One of the most important problems in the wine world, today, is cork taint, which often has been ... more One of the most important problems in the wine world, today, is cork taint, which often has been chemically identified as 2,4,6-trichloroanisole (TCA). The perception limit of this compound is very low (close to 10 and 40 ng / l for white and red wines, respectively), so, even at such low concentrations, its presence becomes a problem in wine quality. A method for the analysis of TCA in white and red wines has been developed in our laboratory, using headspace solid-phase microextraction and gas chromatography with electron-capture detection. The method, which has been optimized using an experimental design, involves the use of fibres coated with polydimethylsiloxane (PDMS) and allows the analysis of TCA at very low concentrations (under 500 ng / l) with good accuracy (RSD#10%). The limits of quantification of the method are 5 and 8 ng / l for white and red wines, respectively, while the limit of detection is 1 ng / l for both types of wine.
Process analytical technologies (PATs) have transformed the beverage production management by pro... more Process analytical technologies (PATs) have transformed the beverage production management by providing real-time monitoring and control of critical process parameters through non-destructive measurements, such as those obtained with infrared (IR) spectroscopy and enabling process readjustment if necessary. New requirements in the analysis of beverages call for new methods, so in this article, we propose a method based on the construction of multivariate statistical process control (MSPC) charts from a new dissimilarity index (the evolving window dissimilarity index, EWDI) to monitor fermentation processes. The EWDI was applied to monitor wine alcoholic fermentation, the biochemical transformation of sugars into ethanol. Small-scale fermentations were carried out and analyzed using a portable mid-infrared spectrometer. In some of them, process deviations due to nitrogen deficiency or temperature changes were intentionally promoted to evaluate the performance of the EWDI. The MSPC charts build by using the fermentations carried out under normal operating conditions allowed identifying deviations of the fermentation in its early stages. Furthermore, the shape of the EWDI curve over time provides insights about the specific type of deviation occurring. These results show the potential of this new approach to improve the monitoring and control of key process stages in biochemical processes in the food industry, which allows maximizing quality and minimizing losses.
This paper gives an introduction to multivariate calibration from a chemometrics perspective and ... more This paper gives an introduction to multivariate calibration from a chemometrics perspective and reviews the various proposals to generalize the well-established univariate methodology to the multivariate domain. Univariate calibration leads to relatively simple models with a sound statistical underpinning. The associated uncertainty estimation and figures of merit are thoroughly covered in several official documents. However, univariate model predictions for unknown samples are only reliable if the signal is sufficiently selective for the analyte of interest. By contrast, multivariate calibration methods may produce valid predictions also from highly unselective data. A case in point is quantification from near-infrared (NIR) spectra. With the ever-increasing sophistication of analytical instruments inevitably comes a suite of multivariate calibration methods, each with its own underlying assumptions and statistical properties. As a result, uncertainty estimation and figures of merit for multivariate calibration methods has become a subject of active research, especially in the field of chemometrics.
Determination of chemical properties in 'calçot' (Allium cepa L.) by near infrared spectroscopy a... more Determination of chemical properties in 'calçot' (Allium cepa L.) by near infrared spectroscopy and multivariate calibration (a) Silvia Sans, (b) Joan Ferré, (b) Ricard Boqué, (a)(c) José Sabaté, (a)(c) Joan Casals, (a)(c) Joan Simó
Aerial imagery is regularly used by crop researchers, growers and farmers to monitor crops during... more Aerial imagery is regularly used by crop researchers, growers and farmers to monitor crops during the growing season. To extract meaningful information from large-scale aerial images collected from the field, high-throughput phenotypic analysis solutions are required, which not only produce high-quality measures of key crop traits, but also support professionals to make prompt and reliable crop management decisions. Here, we report AirSurf, an automated and open-source analytic platform that combines modern computer vision, up-to-date machine learning, and modular software engineering in order to measure yield-related phenotypes from ultra-large aerial imagery. To quantify millions of in-field lettuces acquired by fixed-wing light aircrafts equipped with normalised difference vegetation index (NDVI) sensors, we customised AirSurf by combining computer vision algorithms and a deep-learning classifier trained with over 100,000 labelled lettuce signals. The tailored platform, AirSurf-Lettuce, is capable of scoring and categorising iceberg lettuces with high accuracy (>98%). Furthermore, novel analysis functions have been developed to map lettuce size distribution across the field, based on which associated global positioning system (GPS) tagged harvest regions have been identified to enable growers and farmers to conduct precision agricultural practises in order to improve the actual yield as well as crop marketability before the harvest.
Spatially offset Raman spectroscopy (SORS) is a non-invasive analytical technique that allows the... more Spatially offset Raman spectroscopy (SORS) is a non-invasive analytical technique that allows the analysis of samples through a container. This makes it an effective tool for studying food and beverage products, as it can measure the sample without being affected by the packaging or the container. In this study, a portable SORS equipment was used for the first time to analyse the alcoholic fermentation process of white wine. Different sample measurement arrangements were tested in order to determine the most effective method for monitoring the fermentation process and predicting key oenological parameters. The best results were obtained when the sample was directly measured through the glass container in which the fermentation was occurring. This allowed for the accurate monitoring of the process and the prediction of density and pH with a root mean square error of cross-validation (RMSECV) of 0.0029 g·L−1 and 0.04, respectively, and R2 values of 0.993 and 0.961 for density and pH, ...
Abstract The goal of this article is to guide the reader through the critical points to be faced ... more Abstract The goal of this article is to guide the reader through the critical points to be faced when monitoring a fermentation following a Process Analytical Technology (PAT) approach. To achieve this purpose Attenuated Total Reflectance – Mid-Infrared (ATR-MIR) spectroscopy coupled to chemometric techniques are proposed. Each of the crucial steps (set up of microvinifications, sampling, spectroscopic analysis and chemometric data treatment) is deeply investigated, revealing how the sampling is decisive for the subsequent modeling phase, suggesting how to set parameters to obtain good quality signals, and explaining how to prepare the data for the chemometric modeling and to perform the calculations. The modeling strategies here presented, based mainly on basic chemometric tools such as principal component analysis and partial least square regression, proved to be effective to the purposes and affordable even for non-expert chemometric users. The article shows, using real examples, how to obtain or predict several parameters from a fermentation data set – control of the fermentation evolution, prediction of oenological parameters during the alcoholic fermentation and detection of deviations from the normal operation condition.
Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy, Jan 15, 2016
In this study the effect of thermal treatment on the enhancement of synchronous fluorescence spec... more In this study the effect of thermal treatment on the enhancement of synchronous fluorescence spectroscopic method for discrimination and quantification of pure extra virgin olive oil (EVOO) samples from EVOO samples adulterated with refined oil was investigated. Two groups of samples were used. One group was analyzed at room temperature (25 °C) and the other group was thermally treated in a thermostatic water bath at 75 °C for 8h, in contact with air and with light exposure, to favor oxidation. All the samples were then measured with synchronous fluorescence spectroscopy. Synchronous fluorescence spectra were acquired by varying the wavelength in the region from 250 to 720 nm at 20 nm wavelength differential interval of excitation and emission. Pure and adulterated olive oils were discriminated by using partial least-squares discriminant analysis (PLS-DA). It was found that the best PLS-DA models were those built with the difference spectra (75 °C-25 °C), which were able to discrimi...
The increasing portability and accessibility of miniaturized NIR spectrometers are promoting the ... more The increasing portability and accessibility of miniaturized NIR spectrometers are promoting the spread of in-field and online applications. Alongside the successful outcomes, there are also several problems related to the acquisition strategies for each instrument and to experimental factors that can influence the collected signals. An insightful investigation of such factors is necessary and could lead to advancements in experimental set-up and data modelling. This work aimed to identify variation sources when using miniaturized NIR sensors and to propose a methodology to investigate such sources based on a multivariate method (ANOVA—Simultaneous Component Analysis) that considers the effects and interactions between them. Five different spectrometers were chosen for their different spectroscopic range and technical characteristics, and samples of worldwide interest were chosen as the case study. Comparing various portable sensors is interesting since results could significantly v...
Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 2016
A new UV-Visible spectroscopic method assisted with microwave for the determination of glucose in... more A new UV-Visible spectroscopic method assisted with microwave for the determination of glucose in pharmaceutical formulations was developed. In this study glucose solutions were oxidized by ammonium molybdate in the presence of microwave energy and reacted with aniline to produce a colored solution. Optimum conditions of the reaction including wavelength, temperature, pH of the medium and relative concentration ratio of the reactants were investigated. It was found that the optimal wavelength for the reaction is 610nm, the optimal reaction time is 80 seconds, the optimal reaction temperature is 160 C°, the optimal reaction pH is 4, and the optimal concentration ratio aniline/ammonium molybdate solution was found to be 1:1. The limits of detection and quantification of the method are 0.82 and 2.75 ppm for glucose solution, respectively. The use of microwaves improved the speed of the method while the use of aniline improved the sensitivity of the method by shifting the wavelength.
3.3.1. Uncertainty of the assessment of trueness, utrueness 3.3.2. Uncertainty of sample pretreat... more 3.3.1. Uncertainty of the assessment of trueness, utrueness 3.3.2. Uncertainty of sample pretreatments, upretreatments 3.3.3. Uncertainty of other terms 3.4. Linear and working ranges 3.5. Limit of detection (LOD) 3.5.1. Estimating the standard deviations of the net concentrations 3.5.2. Alternatives for LOD calculation 3.6. Limit of quantification (LOQ) 3.7. Selectivity (specificity) 3.8. Sensitivity 3.9. Ruggedness (or robustness) 4. The basic principles of method validation 5. Performing the method validation 6. Inter-laboratory comparison as a means for method validation 7. In-house validation 8. Reporting method validation References RESUMEN Validación de métodos analíticos. En este artículo se discute el concepto de validación del método, se describen los elementos que la componen y se explica la fuerte relación entre la validación y las características de ajuste. El método de validación se basa en el cumplimiento de una serie de requerimientos, se explica como seleccionar esos requerimientos, la forma en que se suministran evidencias, y que trabajo se debe llevar a cabo en el laboratorio. También se describen, los principios básicos del método de validación y los diferentes caminos para validar una metodología, tanto en la comparación entre laboratorios o como cuando se lleva a cabo una validación dentro del laboratorio. PALABRAS-CLAVE: Características de ajuste-Criterios de funcionamiento-Validación del método-Validación dentro del laboratorio.
One of the most important problems in the wine world, today, is cork taint, which often has been ... more One of the most important problems in the wine world, today, is cork taint, which often has been chemically identified as 2,4,6-trichloroanisole (TCA). The perception limit of this compound is very low (close to 10 and 40 ng / l for white and red wines, respectively), so, even at such low concentrations, its presence becomes a problem in wine quality. A method for the analysis of TCA in white and red wines has been developed in our laboratory, using headspace solid-phase microextraction and gas chromatography with electron-capture detection. The method, which has been optimized using an experimental design, involves the use of fibres coated with polydimethylsiloxane (PDMS) and allows the analysis of TCA at very low concentrations (under 500 ng / l) with good accuracy (RSD#10%). The limits of quantification of the method are 5 and 8 ng / l for white and red wines, respectively, while the limit of detection is 1 ng / l for both types of wine.
Process analytical technologies (PATs) have transformed the beverage production management by pro... more Process analytical technologies (PATs) have transformed the beverage production management by providing real-time monitoring and control of critical process parameters through non-destructive measurements, such as those obtained with infrared (IR) spectroscopy and enabling process readjustment if necessary. New requirements in the analysis of beverages call for new methods, so in this article, we propose a method based on the construction of multivariate statistical process control (MSPC) charts from a new dissimilarity index (the evolving window dissimilarity index, EWDI) to monitor fermentation processes. The EWDI was applied to monitor wine alcoholic fermentation, the biochemical transformation of sugars into ethanol. Small-scale fermentations were carried out and analyzed using a portable mid-infrared spectrometer. In some of them, process deviations due to nitrogen deficiency or temperature changes were intentionally promoted to evaluate the performance of the EWDI. The MSPC charts build by using the fermentations carried out under normal operating conditions allowed identifying deviations of the fermentation in its early stages. Furthermore, the shape of the EWDI curve over time provides insights about the specific type of deviation occurring. These results show the potential of this new approach to improve the monitoring and control of key process stages in biochemical processes in the food industry, which allows maximizing quality and minimizing losses.
This paper gives an introduction to multivariate calibration from a chemometrics perspective and ... more This paper gives an introduction to multivariate calibration from a chemometrics perspective and reviews the various proposals to generalize the well-established univariate methodology to the multivariate domain. Univariate calibration leads to relatively simple models with a sound statistical underpinning. The associated uncertainty estimation and figures of merit are thoroughly covered in several official documents. However, univariate model predictions for unknown samples are only reliable if the signal is sufficiently selective for the analyte of interest. By contrast, multivariate calibration methods may produce valid predictions also from highly unselective data. A case in point is quantification from near-infrared (NIR) spectra. With the ever-increasing sophistication of analytical instruments inevitably comes a suite of multivariate calibration methods, each with its own underlying assumptions and statistical properties. As a result, uncertainty estimation and figures of merit for multivariate calibration methods has become a subject of active research, especially in the field of chemometrics.
Determination of chemical properties in 'calçot' (Allium cepa L.) by near infrared spectroscopy a... more Determination of chemical properties in 'calçot' (Allium cepa L.) by near infrared spectroscopy and multivariate calibration (a) Silvia Sans, (b) Joan Ferré, (b) Ricard Boqué, (a)(c) José Sabaté, (a)(c) Joan Casals, (a)(c) Joan Simó
Aerial imagery is regularly used by crop researchers, growers and farmers to monitor crops during... more Aerial imagery is regularly used by crop researchers, growers and farmers to monitor crops during the growing season. To extract meaningful information from large-scale aerial images collected from the field, high-throughput phenotypic analysis solutions are required, which not only produce high-quality measures of key crop traits, but also support professionals to make prompt and reliable crop management decisions. Here, we report AirSurf, an automated and open-source analytic platform that combines modern computer vision, up-to-date machine learning, and modular software engineering in order to measure yield-related phenotypes from ultra-large aerial imagery. To quantify millions of in-field lettuces acquired by fixed-wing light aircrafts equipped with normalised difference vegetation index (NDVI) sensors, we customised AirSurf by combining computer vision algorithms and a deep-learning classifier trained with over 100,000 labelled lettuce signals. The tailored platform, AirSurf-Lettuce, is capable of scoring and categorising iceberg lettuces with high accuracy (>98%). Furthermore, novel analysis functions have been developed to map lettuce size distribution across the field, based on which associated global positioning system (GPS) tagged harvest regions have been identified to enable growers and farmers to conduct precision agricultural practises in order to improve the actual yield as well as crop marketability before the harvest.
Spatially offset Raman spectroscopy (SORS) is a non-invasive analytical technique that allows the... more Spatially offset Raman spectroscopy (SORS) is a non-invasive analytical technique that allows the analysis of samples through a container. This makes it an effective tool for studying food and beverage products, as it can measure the sample without being affected by the packaging or the container. In this study, a portable SORS equipment was used for the first time to analyse the alcoholic fermentation process of white wine. Different sample measurement arrangements were tested in order to determine the most effective method for monitoring the fermentation process and predicting key oenological parameters. The best results were obtained when the sample was directly measured through the glass container in which the fermentation was occurring. This allowed for the accurate monitoring of the process and the prediction of density and pH with a root mean square error of cross-validation (RMSECV) of 0.0029 g·L−1 and 0.04, respectively, and R2 values of 0.993 and 0.961 for density and pH, ...
Abstract The goal of this article is to guide the reader through the critical points to be faced ... more Abstract The goal of this article is to guide the reader through the critical points to be faced when monitoring a fermentation following a Process Analytical Technology (PAT) approach. To achieve this purpose Attenuated Total Reflectance – Mid-Infrared (ATR-MIR) spectroscopy coupled to chemometric techniques are proposed. Each of the crucial steps (set up of microvinifications, sampling, spectroscopic analysis and chemometric data treatment) is deeply investigated, revealing how the sampling is decisive for the subsequent modeling phase, suggesting how to set parameters to obtain good quality signals, and explaining how to prepare the data for the chemometric modeling and to perform the calculations. The modeling strategies here presented, based mainly on basic chemometric tools such as principal component analysis and partial least square regression, proved to be effective to the purposes and affordable even for non-expert chemometric users. The article shows, using real examples, how to obtain or predict several parameters from a fermentation data set – control of the fermentation evolution, prediction of oenological parameters during the alcoholic fermentation and detection of deviations from the normal operation condition.
Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy, Jan 15, 2016
In this study the effect of thermal treatment on the enhancement of synchronous fluorescence spec... more In this study the effect of thermal treatment on the enhancement of synchronous fluorescence spectroscopic method for discrimination and quantification of pure extra virgin olive oil (EVOO) samples from EVOO samples adulterated with refined oil was investigated. Two groups of samples were used. One group was analyzed at room temperature (25 °C) and the other group was thermally treated in a thermostatic water bath at 75 °C for 8h, in contact with air and with light exposure, to favor oxidation. All the samples were then measured with synchronous fluorescence spectroscopy. Synchronous fluorescence spectra were acquired by varying the wavelength in the region from 250 to 720 nm at 20 nm wavelength differential interval of excitation and emission. Pure and adulterated olive oils were discriminated by using partial least-squares discriminant analysis (PLS-DA). It was found that the best PLS-DA models were those built with the difference spectra (75 °C-25 °C), which were able to discrimi...
The increasing portability and accessibility of miniaturized NIR spectrometers are promoting the ... more The increasing portability and accessibility of miniaturized NIR spectrometers are promoting the spread of in-field and online applications. Alongside the successful outcomes, there are also several problems related to the acquisition strategies for each instrument and to experimental factors that can influence the collected signals. An insightful investigation of such factors is necessary and could lead to advancements in experimental set-up and data modelling. This work aimed to identify variation sources when using miniaturized NIR sensors and to propose a methodology to investigate such sources based on a multivariate method (ANOVA—Simultaneous Component Analysis) that considers the effects and interactions between them. Five different spectrometers were chosen for their different spectroscopic range and technical characteristics, and samples of worldwide interest were chosen as the case study. Comparing various portable sensors is interesting since results could significantly v...
Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 2016
A new UV-Visible spectroscopic method assisted with microwave for the determination of glucose in... more A new UV-Visible spectroscopic method assisted with microwave for the determination of glucose in pharmaceutical formulations was developed. In this study glucose solutions were oxidized by ammonium molybdate in the presence of microwave energy and reacted with aniline to produce a colored solution. Optimum conditions of the reaction including wavelength, temperature, pH of the medium and relative concentration ratio of the reactants were investigated. It was found that the optimal wavelength for the reaction is 610nm, the optimal reaction time is 80 seconds, the optimal reaction temperature is 160 C°, the optimal reaction pH is 4, and the optimal concentration ratio aniline/ammonium molybdate solution was found to be 1:1. The limits of detection and quantification of the method are 0.82 and 2.75 ppm for glucose solution, respectively. The use of microwaves improved the speed of the method while the use of aniline improved the sensitivity of the method by shifting the wavelength.
3.3.1. Uncertainty of the assessment of trueness, utrueness 3.3.2. Uncertainty of sample pretreat... more 3.3.1. Uncertainty of the assessment of trueness, utrueness 3.3.2. Uncertainty of sample pretreatments, upretreatments 3.3.3. Uncertainty of other terms 3.4. Linear and working ranges 3.5. Limit of detection (LOD) 3.5.1. Estimating the standard deviations of the net concentrations 3.5.2. Alternatives for LOD calculation 3.6. Limit of quantification (LOQ) 3.7. Selectivity (specificity) 3.8. Sensitivity 3.9. Ruggedness (or robustness) 4. The basic principles of method validation 5. Performing the method validation 6. Inter-laboratory comparison as a means for method validation 7. In-house validation 8. Reporting method validation References RESUMEN Validación de métodos analíticos. En este artículo se discute el concepto de validación del método, se describen los elementos que la componen y se explica la fuerte relación entre la validación y las características de ajuste. El método de validación se basa en el cumplimiento de una serie de requerimientos, se explica como seleccionar esos requerimientos, la forma en que se suministran evidencias, y que trabajo se debe llevar a cabo en el laboratorio. También se describen, los principios básicos del método de validación y los diferentes caminos para validar una metodología, tanto en la comparación entre laboratorios o como cuando se lleva a cabo una validación dentro del laboratorio. PALABRAS-CLAVE: Características de ajuste-Criterios de funcionamiento-Validación del método-Validación dentro del laboratorio.
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