Tratamiento numérico de los datos en el análisis cuantitativo por espectrometría vibracional.

RESUMEN La presente Tesis integra un conjunto de trabajos relacionados con la aplicación de algunos de los distintos tratamientos numéricos que pueden aplicarse a los datos analíticos obtenidos mediante diferentes técnicas de medida en la espectroscopía vibracional, buscando así potenciar y aumentar el rendimiento de los distintos procesos analíticos desarrollados, asegurando una mayor calidad de los resultados obtenidos. Así, con el ánimo de mostrar el amplio abanico de posibilidades que ofrece, no sólo la espectrometría vibracional, sino la aplicación de la Quimiometría sobre los datos instrumentales obtenidos a través de aquella, se seleccionaron una serie de muestras de naturaleza muy diversa en cuanto a composición, estado y niveles de concentración de los analitos de interés, a la par que de un uso altamente extendido; englobando productos farmacéuticos, alimentos (zumos, batidos, yogures, chocolates, vinagres), formulaciones comerciales de productos fitosanitarios o virutas de cuero empleadas para el tratamiento de aguas contaminadas. En concreto, los trabajos englobados en esta Tesis Doctoral pretenden ser una guía útil en la que se pone de manifiesto la evolución desde metodologías analíticas que requieren un determinado tratamiento químico de la muestra para conseguir cierta selectividad y por ello precisan de un menor tratamiento matemático de los datos, hasta aquellas metodologías que requieren un mínimo o ningún tratamiento químico previo de las muestras pero que, en consecuencia, necesitan de un tratamiento numérico más relevante y complejo de los datos instrumentales. Con todo ello es posible evaluar las prestaciones de la Quimiometría combinada con la espectroscopía vibracional infrarroja para el desarrollo de metodologías analíticas que pueden considerarse como una seria alternativa para los laboratorios que desarrollan y optimizan métodos analíticos para el control de calidad de productos. Para los distintos estudios se han utilizado diferentes modos de medida (Transmitancia, Reflectancia Total Atenuada o Reflectancia Difusa) tanto en la región media (MIR) como en la región próxima (NIR) del espectro infrarrojo. Así pues, se encuentran de un lado aquellos métodos de análisis basados en el empleo de la calibración univariante (orden cero) para relacionar la señal analítica registrada (o su derivada) con la propiedad que se pretendía cuantificar. Estos procedimientos simples se han aplicado a la determinación de pesticidas y principios activos en productos fitosanitarios y fármacos, respectivamente. Por otro lado, es posible encontrar aquellos métodos en los que el problema se resolvió empleando una serie de algoritmos matemáticos, con el fin de intentar predecir la propiedad de interés a partir de respuestas instrumentales no selectivas. Dentro de este grupo de trabajos se han empleado diferentes técnicas de calibración multivariante para la obtención de resultados, tanto para la clasificación como para la determinación de las propiedades y los parámetros de interés. En este caso, se ha hecho uso del Análisis en Componentes Principales (PCA), la Regresión Parcial en Mínimos Cuadrados (PLSR), así como las Redes Neuronales Artificiales (ANN), seleccionando para cada uno de los estudios la técnica más adecuada que permitiese asegurar la calidad de los resultados obtenidos a través de una máxima capacidad predictiva. Finalmente, se ha desarrollado una metodología basada en la generación de información de segundo orden a partir de la combinación de la multiconmutación y la espectroscopía vibracional para la determinación del grado de acidez en muestras de vinagre, empleando el método PARAFAC para el tratamiento de la información vibracional generada. Los resultados obtenidos mediante la aplicación de los diferentes modelos desarrollados han resultado ser de una adecuada calidad, por lo que las metodologías propuestas, tras ser validadas a través de la determinación de sus correspondientes características analíticas, pueden considerarse adecuadas para realizar un correcto control de calidad de los diferentes productos considerados en esta Tesis Doctoral. __________________________________________________________________________________________________In this thesis, several works, related to the use and development of different chemometric techniques applied to data treatment obtained from different sampling techniques (Transmittance, Attenuated Total Reflectance or Diffuse Reflectance) based on vibrational spectroscopy (Mid-IR and Near-IR ranges) are presented. In fact, their performance in the determination of different properties and quality parameters on a wide range of samples such as pharmaceuticals, food (juices, milk shakes, yoghurts, chocolates, and vinegars), agrochemicals products and tanned solid wastes used for removing hydrocarbons from polluted waters, are evaluated. Specifically, works included in this thesis expect to be a useful guide which tries to show up evolution from analytical methodologies requiring, in order to achieve certain selectivity, some chemical treatment on sample and for this fact they precise low data treatment; until that methodologies which requires no previous chemical treatment but, therefore, they precise relevant and complex mathematical treatment on instrumental data. For quantifying each property/parameter, a calibration model has been designed and optimized to get good results. In this sense, some works include analytical methods based on univariate calibration (zero order). On the other hand, analytical procedures using multivariate calibration (first order) models, which employ a series of mathematics algorithms on the different no-selective instrumental responses, are also described. Among different multivariate calibration techniques, Principal Component Analysis (PCA), Partial Least Squares Regression (PLSR), and Artificial Neural Networks (ANN), all of them with an appropriate mathematical pre-treatment, has been considered not only for classification but also to quantify properly the properties and parameters of different chemicals on the several samples under study. The most appropriate technique for each study has been used in order to asses the quality of the obtained results through the maximum predictive capabilities. Finally, a methodology based on the second-order data generation, combining multicommutation and vibrational spectroscopy, has been developed for the determination of acidity content in vinegar samples using multi-way decomposition method PARAFAC. Obtained results evidence that developed models are good, so established procedures, validated through their predictive capabilities, could be used to carry out a right quality control of the different samples considered in this Thesis

Laser-induced breakdown spectroscopy of samples of astrochemical interest handled as individual particles by means of non-inertial acoustic confinement.

The present communication will show experiments performed with an acoustic levitator capable of trapping individual solid particles of different sizes (preferably in the range between 0.1 - 5 mm), shapes, and chemical properties in air. The levitator offers significant advantages over conventional handling approaches for particulate matter as it just requires picking up the desired particle, place it in the levitation device, and performing fine adjustment to bring the particle to the focal point of the laser beam. Single-shot or accumulative shots can be performed depending on the laser energy required, allowing the recording of excellent signal-to-noise ratio LIBS spectra.Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tech

The sound of geological targets on Mars from the absolute intensity of laser-induced sparks shock waves

Inspection of geological material is one of the main goals of the Perseverance rover during its journey across the landscape of the Jezero crater in Mars. NASA's rover integrates SuperCam, an instrument capable of performing standoff characterization of samples using a variety of techniques. Among those tools, SuperCam can perform laser-induced breakdown spectroscopy (LIBS) studies to elucidate the chemical composition of the targets of interest. Data from optical spectroscopy can be supplemented by simultaneously-produced laser-produced plasma acoustics in order to expand the information acquired from the probed rocks thanks to the SuperCam's microphone (MIC) as it can be synchronized with the LIBS laser. Herein, we report cover results from LIBS and MIC during Perseverance's first 380 sols on the Martian surface. We study the correlation between both recorded signals, considering the main intrasample and environmental sources of variation for each technique, to understand their behavior and how they can be interpreted together towards complimenting LIBS with acoustics. We find that louder and more stable acoustic signals are recorded from rock with compact surfaces, i.e., low presence loose particulate material, and harder mineral phases in their composition. Reported results constitute the first description of the evolution of the intensity in the time domain of shockwaves from laser-produced plasmas on geological targets recorded in Mars. These signals are expected contain physicochemical signatures pertaining to the inspected sampling positions. As the dependence of the acoustic signal recorded on the sample composition, provided by LIBS, is unveiled, the sound from sparks become a powerful tool for the identification of mineral phases with similar optical emission spectra.Many people helped with this project in addition to the co-authors, including hardware and operation teams, and we are most grateful for their support. This project was supported in the USA by NASA’s Mars Exploration Program and in France is conducted under the authority of CNES. Research funded by projects UMA18-FEDERJA-272 from Junta de Andalucía and PID2020-119185GB-I00 from Ministerio de Ciencia e Innovacion, of Spain. P.P. is grateful to the European Union’s Next Generation EU (NGEU) plan and the Spanish Ministerio de Universidades for his Margarita Salas fellowship under the program ′′Ayudas para la Recualificacion del Sistema Universitario Español′′. RCW was funded by JPL contract 1681089. A.U was funded by NASA Mars 2020 Participating Scientist program 80NSSC21K0330. Funding for open access charge: Universidad de Málaga / CBU

Deep-UV laser-induced breakdown spectrometry and laser-ionization mass spectrometry for astrochemistry studies.

The recent ambitions of different national space agencies to return to the Moon and to potentially set up a permanent moon base soon, have triggered the interest to adapt different analysis techniques to the conditions of our satellite. The Moon has virtually no atmosphere, with a vacuum level in the range of the pico mbar. Under such conditions, and after the formation of a laser-induced plasma, the possibility of direct recording of LIBS spectra below 200 nm (DUV/VUV LIBS) or performing mass spectrometry out of the generated ions (LIMS) can be done without the use of pumping system. This communication will show the results obtained in the laboratory under ultra-high vacuum conditions monitoring the photons and ions of solid samples of interest in astrochemical research. For LIBS, a flat-field XUV spectrometer was used, with capability to cover a spectral range from 30-250 nm. Such region, very unexplored in conventional LIBS offers several advantages as reduced interferences and a higher emission intensity from elements of interest in astrochemistry as CHNOPS. For LIMS, a reflectron-type time-of-flight mass spectrometer was used, allowing the simultaneous recording of mass spectra in the 1-1000 range. A deep discussion on the two experimental configurations will be provided, detailing the experimental parameters affecting the signal in both cases. Different examples will be shown, with special emphasis in non-consolidated matter that can be assimilated to the moon regoliths.Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tech