Source Separation in Chemical Analysis : Recent Achievements and Perspectives

International audienceSource separation is one of the most relevant estimation problems found in chemistry. Indeed, dealing with mixtures is paramount in different kinds of chemical analysis. For instance, there are some cases where the analyte is a chemical mixture of different components, e.g., in the analysis of rocks and heterogeneous materials through spectroscopy. Moreover, a mixing process can also take place even when the components are not chemically mixed. For instance, in ionic analysis of liquid samples, the ions are not chemically connected, but, due to the lack of selectivity of the chemical sensors, the acquired responses may be influenced by ions that are not the desired ones. Finally, there are some situations where the pure components cannot be isolated chemically since they appear only in the presence of other components. In this case, BSS may provide these components that cannot be retrieved otherwise. In this paper, our aim is to shed some light on the use of BSS in chemical analysis. In this context, we firstly provide a brief overview on source separation (Section II), with particular attention to the classes of linear and nonlinear mixing models (Sections III and IV, respectively). Then, (in Section V), we will give some conclusions and focus on challenging aspects that are found in chemical analysis. Although dealing with a relatively new field of applications, this article is not an exhaustive survey of source separation methods and algorithms, since there are solutions originated in closely related domains (e.g. remote sensing and hyperspectral imaging) that suit well several problems found in chemical analysis. Moreover, we do not discuss the supervised source separation methods, which are basically multivariate regression techniques, that one can find in chemometrics

An overview of signal processing issues in chemical sensing

International audienceThis tutorial paper aims at summarizing some problems, ranging from analytical chemistry to novel chemical sensors, that can be addressed with classical or advanced methods of signal and image processing. We gather them under the denomination of "chemical sensing". It is meant to introduce the special session "Signal Processing for Chemical Sensing" with a large overview of issues which have been and remain to be addressed in this application domain, including chemical analysis leading to PARAFAC/tensor methods, hyper spectral imaging, ion-sensitive sensors, artificial nose, chromatography, mass spectrometry, etc. For enlarging and illustrating the points of view of this tutorial, the invited papers of the session consider other applications (NMR, Raman spectroscopy, recognition of explosive compounds, etc.) addressed by various methods, e.g. source separation, Bayesian, and exploiting typical chemical signal priors like positivity, linearity, unit-concentration or sparsity

Blind source separation and feature extraction in concurrent control charts pattern recognition: Novel analyses and a comparison of different methods

International audienceControl charts are among the main tools in statistical process control (SPC) and have been extensively used for monitoring industrial processes. Currently, besides the single control charts, there is an interest in the concurrent ones. These graphics are characterized by the simultaneous presence of two or more single control charts. As a consequence, the individual patterns may be mixed, hindering the identification of a non-random pattern acting in the process; this phenomenon is refered as concurrent charts. In view of this problem, our first goal is to investigate the importance of an efficient separation step for pattern recognition. Then, we compare the efficiency of different Blind Source Separation (BSS) methods in the task of unmixing concurrent control charts. Furthermore, these BSS methods are combined with shape and statistical features in order to verify the performance of each one in pattern classification. In additional, the robustness of the better approach is tested in scenarios where there are different non-randomness levels and in cases with imbalanced dataset provided to the classifier. After simulating different patterns and applying several separation methods, the results have shown that the recognition rate is widely influenced by the separation and feature extraction steps and that the selection of efficient separation methods is fundamental to achieve high classification rates

A kk-additive Choquet integral-based approach to approximate the SHAP values for local interpretability in machine learning

Besides accuracy, recent studies on machine learning models have been addressing the question on how the obtained results can be interpreted. Indeed, while complex machine learning models are able to provide very good results in terms of accuracy even in challenging applications, it is difficult to interpret them. Aiming at providing some interpretability for such models, one of the most famous methods, called SHAP, borrows the Shapley value concept from game theory in order to locally explain the predicted outcome of an instance of interest. As the SHAP values calculation needs previous computations on all possible coalitions of attributes, its computational cost can be very high. Therefore, a SHAP-based method called Kernel SHAP adopts an efficient strategy that approximate such values with less computational effort. In this paper, we also address local interpretability in machine learning based on Shapley values. Firstly, we provide a straightforward formulation of a SHAP-based method for local interpretability by using the Choquet integral, which leads to both Shapley values and Shapley interaction indices. Moreover, we also adopt the concept of $k$-additive games from game theory, which contributes to reduce the computational effort when estimating the SHAP values. The obtained results attest that our proposal needs less computations on coalitions of attributes to approximate the SHAP values

A Blind Source Separation Method for Chemical Sensor Arrays based on a Second-order mixing model

International audienceIn this paper we propose a blind source separation method to process the data acquired by an array of ion-selective electrodes in order to measure the ionic activity of different ions in an aqueous solution. While this problem has already been studied in the past, the method presented differs from the ones previously analyzed by approximating the mixing function by a second-degree polynomial, and using a method based on the differential of the mutual information to adjust the parameter values. Experimental results, both with synthetic and real data, suggest that the algorithm proposed is more accurate than the other models in the literature

A Sparsity-Based Method for Blind Compensation of a Memoryless Nonlinear Distortion: Application to Ion-Selective Electrodes

International audience— In this paper, we propose a method for blind compensation of a memoryless nonlinear distortion. We assume as prior information that the desired signal admits a sparse representation in a transformed domain that should be known in advance. Then, given that a nonlinear distortion tends to generate signals that are less sparse than the desired one, our proposal is to build a compensating function model that gives rise to a maximally sparse signal. The implementation of this proposal has, as central elements, a criterion built upon an approximation of the 0-norm, the use of polynomial functions as compensating structures, and an optimization strategy based on sequential quadratic programming. We provide a theoretic analysis for an 0-norm criterion and results considering synthetic data. We also employ the method in an actual application related to chemical analysis via ion-selective electrode arrays

Theoretical Studies and Algorithms Regarding the Solution of Non-invertible Nonlinear Source Separation

International audienceIn this paper, we analyse and solve a source separation problem based on a mixing model that is nonlinear and non-invertible at the space of mixtures. The model is relevant considering it may represent the data obtained from ion-selective electrode arrays. We apply a new approach for solving the problems of local stability of the recurrent network previously used in the literature, which allows for a wider range of source concentration. In order to achieve this, we utilize a second-order recurrent network which can be shown to be locally stable for all solutions. Using this new network and the priors that chemical sources are continuous and smooth, our proposal performs better than the previous approach