Flow injection analysis applied to a voltammetric electronic tongue

A measurement system, based on flow injection analysis (FIA) technique applied to a voltammetric electronic tongue is described. A reference solution was thus continuously pumped through a cell with a voltammetric electronic tongue, and test samples were injected into the flow stream. Responses were obtained by measuring the resulting pulse height. The FIA technique offered several advantages, since relative measurements are performed, the system is less influenced by sensor baseline drift, calibration samples and/or washing solutions can be injected within a measurement series, and the system is well adapted for automatization. The system was used to analyze standard solutions of H₂O₂, KCl, CuNO₃, K₄[Fe(CN)₆], K₃[Fe(CN)₆] and NaCl, and results obtained were treated with multivariate data analysis. Principal component analysis performed showed that electrode drift could be considerably decreased, and the set-up was also used for classification of different apple juices.     

Multicomponent analysis of fermentation growth media using the electronic tongue (ET)

A potentiometric electronic tongue (ET) consisting of eight cross-sensitive chemical sensors and a standard pH electrode has been applied for analysis of simulated fermentation solutions typical for fermentation processes with Aspergillus niger. The electronic tongue has been found capable of simultaneous determination of ammonium, citrate and oxalate in complex media with good precision (typical error within 8%). The system preserved high sensitivity to the targeted substances also in the presence of sodium azide, which is commonly used for suppressing microbial activity in real-world fermentation samples. Sensor performance was fast and reproducible which promises well for routine application of the electronic tongue for fermentation process monitoring.     

Development of an electronic tongue based on a PEDOT-modified voltammetric sensor

Three different electrodes were tested for use as nonspecific amperometric sensors for blind analysis on real matrices, namely different fruit juices from different fruits or different brands. The first two electrodes were traditional Pt and Au electrodes, while the third one was modified with poly(3,4-ethylenedioxythiophene) conducting polymer. The sensors were tested separately, tested coupled to each other, and also tested together. The responses of the electrode system(s) were first screened via PCA and then their discriminant capabilities were quantified in terms of the sensitivities and specificities of their corresponding PLS-DA multivariate classification models. Particular attention was paid to analyzing the evolution of the response over subsequent potential sweeps. The modified electrode demonstrated the most discriminating ability, and it was the only system capable of satisfactorily performing the most complex task attempted during the analysis: discriminating between juices from the same fruit but from different brands. Moreover, the electrode "cleaning" procedure required between two subsequent potential sweeps was much simpler for the modified electrode than for the others. This electrode system was therefore shown to be a good candidate for use as an informative element in an electronic tongue applied to the analysis of other food matrices.     

Multivariate optimisation of electrochemically pre-treated electrodes used in a voltammetric electronic tongue

The use of experimental design as a tool to optimise electrochemically cleaned electrodes applied in a voltammetric electronic tongue is described. A simple and quick activation of electrode surfaces is essential for this type of device, especially for on-line applications in industrial processes. The electronic tongue consisted of four metal electrodes, e.g. Au, Ir, Pt, and Rh in a three-electrode configuration. Current was measured as a function of large potential pulses of decreasing amplitude applied to each electrode. Preliminary results showed that electrochemical cleaning activated the electrode surfaces to similar extent as polishing. Settings of potential and time for each electrode was determined with experimental design in a solution containing 1.0 mM K₄[Fe(CN)₆] in 0.1 M phosphate buffer (pH 6.8). Electrode surfaces were deactivated in-between measurements in a complex liquid, like tea. Optimal settings for potential and time in the electrochemical cleaning procedure at each electrode were chosen at recoveries of 100% (compared to polished electrodes). The recoveries were larger than 100% when too large potentials and times were applied. This could be explained by the fact that the electrode areas increased and therefore also the current responses. Principal component analysis (PCA) was used to investigate the stability of the electrode settings at 100% recoveries. No obvious trends of drift in the signals were found.     

Determination of total polyphenol index in wines employing a voltammetric electronic tongue

This work reports the application of a voltammetric electronic tongue system (ET) made from an array of modified graphite-epoxy composites plus a gold microelectrode in the qualitative and quantitative analysis of polyphenols found in wine. Wine samples were analyzed using cyclic voltammetry without any sample pretreatment. The obtained responses were preprocessed employing discrete wavelet transform (DWT) in order to compress and extract significant features from the voltammetric signals, and the obtained approximation coefficients fed a multivariate calibration method (artificial neural network-ANN-or partial least squares-PLS-) which accomplished the quantification of total polyphenol content. External test subset samples results were compared with the ones obtained with the Folin–Ciocalteu (FC) method and UV absorbance polyphenol index (I₂₈₀) as reference values, with highly significant correlation coefficients of 0.979 and 0.963 in the range from 50 to 2400 mg L⁻¹ gallic acid equivalents, respectively. In a separate experiment, qualitative discrimination of different polyphenols found in wine was also assessed by principal component analysis (PCA).     

Application of a potentiometric electronic tongue as a classification tool in food analysis

This paper reports on the application of a potentiometric sensor array to the food analysis field, in order to distinguish simple tastes and to classify food samples. This array is formed by a set of non-specific all-solid-state potentiometric sensors and has been used in combination with principal component analysis (PCA) for the classification of food samples in batch and in flow injection mode. First attempt was to classify synthetic samples prepared with controlled variability. Once this ability is proven, satisfactory classification results are presented for commercial waters, orange-based drinks and tea samples. An interesting correlation is achieved between the natural juice content and its first calculated component, which allows for a very simple tool for screening purposes.     

A self-polishing platinum ring voltammetric sensor and its application to complex media

A self-polishing voltammetric sensor was recently developed and has been applied to samples of urea, milk and sewage water. The polishing device continuously grinds a platinum ring electrode, offering a reproducible and clean electrode surface. Principal component analysis (PCA) and partial least squares (PLS) techniques were applied to interpret the data and to build prediction models. In an evaluation of samples with different urea concentrations, the grinding step allows for repeatable measurements, similar to those after electrochemical cleaning. Furthermore, for the determination of sewage water concentrations in drinking water and for the evaluation of different fat contents in milk samples, the polishing eliminates sensor drift produced by electrode fouling. The results show that the application of a self-polishing unit offers a promising tool for electrochemical studies of difficult analytes and complex media.     

Mimicking Daphnia magna bioassay performance by an electronic tongue for urban water quality control

Toxicity is one of the key parameters of water quality in environmental monitoring. However, being evaluated as a response of living beings (as their mobility, fertility, death rate, etc.) to water quality, toxicity can only be assessed with the help of these living beings. This imposes certain restrictions on toxicity bioassay as an analytical method: biotest organisms must be properly bred, fed and kept under strictly regulated conditions and duration of tests can be quite long (up to several days), thus making the whole procedure the prerogative of the limited number of highly specialized laboratories. This report describes an original application of potentiometric multisensor system (electronic tongue) when the set of electrochemical sensors was calibrated against Daphnia magna death rate in order to perform toxicity assessment of urban waters without immediate involvement of living creatures. PRM (partial robust M) and PLS (projections on latent structures) regression models based on the data from this multisensor system allowed for prediction of toxicity of unknown water samples in terms of biotests but in the fast and simple instrumental way. Typical errors of water toxicity predictions were below 20% in terms of Daphnia death rate which can be considered as a good result taking into account the complexity of the task.     

Evaluation of Italian wine by the electronic tongue: recognition, quantitative analysis and correlation with human sensory perception

The electronic tongue based on a sensor array comprising 23 potentiometric cross-sensitive chemical sensors and pattern recognition and multivariate calibration data processing tools was applied to the analysis of Italian red wines. The measurements were made in 20 samples of Barbera d’Asti and in 36 samples of Gutturnio wine. The electronic tongue distinguished all wine samples of the same denomination and vintage, but from different vineyards. Simultaneously the following quantitative parameters of the wines were measured by the electronic tongue with precision within 12%: total and volatile acidity, pH, ethanol content, contents of tartaric acid, sulphur dioxide, total polyphenols, glycerol, etc. The electronic tongue is sensitive to multiple substances that determine taste and flavour of wine and, hence, the system was capable of predicting human sensory scores with average precision of 13% for Barbera d’Asti wines and 8% for Gutturnio wines.     

Rapid honey characterization and botanical classification by an electronic tongue

In this paper a commercial electronic tongue (αAstree, Alpha M.O.S.) was applied for botanical classification and physicochemical characterization of honey samples. The electronic tongue was comprised of seven potentiometric sensors coupled with an Ag/AgCl reference electrode. Botanical classification was performed by PCA, CCA and ANN modeling on 12 samples of acacia, chestnut and honeydew honey. The physicochemical characterization of honey was obtained by ANN modeling and the parameters included were electrical conductivity, acidity, water content, invert sugar and total sugar. The initial reference values for the physicochemical parameters observed were determined by traditional methods. Botanical classification of honey samples obtained by ANN was 100% accurate while the highest correlation between observed and predicted values was obtained for electrical conductivity (0.999), followed by acidity (0.997), water content (0.994), invert sugar content (0.988) and total sugar content (0.979).All developed ANN models for rapid honey characterization and botanical classification performed excellently showing the potential of the electronic tongue as a tool in rapid honey analysis and characterization. The advantage of using such a technique is a simple sample preparation procedure, there are no chemicals involved and there are no additional costs except the initial measurements required for ANN model development.     

Remote environmental monitoring employing a potentiometric electronic tongue

This work investigates the use of electronic tongues for environmental monitoring. Electronic tongues were based on arrays of potentiometric sensors plus a complex data processing by artificial neural networks and data transmission by radiofrequency. A first application, intended for a system simulating real conditions in surface water, performed a simultaneous monitoring of ammonium, potassium, sodium, chloride, and nitrate ions. The proposed system allowed us to assess the effect of natural biodegradation stages for these species. A second application was used to monitor concentrations of ammonium, potassium, and sodium in the ‘Ignacio Ramírez’ dam (Mexico). The electronic tongue used here allowed us to determine the content of the three cations in real water samples, although a high matrix effect was encountered for sodium determination. The implemented radio transmission worked robustly during all the experiments, thus demonstrating the viability of the proposed systems for automated remote applications.     

Simultaneous titration of ternary alkaline-earth mixtures employing a potentiometric electronic tongue

A fast novel complexometric titration procedure is proposed, in which equivalence concentrations were determined using a potentiometric electronic tongue. The titration consists in a reduced number of fixed additions of titrant and the recording of the potentials of an array of ion-selective electrodes with cross-selectivity response. The generated data (number of sensors × number of additions) were used as input data to an artificial neural network response model previously trained with standards. The application of this procedure is demonstrated with automated EDTA titrations of Ca²⁺, Mg²⁺ and Sr²⁺ mixtures, up to 3.3 mM total ion concentration. In the studied case, good results predicting the three concentrations were obtained using five 1 mL fixed volume additions plus the readings of eight sensors. The unique additional step required was the pH buffering of the sample to pH 9.5. Good comparisons were observed between obtained and expected concentrations for the three cations with the external validation samples (n = 17, with RMSE values of 0.18, 0.28 and 0.32 mM for Ca²⁺, Mg²⁺ and Sr²⁺, respectively). The proposed procedure was applied to mineral waters and compared with reference methods.     

An electronic tongue for gliadins semi-quantitative detection in foodstuffs

An all-solid-state potentiometric electronic tongue with 36 polymeric membranes has been used for the first time to detect gliadins, which are primarily responsible for gluten intolerance in people suffering from celiac disease. A linear discriminant model, based on the signals of 11 polymeric membranes, selected from the 36 above using a stepwise procedure, was used to semi-quantitatively classify samples of a “Gluten-free” foodstuff (baby milked flour), previously contaminated with known amounts of gliadins (<10, 20-50 or >50 mg/kg), as “Gluten-free”, “Low-Gluten content” or “Gluten-containing”. For this food matrix, the device had sensitivity towards gliadins of 1-2 mg/kg and overall sensitivity and specificity of 77% and 78%, respectively. Moreover, the device never identified an ethanolic extract containing gliadins as “Gluten-free”. Finally, the system also allowed distinguishing “Gluten-free” and “Gluten-containing” foodstuffs (15 foods, including breads, flours, baby milked flours, cookies and breakfast cereals) with an overall sensitivity and specificity greater than 83%, using the signals of only 4 selected polymeric membranes (selected using a stepwise procedure). Since only one “Gluten-containing” foodstuff was misclassified as “Gluten-free”, the device could be used as a preliminary tool for quality control of foods for celiac patients.     

Ethylenediamine in the voltammetric determination of copper in sea water at a rotating mercury film electrode

The use of ethylenediamine in the voltammetric study of copper in natural sea water was evaluated for applicability with rotating thin mercury film electrodes. It was shown that this method increases the analytical sensitivity for copper at such electrodes by at least a factor of 4, and improves the detection of pH 8 labile copper.     

Development of a drinking water regulation for perchlorate in California

Perchlorate is an environmental contaminant often associated with military installations and rocket propellant manufacture and testing facilities across the U.S. Highly water soluble, perchlorate has been found by federal and state agencies at almost 400 sites within the U.S. in groundwater, surface water, soil or public drinking water. There is no federal drinking water standard for perchlorate, but it is on the drinking water Contaminant Candidate List, and falls under the Unregulated Contaminant Monitoring Rule (UCMR) for which monitoring is required. The recent National Academy of Science (NAS) report on the potential health effects of perchlorate recommended a perchlorate reference dose of 0.0007 mg/kg of body weight which would be equivalent to a drinking water concentration of 24.5 μg/L.In California, approximately 395 wells in 96 water systems have been shown to contain perchlorate, and about 90% of these are located in Southern California. Water taken from the Colorado River, a major surface water supply to Southern California, has had reported detections of perchlorate ranging from non-detect to 9 μg/L. California has established a Public Health Goal (PHG) of 6 μg/L for perchlorate, and a proposed drinking water regulation is imminent. This review details the regulatory process involved with particular attention given to the occurrence of perchlorate in California drinking water sources and analytical methodology utilized.     

Detection and quantification of PAH in drinking water by front-face fluorimetry on a solid sorbent and PLS analysis

The direct determination in drinking water of perylene, chrysene, pyrene, benzo[a]pyrene, and benzo[k]fluoranthene, by front-face synchronous fluorimetry on a commercial SPE disk, has been evaluated. Sorbent treatment, influence of humic substances, and pH effect are discussed. In pure water the detection limits were estimated to be in the range 0.03–0.01 g L^–1. A working pH in the range 10–11 was found to minimize the fluorescence quenching effect of humic substances. The proposed method combined with a partial-least-square (PLS) treatment was tested for quantitative analysis of mixtures of four PAH in a spiked drinking water.     

Fermentation monitoring using multisensor systems: feasibility study of the electronic tongue

The electronic tongue based on an array of 30 non-specific potentiometric chemical sensors has been applied to qualitative and quantitative monitoring of a batch fermentation process of starting culture for light cheese production. Process control charts were built by using PLS regression and data from fermentations run under normal operating conditions. Control charts allow discrimination of samples from fermentation batches run under abnormal operating conditions from normal ones at as early as 30–50% of fully evolved fermentations. The capability of the electronic tongue to quantify concentrations of important organic acids (citric, lactic and orotic) in the present type of fermentation media was demonstrated. Average prediction errors were assessed in the range 5–13% based on test set validation. Correlation between peptide profiles determined using HPLC and the electronic tongue output was also established. The electronic tongue was demonstrated to be a promising tool for fermentation process monitoring and quantitative analysis of growth media.http://www.electronictongue.com     

Analysis of volatiles and semivolatiles in drinking water by microextraction and thermal desorption

A new technique to analyze aqueous samples for nanograms per liter levels of volatile and semivolatile compounds using microextraction and thermal desorption into a gas chromatograph/ion trap mass spectrometer (GC/MS) is described. This method is inherently sensitive (50 mL of aqueous sample is extracted prior to each desorption), uses no solvents, and detects volatiles and semivolatiles in the same analysis. Aqueous standards and environmental samples are pumped through a length of porous-layer open-tubular capillary column, which is then thermally desorbed onto a 30 m × 0.25 mm i.d. analytical column interfaced to an ion trap mass spectrometer for subsequent separation and detection. Sharp chromatographic peaks and reproducible retention times (RT) were observed. Replicate injections of surrogates (n = 6) averaged 32.6% R.S.D. Analysis of domestic tap water detected 55 analytes, some at the low-nanograms per liter level, and detected 3 halogenated ethenes, not previously reported in drinking water. Analysis of an aqueous sample from a municipal ground water source detected the presence of numerous semivolatile compounds at trace-levels.