthermore, the two rice
vinegar samples, i.e. the Jingbiao Micu and the Longmen Micu,
show a great difference in Fig. 5. The Jingbiao Micu is very
similar to the white vinegars because of the same fermentation
method and the similar raw materials, while the Longmen Micu
is basically the same as the aromatic vinegars, which are all fermented in solid and produced from rice and wheat bran, etc.
This can explain that the aromatic vinegars were divided into
two isolated areas by the rice vinegars in Fig. 3.
Comparing the relationships between the responses of the
electronic nose and the raw materials of the vinegars was a hard
work in our experiment, because the each vinegar used more
than three or four different materials. We noticed that most of
the vinegars used stick rice, rice or sorghum, and/or wheat bran,
sugar and salt as the raw materials, except that the Longmen
Micu and the white vinegars used rice and alcohol as the raw
materials. We also perceived that some vinegar were added with
sodium benzoate or potassium sorbate as antiseptic substances to
prolong the vinegars storage life. Based on our best knowledge,

these chemical additives must contribute to the responses of gas


sensors and some patterns should be found by PCA analysis. So
the PCA results were redrawn in four groups, i.e. using alcohol,
adding sodium benzoate, adding potassium sorbate and others,
in Fig. 6. The PCA results in Fig. 6 support our contention for the
effect of the raw materials in vinegars, such as alcohol, sodium
benzoate and potassium sorbate. Only the Hengshun Xiangcu
separated from the adding sodium benzoate group because of
the lower total acidity (Fig. 4).
Traditionally, Chinese vinegars have a strong regional characteristic. For example, Jiangsu province is usually famous of
their aromatic vinegars as well as the mature vinegars in Shanxi
province. Although the production areas of the same type vinegars have been changed recently, good separation could still be
seen in Fig. 7, whatever the type, raw materials, total acidity and
fermentation method the vinegars belong to. This phenomenon
should be owed to the same production area of the main raw
material (rice, sticky rice or sorghum) of the vinegars. For example, the Longmen Micu, Longmen Baicu and Longmen Xiangcu,
which were produced in the same production area but belonged
to the different type and had different total acidity, constituted a
fairly good group of Beijing in Fig. 7.
The results of PCA analysis show that characterizing the Chinese vinegars by the electronic nose is highly related to their
type, raw materials, total acidity, fermentation method and production area. More or less overlaps were occurred in the PCA
plane when divided by the aforementioned factors except that
two distinct clusters could be formed according to their fermentation methods. It shows that all these influencing factors were
not independent when the vinegars were measured by the electronic nose. Because the relationships amongst the influencing
factors cannot be found intuitively by the PCA analysis, CA was
applied to investigate the internal similarities of all samples in
the large.
3.2. CA analysis
Roughly speaking, CA can yield a data description in terms
of clusters or groups of data points that possess strong internal
similarities. CA is a more direct tool to find subclasses than PCA.
We used CA analysis to study the relationships and the scale of
each influencing factor, such as type, raw materials, total acidity,
fermentation method and production area, when the vinegars
were surveyed by the electronic nose. A Euclidean metric was
used in the CA with an average between groups method of
linkage. Considering the large amount of the measurements, the
average responses of eight measurements to each of 17 vinegar
samples were applied to CA analysis and the CA dendrogram is
shown in Fig. 8.
Two different groups could be seen in the dendrogram, the
first group included samples 3, 912 referred to mature vinegar,
and samples 1, 48, 1316 formed the second group referred
to aromatic vinegar, rice vinegar and white vinegar. It is shown
that the rice vinegar and white vinegar were more similar to
the aromatic vinegar than to the mature vinegar. The Euclidean
distance between the two white vinegars (samples 15 and 16)
was close and satisfied. Contrastively, the Jingbiao Micu and the

Q. Zhang et al. / Sensors and Actuators B 119 (2006) 538546

Fig. 8. CA dendrogram based on the average responses of 9 sensors to the 17


vinegar samples. (1) Hengshun Xiangcu; (2) Beigushan Xiangcu; (3) Yanhui
Xiangcu; (4) Jinyou Xiangcu; (5) Zhengjiang Xiangcu; (6) Longmen Xiangcu;
(7) Weichunyuan Xiangcu; (8) Shuita Chencu; (9) Donghu Chencu; (10) Beigushan Chencu; (11) Zhengjiang Chencu; (12) Weichunyuan Chencu; (13)
Jinbiao Micu; (14) Longmen Micu; (15) Meiweixian Baicu; (16) Longmen
Baicu; (17) Haitian Pingguocu.

Longmen Micu, which belonged to the rice vinegar, closed to


the white vinegar and the aromatic vinegar, respectively. This
agrees with the PCA results and the reason has been discussed
before. We noticed that samples 3 and 8, the Yanhui Xiangcu and
the Shuita Chencu, respectively, were misclassified in Fig. 8. At
the same time, the samples 2 and 17, the Beigushan Xiangcu
and the Haitian Pingguocu, respectively, did not enter any group
until near the end of the dendrogram. The Haitian Pingguocu
separated from other vinegars because it has the lowest total
acidity and high contents of sugar and represented the fruit vinegar singly in the experiment. However, the results of the other
misclassified samples were inconsistent with the PCA results.

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Therefore, the PCA results of the same data were plotted onto the
first three PCs, as shown in Fig. 9, to investigate the difference.
Most of the data points roughly took up similar positions (Fig. 2)
except that the Beigushan Xiangcu data points sharply changed
its position from the bottom to the top (refer to Figs. 2 and 9).
This is the reason why the Beigushan Xiangcu did not enter
any group in Fig. 8 though the Beigushan Xiangcu data points
were very close to mature vinegar data points in Fig. 2. The
Yanhui Xiangcu closed to the mature vinegars and the Shuita
Chencu still attached to the aromatic vinegars in Fig. 9 as well
as in Fig. 3. Though we successfully explained the difference
between the results of PCA and those of CA, there is a limitation to this research in explaining the misclassified samples in
the CA analysis. Further research will be devoted to removing
this limitation. More characteristics of the vinegars are needed
for understanding the gas-sensing properties and eliminating the
misclassifications. Sensory analysis [1,2] and analytical chemistry [310] are expected to be the best accessorial tools to
investigate the vinegars.
Samples 13, 15 and 16 closed together and represented the
group of liquid fermentation except sample 17, Haitian Pingguocu. The reason of misclassification of the Haitian Pingguocu
was discussed before. Classifying the vinegars according to their
total acidity, raw materials or production area was not satisfied
enough in CA analysis. Taken as a whole, these results indicate
that the type and fermentation method are more effective than
the other influencing factors discussed in this paper when the
vinegars are analyzed by the electronic nose.
3.3. LVQ analysis
LVQ networks classify input vectors into target classes by
using a competitive layer to find subclasses of input vectors, and
then combining them into the target classes. An LVQ network
has a first competitive layer and a second linear layer. The competitive layer learns to classify input vectors in much the same

Fig. 9. PCA results of the vinegars data obtained from sensor array; score plot in the PC1, PC2 and PC3.

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Q. Zhang et al. / Sensors and Actuators B 119 (2006) 538546

Table 3
Classification results for 17 vinegars by using LVQ according to their type
Samples

Aromatic vinegar
Mature vinegar
Rice vinegar
White vinegar
Fruit vinegar

28
20
8
8
4

Classified as
Aromatic vinegar

Mature vinegar

16
4

16

Rice vinegar

White vinegar

3
8

Fruit vinegar

The classification accuracy is 72.1%.


Table 4
Classification results for 17 vinegars by using LVQ according to their total acidity
Samples

Classified as
4.0 g/100 ml

4.0 g/100 ml
4.44.5 g/100 ml
5.05.5 g/100 ml
6.0 g/100 ml

16
16
24
12

4.44.5 g/100 ml

5.05.5 g/100 ml

6.0 g/100 ml

16
3

1
5

16
16
3

4
4

The classification accuracy is 77.9%.


Table 5
Classification results for 17 vinegars by using LVQ according to their fermentation method
Samples

Classified as
Solid fermentation

Solid fermentation
Liquid fermentation

way as the competitive layers. The linear layer transforms the


competitive layers subclasses into target classifications defined
by the user. Shaffer et al. has compared seven different pattern recognition algorithms and recommended LVQ is the best
for chemical sensor array pattern recognition while speed and
memory requirements are not [21]. In our modelling, the number of competitive layer neurons was 45, learning rate was set as
0.09, and then LVQ network was trained for 40,000 epochs. The
classification results for 17 vinegars by using LVQ are listed in
Tables 37 according to their type, raw materials, total acidity,
fermentation method and production area, respectively.

52
16

Liquid fermentation

48

4
16

The classification accuracy is 94.1%.

Table 6
Classification results for 17 vinegars by using LVQ according to their raw materials
Samples

Classified as
Using alcohol

Using alcohol
Adding sodium benzoate
Adding potassium sorbate
The others

12
8
20
28

Adding sodium benzoate

Adding potassium sorbate

The others

16
4

16

12
8
4
4

The classification accuracy is 76.5%.


Table 7
Classification results for 17 vinegars by using LVQ according to their production area
Samples

Classified as
Jiangsu province

Jiangsu province
Shanxi province
Beijing
Guangdong province
Guizhou province

28
8
12
12
8

The classification accuracy is 82.4%.

Shanxi province

16

Beijing
4

Guangdong province
4

Guizhou province
4

8
12
12
8

Q. Zhang et al. / Sensors and Actuators B 119 (2006) 538546

The accuracy in terms of predicting tested vinegar measurements was 72.1%, 76.5%, 77.9%, 94.1% and 82.4% according to
type, raw materials, total acidity, fermentation method and production area, respectively. It was evident that all the influencing
factors which were chosen to characterize the Chinese vinegars
in this experiment were suitable and effective because of their
relative high accuracies. The LVQ results basically matched the
results of PCA and CA. The accuracy according to the fermentation method was highest and only 4 of 68 testing measurements
were misclassified. There is no significant difference in the accuracy to the rest of influencing factors and all of them were about
80% except the accuracy to the type. The fact that the accuracy
to the vinegar type was not satisfied is attributable to the similarities among the aromatic vinegar, rice vinegar and white vinegar
which have been discussed in the CA analysis.
4. Conclusions
Vinegar is favorite food and a large amount of vinegar is produced and consumed every year in China. There is no effective
method or instrument for real-time, on-line and in situ detecting
the vinegars yet, though Chinese government has paid more and
more attentions on the quality control of vinegar. Sensory analysis and chemical analysis are widely used for vinegar quality
evaluation in Europe, but the electronic nose seems to be the
most promising method for vinegar classification.
In this paper, we analyzed 17 commercial Chinese vinegars,
acetic acid and 5% diluted acetic acid by an electronic nose
under laboratory conditions. The electronic nose contained nine
nano ZnO thick film gas sensors, which were doped with 5
and 10 wt.% TiO2 , 5 and 10 wt.% MnO2 , 1 wt.% V2 O5 , 5 wt.%
Bi2 O3 , 0.6 and 2.4 wt.% Ag, and 5 wt.% W. PCA and CA were
applied to examine the presence of classes inside the sample population and LVQ was used to perform the role of recognition and
classification of the vinegars. The findings of the study indicated
that the gas-sensing properties of acetic acid and 5% diluted
acetic acid were very different from those of vinegars. Though
the main ingredient is acetic acid in vinegars, their total acidity is not a critical element to characterize the Chinese vinegars
because of the lower classification accuracy by LVQ analysis. It
was evident from the experimental data that characterizing the
Chinese vinegars by the electronic nose was highly related to
their type, raw materials, total acidity, fermentation method and
production area, and all these influencing factors were not independent. The CA results indicated that the type and fermentation
method were more effective than other influencing factors when
the vinegars were analyzed by the electronic nose. The accuracy
of LVQ was 72.1%, 76.5%, 77.9%, 94.1% and 82.4% according
to the type, raw materials, total acidity, fermentation method and
production area, respectively. It was shown that the electronic
nose was a very promising tool to vinegar characterization. The
present study was made in order to establish a gas-sensing fingerprint database of Chinese vinegars and develop a commercial
electronic nose on the Chinese vinegars quality control.
A further investigation might explore thorough understanding of the gas-sensing properties and the components of vinegars. Sensory analysis and analytical chemistry can be used as

545

the accessorial tools to examine vinegar ingredients and aid to


understand the vinegars gas-sensing characterization.
Acknowledgements
The financial support by the National Natural Science Foundation of China (NFSC, Grant Nos. 50271029 and 50041024),
the Key Project for Science and Technology Research of Ministry of Education (Grant No. 00084), Science and Technology
Planning Project of Wuhan (Grant No. 20011007088-5) is gratefully acknowledged.
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Biographies
Qinyi Zhang received his BSc from Wuhan University of Technology in 1993
on material science and engineering. At present, he is a researcher of Wuhan
University of Technology and a PhD student at the Huazhong University of
Science and Technology. His research interests include application of electronic
noses, neural networks and nanomaterials.
Shunping Zhang received his BSc from Huazhong University of Science and
Technology in 2004 on material science and engineering. Currently he is working
on electronic noses as a PhD student at the Huazhong University of Science and
Technology.
Changsheng Xie received his PhD from Huazhong University of Science and
Technology in 1985 on material science and engineering. He is professor of

material science and engineering at Huazhong University of Science and Technology. His research interests include the synthesizing of nanomaterials and
electronic noses.
Dawen Zeng received his BSc in 1993 from Tsinghua University and PhD in
1998 from Huazhong University of Science and Technology on material science
and engineering. He is an associate professor of material science and engineering at Huazhong University of Science and Technology. His research interests
include the synthesizing of nanomaterials and electronic noses.
Chaoqun Fan received her BSc from Wuhan University of Technology in 2005 on material science and engineering. At present, she is a
graduate student at the Huazhong University of Science and Technology. Her research interests are in the field of applications of electronic
noses.
Dengfeng Li received his BSc from Wuhan University of Technology in 2003
on material science and engineering. At present, he is a graduate student at the
Huazhong University of Science and Technology. His current research interests
involve electronic noses and chemical sensors.
Zikui Bai is graduated from the Huazhong University of Science and Technology on material science and engineering in 2005. At present, he is a PhD
student at the Huazhong University of Science and Technology. His current
research interests involve electronic noses and preparation of chemical sensor
array.