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IEEE TRANSACTIONS ON INSTRUMENTATION AND MEASUREMENT, VOL. 51, NO. 6, DECEMBER 2002

Coffee Analysis With an Electronic Nose

Matteo Pardo and Giorgio Sberveglieri
AbstractWe present the Pico-1 electronic nose based on thin-film semiconductor sensors and an application to the analysis of two groups of seven coffees each. Cups of coffee were also analyzed by two panels of trained judges who assessed quantitative descriptors and a global index (called Hedonic Index, HI) characterizing the sensorial appeal of the coffee. Two tasks are performed by Pico-1. First, for each group, we performed the classification of the seven different coffee types using principal component analysis and multilayer perceptrons for the data analysis. Classification rates were above 90%. Secondly, the panel test descriptors were predicted starting from the measurements performed with Pico-1. The standard deviations for the prediction of the HI are comparable to the uncertainty of the HI itself (0.2 on a 1 to 9 scale for one group of coffees). Index TermsChemical sensors, classification, data analysis, electronic nose (EN), multilayer perceptrons, thin films.

I. INTRODUCTION LECTRONIC noses (EN), in the broadest meaning, are instruments that analyze gaseous mixtures for discriminating between different (but similar) mixtures and, in the case of simple mixtures, quantify the concentration of the constituents. ENs consist of a sampling system (for a reproducible collection of the mixture), an array of chemical sensors, electronic circuitry and data analysis software [1]. Chemical sensors, which are the heart of the system, can be divided into three categories according to the type of sensitive material used: inorganic crystalline materials (e.g., semiconductors, as in MOSFET structures, and metal oxides); organic materials and polymers; and biologically derived materials. The use of ENs for food quality analysis tasks is twofold. ENs are normally used to discriminate different classes of similar odor-emitting products [2], [3]. In particular, ENs already served to distinguish between different coffee blends and between different coffee roasting levels [2], [4], [5]. On the other hand, ENs can also be used to predict sensorial descriptors of food quality as determined by a panel (often one generically speaks of correlating EN and sensory data). ENs can, therefore, represent a valid help for routine food analysis. The combination of gas chromatography and mass spectroscopy (GCMS) is by far the most popular technique for the identification of volatile compounds in foods and beverages [6]. This is because the separation achieved by the gas chromatographic technique is complemented by the high sensitivity of mass spectroscopy and its ability to identify the molecules eluting from the column on the basis of their fragmentation
Manuscript received May 29, 2001; revised September 18, 2002. The authors are with Gas Sensor Laboratory, Department of Chemistry and Physics, INFM, University of Brescia, Brescia, Italy (e-mail: pardo@tflab.ing.unibs.it). Digital Object Identifier 10.1109/TIM.2002.808038

patterns. Detection limits as low as 1 ppb are frequently reached. The main drawbacks of the approach are, however, the cost and complexity of the instrumentation and the time required to fully analyze each sample (around one hour for a complete chromatogram). Comparatively, ENs are simpler, cheaper devices. They recognize a fingerprint, that is, global information of the samples to be classified. For food products, the sensory characteristics determined by a panel are important for quality assessment [7]. While man still is the most efficient instrument for sensorial evaluation, the formation of a panel of trained judges involves considerable expenses. Commercial coffees are blends, which, for economic reasons, contain (monovarietal) coffees of various origins. For the producers, the availability of analysis and control techniques is of great importance. There is extensive literature on the characterization of coffee using the chemical profile of one of its fractions, such as the headspace of green or roasted beans or the phenolic fraction. In the literature up to 700 diverse molecules have been identified in the headspace [8]. Their relative abundance depends on the type, provenance and manufacturing of the coffee. It is to be noticed that none of these molecules can alone be identified as a marker. On the contrary, one has to consider the whole spectrum, as for instance, the gas chromatographic profile. II. EXPERIMENTAL A. Pico-1 Electronic Nose Five semiconductor, SnO -based thin-films sensors were utilized. Two are pure SnO sensors; one is catalyzed with gold, one with palladium, and one with platinum. They were grown by sputtering with the RGTO technique [9]. The surface of the film after the thermal oxidation step of the RGTO technique presents porous, nano-sized agglomerates which are known to be well suited for gas absorption [10]. A thin layer of noble metals was deposited as catalyst on three sensors to improve sensitivity and selectivity. Thin-film sensors produced by sputtering are comparatively stable and sensitive. Furthermore, since the growing conditions are controllable, they can be tailored toward the particular application. Even if catalyzed, the sensors are not selective, and, therefore, sensor arrays together with multivariate pattern recognition techniques are used. The odor sampling system depends on the type of sample and on its preparation. For simple gas mixtures, one uses automated gas mixing stations consisting of certified gas bottles, switches and mass flow controllers [11]. In the case of complex odors like food odors, the volatile fraction (the so-called headspace) is formed inside a vial where a certain amount of odor-emitting sample is placed. The vapor can then be collected either by flushing a carrier inside the vial (dynamic headspace scheme)

0018-9456/02$17.00 2002 IEEE

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Fig. 1. Scheme of the EN developed in the Gas Sensor Lab (static headspace sampling with syringe).

or extracted with a syringe and injected, at constant velocity, in the air flow which is used as carrier (static headspace scheme). The electromechanical part of the EN used in this experiment consists of (see a scheme in Fig. 1). 1) An autosampler (Hs 850 CE Instruments). This device is a standard component of cromatographs; its utility is a high sample throughput and a high reproducibility due to the automation of the measurement process. It consists of a sample carousel, where the vials containing the odor-emitting sample are held, an oven, where the sample is pre-conditioned, and a movable mechanical arm with syringe (A). 2) A mass flow controller (B) to set the flow of the carrier gas. 3) A stained steel chamber (C) which can contain up to five chemical sensors plus the humidity sensor. 4) Control electronics (D) permitting steering of the system (autosampler, mass flow controllers, and sensors) via PC. The typical measurement consists of the exposure of the sensors to a concentration step, that is, a change of odor concentration from zero to (each component of the vector stands for a gas component) and back to zero again, and of the recording of the subsequent change in resistance. The classical feature extracted from the response curve is the relative change in resistance. A set of Matlab functions (toolbox) has been developed for analyzing the data [12]. The toolbox permits performing the following tasks. Data cleaning (median filter for spikes removal, possible noise averaging) and plotting (for gaining a first impression of the response curves). Software for drift compensation is currently under study [5]. Exploratory analysis (visual). First, various plots of the response curves and of the features can be drawn for each sensor separately (univariate analysis). The most important multivariate tool for exploratory analysis is principal

component analysis (PCA) (score and loading plots) [13]. PCA is implemented with a simple user interface giving the possibility of selecting the sensors and classes to be displayed and of grouping classes together. PCA also serves for feature reduction before the use of multilayer perceptrons (MLP). Learning with MLP [13]. The inputs to the MLP are the projections of the data on the first m principal components (the so-called PCA scores). The number of inputs m (PCA dimensions) is then a variable to be optimized. To prevent overfitting, early stopping (ES) [14] or weight decay regularization [15] can be used [16]. A division into two sets (training and testing) or into three sets for ES (training set is subdivided in training and validation sets) is possible. The error function is minimized with the Levenberg Marquardt algorithm [17]. Ten network initializations are usually performed, and the net with the best result on the test set is held. Decomposition of the global learning tasks in successive classification subtasks [18] (hierarchical classification). First, the classification between the more distinct clusters is performed; then the finer differences are determined in subsequent steps. This is particularly useful when dealing with a large number of classes and a small number of data. Ensembles of MLPs based on output coding decomposition [19] have also been studied [20]. Work is in progress on the topics of boosting and bagging for increased classification accuracy. B. Measurements Measurements were done on ground coffee. Two groups of coffees were analyzed. The first one consists of six single varieties (SV) and the blend Italian certified espresso (ICE) for reference (this group will be called SV), and the second one

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TABLE I FIRST GROUP OF COFFEES: SINGLE VARIETIES

+ ICE

four qualitative descriptors and over the panelists is considered as a reliable global parameter characterizing the sensorial appeal of a coffee. This quantity is pictorially termed the Hedonic Index (HI). The two averages help to reduce the uncertainty (standard deviation) by a factor , where is the number of sensorial judges qualitative descriptors. For measurements, i.e., . the SV group, the standard deviation of the HI is The detailed procedures adopted for testing the Espresso in this study are described in [22]. III. RESULTS A. Classification A global impression of the measurements can be gained from the PCA plots in Figs. 2 and 3. We note the following. 1) Drift is present, and it affects the first PC. Nonetheless, the visual separation obtained with the second and third PCs was not seen to be any better. 2) The various extractions are of no use for distinguishing between the coffees; instead, they can serve to have a richer data set. The difference between extractions exists but can not be distinguished from the temporal drift. 3) For SVs (Fig. 2), coffee #7 forms a distinct cluster; in fact, this is a very roasted coffee, and it is considered to be of the worst quality. The ICE points (class #1) form two somewhat distinct clusters. The measurements of the cluster on the bottom right were made with the second and third carousel: it is possible that the blends headspace evolved differently with time with respect to that of the SVs. The first carousel of ICE measurements on the contrary is similar to the other coffees. A third fact about the SV is that coffees #3 and #5 are mixed. This makes sense since the coffees are of the same type, both being washed arabic beans of good quality (see Table I). 4) For blends (Fig. 3), the rancid coffee stands out (#6), while the ICE and ICE with unripe beans are confused (#1 and #5). This can be due to the fact that the difference between the two coffees is given mainly by molecules with low volatility, which therefore are not analyzed by the EN. In fact, sensorially one distinguishes the unripe coffee from its astringent taste and not from the odor. The PCA plots show just the most evident trends in the data. This is often the case with many classes and many measurements done over a relatively long time period on similar substances. If one considers a subset of the data, measured on a smaller time period, one can obtain a better visual separation, as is the case in Fig. 4. The MLPs give the actual classification; the PCA acts here as preprocessing to reduce the inputs by eliminating noise and correlation from the data [13]. One pattern out of four is put in the test set. In Table III, we see the confusion matrix for the classification of SVs that has been obtained by using three principal components. Ten patterns out of 56 were misclassified (82% correct classification), and most of the errors were made on classes #3 and #5 (the same that are superposed in the PCA

TABLE II SECOND GROUP OF COFFEES: BLENDS

consists of seven blends, including the ICE, see Tables I and II. The fourth row of the tables contains a brief characterization of the coffees, where the commercial value is indicated with and . Two grams of ground coffee are introduced into a vial with a volume of 20 cm which is crimped with seal and septa. The vial is then left in an incubation oven at 50 C for 30 min in order to generate the aroma. Ten vials for every coffee type of the first group and 12 vials for every coffee type of the second group were prepared. Three successive extractions were performed from the same vial. All together there are measurements for the first group and measurements for the second group. While the data set is not large for machine learning standards, where it is usual to have hundreds of examples for each class [21], this is a considerable dataset to be collected with an E-Nose, where complete datasets normally do not exceed 100200 examples (while it is rather common to have less then 10 instances for each class). Experimental parameters like sample conditioning temperature and fluxes were optimized to reduce the sensor stress and to increase the measurement rate, while still reaching the sensors steady-state conditions (which are believed to be more reproducible). The time interval between the extractions sufficient for the headspace to reach equilibrium conditions was found to be 40 min. As for the sensorial analysis, the panels (formed respectively by 18 and 14 judges) judged the final product (cups of espresso coffee) according to ten quantitative descriptors (color intensity, cream texture, olfactory intensity, roasted, body, acidity, bitterness, astringency, global positive odor, and global negative odor) and four qualitative descriptors (attractiveness, finesse, balance, and richness). Each descriptor is given a mark from one to nine. One sample for every coffee type (plus a random repetition per group) is tasted. In the quantitative analysis, the panel is given a reference for adjusting its judgements, while this is not the case for the qualitative analysis which should provide a personal, hedonic impression. Since the qualitative values are not calibrated, their spread is considerable. Therefore, for every coffee type, the mean over the

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Fig. 2. PCA plots drawn with all the data, single varieties (SV).

Fig. 3. PCA plots drawn with all the data, blends.

plot in Fig. 2). If we join these two classes, the correct classification rate increases to 95%. This can be considered as the first step of a hierarchical classification of the data (classification tree) [18]. For the blends, we got 54 out of 62 correctly classified patterns (87% correct classification), which rises to 57 out of 62 if we join classes #1 and #5 (92% correct classification). Both for the SV and for the blends it is possible to use a hierarchical classification procedure (classification tree) [18] or ensembles of classifiers [20] to further improve the results.

B. Correlation Between EN and Panel Test Data Still using PCA MLP we tried to predict both the HI and single quantitative descriptors starting from the Pico-1 measurements. This is a regression problem, since the sensorial quantities are graded on a discrete but ordered scale. Since the panel assigns only a single mark to a certain coffee type, this mark was assumed to be the target for every EN measurement on that coffee type (as if the panel made no errors). The best results for the HI prediction were obtained for the SV, see

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Fig. 4.

PCA on a subset of the blends: second extraction, third carousel. TABLE III CONFUSION MATRIX FOR THE CLASSIFICATION OF SV. NOTE THE MIXING BETWEEN CLASS 3 AND 5

Fig. 5. As usual, for regression problems, the predicted outputs are depicted as a function of the true outputs. In the best possible line. The quality of the solution, all the points fall on the obtained prediction can be judged graphically by the distance of line and can be summarized the predicted data from the with either the sum of square error or with the correlation coefin Fig. 5). ficient ( One has to consider that the error in the EN prediction on any given coffee type is to be confronted with the uncertainty (spread) in the panel rating. The spread of the HI predictions in Fig. 5 is comparable to the uncertainties in the HI panel rating (0.2 on a 1 to 9 scale). Remember that the HI determined from the panel is an average and therefore more robust. Analogously, it is possible to average on a certain number of EN predictions in order to diminish the prediction error. This means measuring more coffee samples of the same type to predict the HI for that coffee type. For the prediction of single quantitative descriptors, results are not as good as for the HI. The relation between the EN measurement and each quantitative descriptor separately has been sought with PCA and MLP, just as in the case of the HI. The best predicted descriptors have understandably been the global negative odor and the global positive odor descriptors, with a correlation coefficient of respectively 0.9 and 0.89. This can be easily explained: the volatile substances which gave the EN signal are the same which are analyzed by the panel. Quite sur-

Fig. 5. Regression of the MLP outputs on the true HI for SVs.

prisingly, a strong correlation ( ) has been found between the EN measurements and the cream texture descriptor.

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On the other hand, the worst correlation is the one with the color . Color and odor do not seem to have intensity, where common causes. IV. CONCLUSION In this contribution, we presented a novel E-Nose, the advantages of which consist of the sensor type and the data analysis software. Thin-film semiconductor sensors are stable and sensitive, while the Matlab toolbox permits reliably analyzing small datasets. Two groups of measurements on coffee samples were analyzed. Classification figures of over 90% for both groups have been obtained with PCA and multilayer perceptrons. More importantly, EN data have been correlated with panel test judgments. As far as we know, the prediction of a global sensorial parameter, such as the coffees hedonic index, using just EN data, has never been reported. These results show that it is possible to use the EN for routine work in food quality analysis. ACKNOWLEDGMENT The authors would like to thank L. Odello, for providing the panel test data, and E. Comini, for the preparation of the sensors. REFERENCES
[1] J. Gardner and P. Bartlett, Electronic Noses. Oxford, U.K.: Oxford Univ. Press, 1999. [2] H. Ulmer, J. Mitrovics, G. Noetzel, U. Weimar, and W. Gopel, Odours and flavors identified with hybrid modular sensor systems, Sens. Actuators B, vol. 43, pp. 2433, 1997. [3] P. N. Bartlett, T. M. Elliot, and J. W. Barcher, Electronic noses and their application in the food industry, Food Technol., vol. 51, pp. 4448, 1997. [4] S. Singh, E. Hines, and J. Gardner, Fuzzy neural computing of coffee and tainted-water data from an electronic nose, Sens. Actuators B, vol. 30, pp. 185190, 1996. [5] M. Pardo, G. Niederjaufner, G. Benussi, E. Comini, G. Faglia, G. Sberveglieri, M. Holmberg, and I. Lundstrom, Data preprocessing enhances the classification of different brands of espresso coffee with an electronic nose, Sens. Actuators B, vol. 69, 2000. [6] F. Mellon, Mass spectroscopy, in Spectroscopic Techniques for Food Analysis, R. Wilson, Ed. New York: VCH, 1994. [7] D. Pal, S. Sachdeva, and S. Singh, Methods for determination of sensory quality of foods: A critical approach, J. Food Sci. Technol., vol. 32, pp. 357367, 1995. [8] R. J. Clarke and R. Macrae, Coffee. New York: Elsevier, 1985, vol. 1, Chemistry. [9] G. Sberveglieri, G. Faglia, S. Groppelli, P. Nelli, and A. Camanzi, A new technique for growing large surface area SnO thin film (rgto technique), Semicond. Sci. Technol., vol. 5, no. 41, pp. 12311233, 1990. [10] E. Comini, V. Guidi, C. Frigeri, I. Ricc, and G. Sberveglieri, Nanostructured mixed oxides compounds for gas sensing applications, Sens. Actuators B, vol. 84, no. 1, pp. 2632, 2002.

[11] G. Sberveglieri, L. Depero, S. Groppelli, and P. Nelli, WO sputtered thin films for NO monitoring, Sens. Actuators B, vol. 2627, pp. 8992, 1995. [12] M. Pardo, Multivariate data analysis for gas sensor arrays, Ph.D. dissertation, Universit di Brescia, Brescia, Italy, Mar. 2000. [13] C. M. Bishop, Neural Networks for Pattern Recognition. Oxford, U.K.: Oxford Univ. Press, 1995. [14] W. S. Sarle. Stopped training and other remedies for overfitting. presented at Proc. 27th Symp. Interface Comput. Sci. Stat., pp. 352360, 1995. [Online]. Available: ftp://ftp.sas.com/pub/neural/inter95.ps.Z. [15] F. D. Foresee and M. T. Hagan, GaussNewton approximation to Bayesian regularization, in Proc. Int. Joint Conf. Neural Networks, 1997, pp. 19301935. [16] H. Demuth and M. Beale, Manual of the Neural Network Toolbox, ser. MA. Natick: The MathWorks, Inc., 1998, version 3. [17] M. T. Hagan and M. Menhaj, Training feedforward networks with the marquardt algorithm, IEEE Trans. Neural Networks, vol. 5, pp. 989993, 1994. [18] M. Pardo, G. Sberveglieri, S. Gardini, and E. Dalcanale, A hierarchical classification scheme for an electronic nose, Sens. Actuators B, vol. 69, 2000. [19] T. Dietterich and G. Bakiri, Solving multiclass learning problems via error-correcting output codes, J. Art. Intell. Res., no. 2, pp. 263286, 1995. [20] M. Pardo, G. Sberveglieri, F. Masulli, and G. Valentini, Decompositive classification models for electronic noses, Anal. Chim. Acta, vol. 446, pp. 223232, 2001. [21] C. J. Merz and P. M. Murphy. (1998) UCI repository of machine learning databases. [Online]. Available: www.ics.uci.edu/mlearn/MLRepository.html. [22] L. Odello, Espresso Tasting. Brescia, Italy: Centro Studi e Formazione Assaggiatori, 1998.

Matteo Pardo was born in Genova, Italy, in 1971. He received the M.S. degree in theoretical surface physics from the University of Milano, Milano, Italy, and the Ph.D. degree in information engineering in March, 2000. His research interests are electronic noses and data analysis. In particular, he is interested in the application of modern machine learning techniques (e.g., neural networks and ensembles techniques) to real world problems.

Giorgio Sberveglieri was born on July 17, 1947 and received the degree in physics from the University Parma, Parma, Italy. Since 1988, he has been the Director of the Gas Sensor Laboratory, University of Brescia, Brescia, Italy, which is mainly devoted to the preparation and characterization of thin film chemical sensors. In 1994, he was appointed Full Professor of physics. He is referee of Thin Solid Films, Sensors and Actuators, Sensors and Materials, and other journals and member of scientific Committees of conferences on sensors and material science. During 25 years of scientific activity, he has published more than 200 papers on international journals.