Tenerife como análogo de Marte: Caracterización multianalítica (Raman, DRX, ATR-FTIR, SEM y MossBaeur) de muestras de interés planetario y astrobiológico

La tesis se ha centrado en la identificación Raman de las especies minerales que serán de importancia para futura interpretación de los datos que serán recibidos del instrumento RLS en la misión ESA-ExoMars, especialmente en el contexto geológico. Los estudios realizados en la tesis presentan una identificación mineralógica y geoquímica, fundamentalmente mediante espectroscopía Raman, de las especies minerales de diferentes afloramientos de Tenerife y su posible analogía con Marte. De esta manera, se ha podido desarrollar una base de datos de espectros sobre minerales de entornos y afloramientos volcánicos teniendo en cuenta la mineralogía primaria y los minerales secundarios de procesos alteracionales que afectan a la colección de muestras obtenidas. Entonces, el contexto geológico, la mineralogía y la caracterización Raman ofrecerá una gran cantidad de pistas e indicios sobre la diversidad de materiales volcánicos en Marte y sus procesos relacionados, fundamentalmente en la historia temprana de Marte. Por otro lado, la complementación de los análisis Raman con otras técnicas secundarias, como la espectroscopia infrarroja, difracción de rayos X, microscopia electrónica y la espectroscopia Mossbaüer (siendo técnicas usadas anteriormente en misiones espaciales), son necesarias para incrementar las capacidades del futuro instrumento. De esta manera, mediante un análisis comparativo y detallado, se puede obtener información completa sobre la mineralogía considerando las distintas reglas de selección (tanto de carácter vibracional como excitacional) y tamaño de partícula/grano. Además se han llevado otros experimentos de caracter astrobiológico y astrogeológico relacionados con otro de los objetivos de la Misión ExoMars como la detección de compuestos orgánicos sobre superficies basalticas en condiciones extremas y medidas con el simulador RLS-ESA-ExoMars para maximizar las capacidades y condiciones de trabajo del futuro InstrumentoDepartamento de Física de la Materia Condensada, Cristalografía y Minerealogí

Combined vibrational, structural, elemental and Mössbauer spectroscopic analysis of natural phillipsite (zeolite) from historical eruptions in Tenerife, Canary Islands: Implication for Mars

The outcrop of “Las Arenas” volcano in Tenerife, Canary Islands (Spain) has been presented as Terrestrial volcanic analog for ancient Mars, showing a great variety of alteration processes and interesting mineralogy. The current analysis has been done by means of measurement techniques used or proposed on Martian studies. The new analysis of the zeolite has been carried out using Raman spectroscopy, Mössbauer spectroscopy, X-ray diffraction (XRD), Infrared spectroscopy, Laser induced breakdown spectroscopy and Scanning electron microscopy (SEM-EDX). The zeolite has been carefully analyzed using vibrational spectroscopy and it has been identified as Ca-phillipsite. The other techniques support and confirm the results. The measurements and results using the Raman Laser Spectrometer (RLS) simulator system show the capabilities RLS system in the ESA Exo- Mars mission. The chemometrical methods for the vibrational mineral detection show the advantages of Raman spectroscopy to understand the possible geological context. Furthermore, the proposed diagenesis and formation of the zeolites in southern part of Tenerife island have been confirmed by the twin space prototypes used. A new hypothesis about the origin for the special case of “Las Arenas” volcano Ca-phillipsite has been proposed. Finally, a multi-complementary comparison among the different techniques used on the current studie has been done and, also an analogy with the next space mission has been established. These analyses emphasize the strength of the different techniques and the working synergy of the different techniques together for planetary space missions

Analysis and adsorption-interaction of amino acids on basaltic mineral subjected to different simulated atmospheres

[EN] The research have been conducted in order to have a better understanding of amino acid adsorption on volcanic matrix surface subjected to different extreme environmental conditions (Martian surface environment, space environment, UV-environment, etc.) simulated by The Planetary Atmosphere and Surfaces Chamber (PASC) at the ”INTA-Centro de Astrobiogia”. The spectroscopic measurements were done by Raman and IR spectroscopy (at the Unidad Asociada Uva-CSIC at Centro de Astrobiología) taking into account the capabilities of the combined Raman-IR analyses for astrobiological target such as the detection of biomarkers on the future ESA-ExoMars Mission. Moreover, SEM-EDX analyses have been conducted in order to complement the spectroscopic results, which endeavour the use of spectroscopic systems for space missions. Conclusion: The L-aspartic acid shows to be the most suitable amino acid for this kind of experiment; the amino acid half–life is 104 seconds according to the reference; both spectroscopic techniques, working in synergy, have detected the amino acid degradation, but amino acid mineral interaction was not detected; the experiments have shown the versatility of the simulation chamber (PASC) to perform experiments under different planetary environments.[ES] Los experimentos se han realizado con el objectivo de tener un mejor entendimiento sobre aminoácidos inmovilizados sobre matrices de caracter volcánico y estos han sido sometidos a diferentes ambientes extremos (Ambiente marciano, ambiente espacial, ambiente de radiación UV, etc.) dentro de la Cámara de Simulación de atmosferas y superficies planetarias (PASC) en el Centro de Astrobiología- INTA. Los métodos espectroscópicos usados son la espectroscopía Raman e Infrarroja (en la Unidad Asociada Uva-CSIC al Centro de Astrobiología) teniendo en cuenta las capacidades combinadas de estos sistemas para objetivos astrobiológicos como la detección de biomarcadores en la futura misión ESAExoMars. Además, se realizaron medidas mediante microscopía electrónica (SEM-EDX) las cuales complementan los resultados espectroscópicos y refuerzan el uso de estos sistemas para misiones espaciales. Conclusiones: El ácido L-Aspartico demostró ser el más eficiente para este tipo de experimentos; la vida media de los aminoácido es de 104 teniendo en cuenta las referencias; ambos sistemas espectroscópicos Raman-IR, trabajando conjuntamente, detectaron la degradación de los aminoácidos, pero la interacción entre aminoácido-mineral no fue detectada; los experimentos demostraron la versatilidad de la Cámara de Simulación (PASC) en cuanto a la realizacion de experimentos en distintos ambientes planetarios.Peer reviewe

Nd3+-doped TeO2–PbF2–AlF3 glasses for laser applications

A study of the optical properties of Nd3+ ion in TeO2–PbF2–AlF3 glasses has been carried out for different Nd3+ concentrations. Based on the Judd–Ofelt theory, intensity parameters and radiative properties were determined from the absorption spectra. Focusing on the suitability of this host for laser applications, the spectroscopic quality factor v was obtained with a value of 1.07, a value of the order of other compositions proposed as laser hosts. For the most intense emission corresponding with the 4F3/2?4I11/2 transition (1.06 lm), the absorption and emission and have been calculated with values of 1.20 10 20 cm2, 2.08 10 20 cm2. A positive value for the gain cross-sections has been found for a population inversion factor c of 0.4 in the spectral range from 1060 to 1110 nm. All these results suggest the potentially use of this system as a laser host

Abiotic versus biotic iron mineral transformation studied by a miniaturized backscattering Mössbauer spectrometer (MIMOS II), X-ray diffraction and Raman spectroscopy

Searching for biomarkers or signatures of microbial transformations of minerals is a critical aspect for determining how life evolved on Earth, and whether or not life may have existed in other planets, including Mars. In order to solve such questions, several missions to Mars have sought to determine the geochemistry and mineralogy on the Martian surface. This research includes the two miniaturized Mössbauer spectrometers (MIMOS II) on board the Mars Exploration Rovers Spirit and Opportunity, which have detected a variety of iron minerals on Mars, including magnetite (Fe2+Fe3+2O4) and goethite (α-FeO(OH)). On Earth, both minerals can derive from microbiological activity (e.g. through dissimilatory iron reduction of ferrihydrite by Fe(III)-reducing bacteria). Here we used a lab based MIMOS II to characterize the mineral products of biogenic transformations of ferrihydrite to magnetite by the Fe(III)-reducing bacteria Geobacter sulfurreducens. In combination with Raman spectroscopy and X-ray diffraction (XRD), we observed the formation of magnetite, goethite and siderite. We compared the material produced by biogenic transformations to abiotic samples in order to distinguish abiotic and biotic iron minerals by techniques that are or will be available onboard Martian based laboratories. The results showed the possibility to distinguish the abiotic and biotic origin of the minerals. Mossbauer was able to distinguish the biotic/abiotic magnetite with the interpretation of the geological context (Fe content mineral assemblages and accompanying minerals) and the estimation of the particle size in a non-destructive way. The Raman was able to confirm the biotic/abiotic principal peaks of the magnetite, as well as the organic principal vibration bands attributed to the bacteria. Finally, the XRD confirmed the particle size and mineralogy

Estudio de basaltos mediante espectroscopía de plasma inducido por láser (LIBS) para la fabricación de bloques de lapilli

Se analizaron mediante espectroscopía de plasma inducido por láser (LIBS), espectroscopía Raman y difracción de rayos x (XRD) muestras seleccionadas de diversas zonas de Tenerife, con el objetivo de identificar su composición química elemental y mineralógica. Los resultados mostraron los elementos mayoritarios siguientes: O, F, Na, K, Mg, Al, Si, Ca, Ti y Fe. La identificación de las muestras, mediante espectroscopía Raman y XRD, mostró una mineralogía de tipo basáltica coincidente con los resultados de composición elemental LIBS. Los resultados de los análisis con instrumentación portátil demuestran la aplicabilidad de la espectroscopía LIBS y, en especial, en combinación con la espectroscopía Raman, para su utilización en la detección mineralógica-química en las zonas de extracción de basaltos y picón para la construcción en Tenerife

Influence of hydrothermal activity on the mineralogical-petrophysical properties of an atypical doleritic reservoir rock : a case study of the Gabes Gulf (north Africa, Tunisia)

The Gabes Gulf located in the South Mediterranean Sea (Southeastern part of Tunisia) is a prolific petroleum-producing area with several oil and gas fields and it's the subject of significant discoveries. The area is affected by intense tectonic events and several stages of hydrothermal activities. During drilling at the MX area in NE of the Gabes Gulf, a magmatic intrusion has been encountered within a reservoir rock (i.e., Douleb Formation). The objectives of the present study are (1) to investigate the impact of the hydrothermal activities on this magmatic intrusion and (2) to characterize the potential modifications in its mineralogy and petro-physical properties that can affect the migration/accumulation of hydrocarbons. To do so we combine optical microscopy, X-ray diffraction, scanning electron microscopy, energy dispersive X-ray spectrometry, micro-Raman spectroscopy, electron microprobe analyses, and petro-physical measurements. Our results show that the initial magmatic intrusion (dolerite) is composed mainly of plagioclase, clinopyroxene, and olivine. Based on petrographic observations, this intrusion subjected to several stages of hydrothermal fluid alterations that modified the primary texture and mineralogy. Albite, calcite, ankerite, dolomite, pyrite, quartz, anatase, kaolinite, and chlorite are the main secondary mineral products. During this alteration process, carbonates, pyrite, and quartz precipitated in vesicles, forming amygdules structure with enveloped zones indicating a fluctuation of fluid chemistry during their formation. In addition, petrographic observations indicate an interaction between feldspars exsolution and metasomatic processes in the studied area. The dissolution mechanisms, as well as the textural modifications in the dolerite induced by the hydrothermal activity, are underlined by the presence of spherulites, pores, and micropores. Such modifications significantly improved the porosity of the dolerite body. Conversely, the new mineralization that filled the fractures and micro-fractures, have reduced the inter-pore connections, and thus reduced its permeability. The present work demonstrates the important role of hydrothermal activity on the petro-physical properties of magmatic intrusions and how it could facilitate the migration/accumulation of hydrocarbons. Our results open the door for further investigations to check the potential presence of hydrocarbons within this doleritic intrusion

Raman-Mössbauer-XRD studies of selected samples from “Los Azulejos” outcrop: A possible analogue for assessing the alteration processes on Mars

The outcrop of “Los Azulejos” is visible at the interior of the Cañadas Caldera in Tenerife Island (Spain). It exhibits a great variety of alteration processes that could be considered as terrestrial analogue for several geological processes on Mars. This outcrop is particularly interesting due to the content of clays, zeolite, iron oxides, and sulfates corresponding to a hydrothermal alteration catalogued as “Azulejos” type alteration. A detailed analysis by portable and laboratory Raman systems as well as other different techniques such as X ray diffraction (XRD) and Mössbauer spectroscopy has been carried out (using twin-instruments from Martian lander missions: Mössbauer spectrometer MIMOS-II from the NASA-MER mission of 2001 and the XRD diffractometer from the NASA-MSL Curiosity mission of 2012). The mineral identification presents the following mineral species: magnetite, goethite, hematite, anatase, rutile, quartz, gregoryite, sulphate (thenardite and hexahydrite), diopside, feldspar, analcime, kaolinite and muscovite. Moreover, the in-situ Raman and Micro-Raman measurements have been performed in order to compare the capabilities of the portable system specially focused for the next ESA Exo-Mars mission. The mineral detection confirms the sub-aerial alteration on the surface and the hydrothermal processes by the volcanic fluid circulations in the fresh part. Therefore, the secondary more abundant mineralization acts as the color agent of the rocks. Thus, the zeolite-illite group is the responsible for the bluish coloration, as well as the feldspars and carbonates for the whitish and the iron oxide for the redish parts. The XRD system was capable to detect a minor proportion of pyroxene, which is not visible by Raman and Mössbauer spectroscopy due to the “Azulejos” alteration of the parent material on the outcrop. On the other hand, Mössbauer spectroscopy was capable of detecting different types of iron-oxides (Fe3+/2+-oxide phases). These analyses emphasize the strength of the different techniques and the working synergy of the three different techniques together for planetary space missions.The work was supported by the MICINN with the Project AYA-2008-04529.Peer reviewe

Raman–Mo¨ssbauer–XRD studies of selected samples from ‘‘Los Azulejos” outcrop: A possible analogue for assessing the alteration processes on Mars

The outcrop of ‘‘Los Azulejos” is visible at the interior of the Can˜adas Caldera in Tenerife Island (Spain). It exhibits a great variety of alteration processes that could be considered as terrestrial analogue for several geological processes on Mars. This outcrop is particularly interesting due to the content of clays, zeolite, iron oxides, and sulfates corresponding to a hydrothermal alteration catalogued as ‘‘Azulejos” type alteration. A detailed analysis by portable and laboratory Raman systems as well as other different techniques such as X-ray diffraction (XRD) and Mo¨ssbauer spectroscopy has been carried out (using twin-instruments from Martian lander missions: Mo¨ssbauer spectrometer MIMOS-II from the NASA-MER mission of 2001 and the XRD diffractometer from the NASA-MSL Curiosity mission of 2012). The mineral identification presents the following mineral species: magnetite, goethite, hematite, anatase, rutile, quartz, gregoryite, sulfate (thenardite and hexahydrite), diopside, feldspar, analcime, kaolinite and muscovite. Moreover, the in-situ Raman and Micro- Raman measurements have been performed in order to compare the capabilities of the portable system specially focused for the next ESA Exo-Mars mission. The mineral detection confirms the sub-aerial alteration on the surface and the hydrothermal processes by the volcanic fluid circulations in the fresh part. Therefore, the secondary more abundant mineralization acts as the color agent of the rocks. Thus, the zeolite–illite group is the responsible for the bluish coloration, as well as the feldspars and carbonates for the whitish and the iron oxide for the redish parts. The XRD system was capable to detect a minor proportion of pyroxene, which is not visible by Raman and Mo¨ssbauer spectroscopy due to the ‘‘Azulejos” alteration of the parent material on the outcrop. On the other hand, Mo¨ ssbauer spectroscopy was capable of detecting different types of iron-oxides (Fe3+/2+-oxide phases). These analyses emphasize the strength of the different techniques and the working synergy of the three different techniques together for planetary space missions

ExoMars Raman Laser Spectrometer (RLS): development of chemometric tools to classify ultramafic igneous rocks on Mars

Producción CientíficaThis work aims to evaluate whether the multi-point analysis the ExoMars Raman Laser Spectrometer (RLS) will perform on powdered samples could serve to classify ultramafc rocks on Mars. To do so, the RLS ExoMars Simulator was used to study terrestrial analogues of Martian peridotites and pyroxenites by applying the operational constraints of the Raman spectrometer onboard the Rosalind Franklin rover. Besides qualitative analysis, RLS-dedicated calibration curves have been built to estimate the relative content of olivine and pyroxenes in the samples. These semi-quantitative results, combined with a rough estimate of the concentration ratio between clino- and ortho-pyroxene mineral phases, were used to classify the terrestrial analogues. XRD data were fnally employed as reference to validate Raman results. As this preliminary work suggests, ultramafc rocks on Mars could be efectively classifed through the chemometric analysis of RLS data sets. After optimization, the proposed chemometric tools could be applied to the study of the volcanic geological areas detected at the ExoMars landing site (Oxia Planum), whose mineralogical composition and geological evolution have not been fully understoodProyecto MINECO Retos de la Sociedad. Ref. ESP2017-87690-C3-1-RProyecto MINECO Retos de la Sociedad. Ref. ESP2017-87690-C3-1-