The RNA world hypothesis posits that at some stage in the development of life, RNA functioned as both an informational polymer and a catalyst for important reactions. However, many questions remain as to how RNA molecules might have evolved into living organisms. This thesis uses computer simulations to model processes thought to be important to the development of an RNA world. First, a model is discussed which describes non-enzymatic polymerization of single-stranded RNA from different kinds of activated nucleotides, a necessary first step towards an RNA world. It was found that a system undergoing polymerization of RNA from 5′-activated triphosphates or imidazolides behaves differently from an equilibrium system undergoing reversible polymerization reactions from 2′,3′-cyclic monophosphates, for example. In the 5′-triphosphate case, the system is not in equilibrium but rather in a state of circular reaction flux that must be maintained by an external source of phosphates. This model is then adapted to investigate non-enzymatic template-directed replication of RNA strands. It is found that this process fulfills all the necessary requirements to function as a metabolism which maintains a difference between the outside non-living environment and the internal environment of the cell. Finally, byproducts arising from the template copying mechanism in this model are discussed, including the development of highly regular sequence patterns in the strand population due to selection for the ability to form duplexes with neighbouring strands. Altogether, this thesis illustrates new implications, potential pitfalls, and possibilities of the RNA world hypothesis for the origin of life. In particular, it emphasizes the fundamental link between the processes of replication and metabolism, both of which must have been crucial to the functioning of the earliest protocells. This link has been largely overlooked in scientific literature on the topic to date. / Thesis / Master of Science (MSc) / For millennia, humanity has told stories about the origin of life. Since the 1960s, scientists have hypothesized that RNA is a key player in this origin story. RNA can both hold information and catalyze chemical reactions, meaning only one molecule is needed for both these crucial functions. However, many questions remain about how this would work in practice. This project used computer simulations to model steps along the path from RNA to living organisms. First, a model was developed for the formation of single-stranded RNA from building block molecules. The model was then expanded to include copying of existing RNA strands, and it was found that this process constitutes a metabolism. Finally, it was discovered that over time the copying process produces simple patterns in the sequence of building blocks that make up the RNA strands. Altogether, these findings emphasize the link between replication and metabolism in early cells.

No / The first Raman spectrometers to be used for in situ analysis of planetary material will be launched as part of powerful, rover-based analytical laboratories within the next 6 years. There are a number of significant challenges associated with building spectrometers for space applications, including limited volume, power and mass budgets, the need to operate in harsh environments and the need to operate independently and intelligently for long periods of time (due to communication limitations). Here, we give an overview of the technical capabilities of the Raman instruments planned for future planetary missions and give a review of the preparatory work being pursued to ensure that such instruments are operated successfully and optimally. This includes analysis of extremophile samples containing pigments associated with biological processes, synthetic materials which incorporate biological material within a mineral matrix, planetary analogues containing low levels of reduced carbon and samples coated with desert varnish that incorporate both geo-markers and biomarkers. We discuss the scientific importance of each sample type and the challenges using portable/flight-prototype instrumentation. We also report on technical development work undertaken to enable the next generation of Raman instruments to reach higher levels of sensitivity and operational efficiency.

Investigation of life’s limitations on Earth provides the necessary information to constrain where life outside of Earth may be proliferating or previously existed. This Master’s thesis applied phospholipid fatty acid (PLFA) analysis in combination with organic carbon and 16S rRNA gene data to assess and characterize microbial communities through both microcosms and in situ samples of bentonite clay, which is an intended barrier component for the long-term storage of high-grade nuclear waste. Microcosm experiments were set up to test the impact of water activity in as-received, uncompacted bentonite clays using a high (0.99) and low (0.93) water activity over a one month period. Under aerobic incubation water activities of 0.93 and 0.99 had no resolvable effect between water activity levels on the growth of cells of indigenous communities of microbes in as-received uncompacted bentonite. Growth was detected under both water activities by a significant increase in total PLFA abundance. The increase in PLFA over the period of the study suggested an approximate increase in cells from 4x10^6 to 2x10^7 E.coli equivalent cells/g. The distribution of the PLFA and genetics data suggests the community is composed predominantly of gram-positive aerobic heterotrophs with lesser amounts of anaerobic bacteria and eukaryotes potentially in the form of fungi. Similar cell abundances and community structures were identified in the Tsukinuno Mine bentonite DGR analogue site which is a ~12 to 16 Ma deposit approximately 200 m below the surface. Total PLFA recovered from the core subsamples ranged from 32 pmol PLFA/g to 431 pmol PLFA/g, which corresponds to a range from 7.5x10^5 to 1.2x10^7 E.coli equivalent cells/g, across all cores. The community was composed of both aerobic and anaerobic bacteria consisting of gram-positive and gram-negative bacteria, as well as possible sulfate-reducing bacteria and eukaryotes. / Thesis / Master of Science (MSc)

In this project we search for a planet in a triple-stellar system that could be habitable and a potential host to complex, human-like life. The first step in the search for potentially habitable planets involved examining catalogs of triple-stellar systems with known exoplanets and quadruple-star systems in which one of the stars could be swapped for a planet. Then, for all the potential planets, we estimated whether they lay within the habitable zone. For all systems with planets in the habitable zone, we used previously published climate model simulations of similar systems to gain a better understanding of the potential climate of these planets. Furthermore, the simulation program VPlanet was used to check the dynamical stability of systems in which one of the stars was swapped with a planet. In total, 10 planets were found to be within the habitable zone and were closer examined, with 6 of them being already existing planets and 4 of them being fabricated. Despite all of the planets lying within the habitable zone, they showed varying degrees of suitability for hosting life, with most planets being substantially cooler than Earth. None of the existing exoplanets had a suitable climate for human-like life, and none of the fabricated systems proved to be dynamically stable. However, the fabricated system that demonstrated the highest amount of stability in simulations was the one in which the planet and the stars were most similar in size. This leads us to conclude that optimal dynamical stability is achieved when the system components are of comparable size.

Esta tese se insere no contexto da química prebiótica, que estuda a evolução química que ocorreu antes do surgimento da vida na Terra. Tal área pertence ao ramo de pesquisa da Astrobiologia, que estuda o surgimento, a evolução, distribuição e futuro da vida na Terra ou em outro lugar do Universo. Dentre as várias hipóteses abordadas na química prebiótica, a hipótese mineral é foco de estudo deste trabalho, ou seja, se os minerais podem ter agido como preconcentradores ou protetores de moléculas biologicamente relevantes para a química prebiótica e como catalisadores de reações. A classe mineral de hidróxidos duplo lamelares (HDL) é estudada inicialmente considerando se sua síntese seria possível em um ambiente prebiótico. Desta forma, o HDL foi sintetizado por dois métodos de síntese (coprecipitação e reconstrução) e em quatro composições distintas de água do mar sintética, que mimetizam diferentes fases geológicas da Terra, os resultados mostraram a formação deste mineral em todas as composições de água do mar analisadas. Posteriormente, o estudo da interação de biomoléculas com HDL foi feito visando caracterizar se estas poderiam estar inseridas no espaço interlamelar deste mineral. O íon tiocianato, precursor de biomoléculas, e as bases nitrogenadas adenina, timina, e uracila mostraram-se presentes nas amostras de HDL sintetizadas pelos dois métodos, coprecipitação e reconstrução. As amostras foram caracterizadas por difratometria de raios X, análise termogravimétrica, análise elementar e por espectroscopia vibracional, Raman e no infravermelho. Embora os resultados iniciais indiquem que as biomoléculas possam estar interagindo com o mineral por adsorção e não necessariamente estejam intercaladas, estudos com lavagem das amostras com carbonato de sódio mostraram a troca iônica das biomoléculas pelo ânion inorgânico e sugerem que estas encontravam-se realmente no espaço interlamelar do mineral. Foram feitas então simulações de ambientes extremos nos sistemas HDL + biomoléculas para avaliar se a presença do mineral aumenta a estabilidade das biomoléculas frente a aquecimento, radiação UVC e radiação ionizante já que tais condições extremas estariam presentes na Terra primitiva / This thesis subject is related to prebiotic chemistry, which studies the chemical evolution that happened before the origin of life on Earth. This subject belongs to the Astrobiology research area, which studies the origin, evolution, distribution and future of life on Earth and elsewhere in the Universe. Among the many hypothesis that prebiotic chemistry encompass, the mineral hypothesis is the aim of this thesis, that is, if minerals could have had a role in preconcentrating and protecting molecules relevant to prebiotic chemistry, and also if they could have acted as catalists. The layered double hydroxide (LDH) minerals are studied and the first question is if they could have been synthetized in a prebiotic environment. Four different seawater compositions are analyzed, considering many geological periods of Earth, and two synthesis methods were studied: coprecipitation and reconstruction. The results showed that the LDHs are formed in all seawater types studied. Following these studies, we discuss whether biomolecules could be in the interlayer space of this mineral. Thiocyanate, a biomolecule precursor, and the nucleic acids adenine, thymine and uracil were present in the LDH samples synthetized either by coprecipitation and reconstruction, and they were characterized by X-Ray diffraction, thermogravimetric analysis, elemental analysis and by vibrational spectroscopy: IR and Raman. Although the preliminary results showed that the biomolecules are not necessarily intercalated, but may simply be adsorbed on the minerals, after washing with a sodium carbonate solution, the biomolecules were replaced by the inorganic anion, suggesting that the former was in fact intercalated in the mineral. Extreme conditions simulations were then performed on the LDH plus biomolecules systems to evaluate whether the mineral may act as a protector and stabilize the biomolecules when these were heated or irradiated with UV-C and ionizing radiation, since such scenarios would be common on early Earth

Entender como se originou a vida é um dos desafios propostos pela astrobiologia. Este trabalho busca compreender como argilas aniônicas do tipo hidróxidos duplos lamelares (LDH) interagem com alguns aminoácidos quando submetido a condições presentes no passado do nosso planeta. Para tanto, foi estudada a interação dos aminoácidos cisteína (cys), cistina (cyss) e ácido glutâmico (glu) com duas variações de LDHs: hidrotalcita, que consistem em um LDH de Mg e Al (LDHal), e as piroauritas, um LDH de Mg e Fe III (LDHfe). Os LDHs foram sintetizados com cada um dos três aminoácidos por coprecipitação (cop) e reconstrução (rec). Todos os compostos produzidos foram submetidos a irradiação com UV-C (254 nm), longa exposição à temperatura de 70 °C e ciclos de hidratação e dessecação a 70 °C, tentando simular condições próximas à Terra primitiva. Os resultados obtidos indicam que os aminoácidos estão presentes no espaço interlamelar dos LDHs. Sendo que os LDHfe e os LDHal_glu se mostraram mais inertes, não sofrendo variações significativas com as simulações prebióticas. Para os LDHal_cys ocorreu a formação de ligações do tipo S-S durante a síntese; a irradiação UV-C afetou de maneira distinta os LDHs cop e rec, sendo que apenas nos reconstruídos ocorreu a formação de SO4-2. A simulação de temperatura causou o rompimento das ligações S-S e a formação de ligações S-H, enquanto os ciclos de hidratação, ao que tudo indicam, acarretam a liberação da cisteína do meio interlamelar. Essas características presentes no LDHal_cys estão, em partes, também presentes para os LDHal_cyss. De maneira geral, os LDHs são eficientes na intercalação de aminoácidos e estáveis quanto à temperatura e, em alguns casos, a radiação UV-C. Desta forma os LDHs se mostram como um mineral que pode ter tido a sua importância na Terra prebiótica, sendo aptos a atuar na retenção de aminoácidos, resistência a algumas das condições presentes e com a possibilidade de liberar estas biomoléculas novamente no ambiente, tornando-as disponíveis para o aumento de complexidade química / Understanding how life originated is one of the challenges proposed by astrobiology. This work aims to understand how layered double hydroxides (LDH), a type of anionic clay, may interact with amino acids when submitted to conditions present in prebiotic Earth. It was studied the interaction between amino acids cysteine (cys), cystine (cyss) and glutamic acid (glu) with two LDHs variations: hydrotalcite, LDH of Mg and Al (LDHal), and pyroaurite, a LDH of Mg and Fe III (LDHfe). LDHs were synthesized with each of the three amino acids by coprecipitation (cop) and reconstruction (rec). All the LDHs produced were submitted to UV-C irradiation (254 nm), long exposure to the temperature of 70 °C and cycles of hydration and desiccation at 70 °C, trying to simulated the conditions presents in primordial Earth. The results indicate that amino acids are present in the interlayer region of LDHs. Since LDHfe and LDHal_glu were shown to be more inert, they did not undergo significant variations with the prebiotic simulations. For LDHal_cys the formation of S-S type bonds occurred during the synthesis; the UV-C irradiation differently affected the LDHs cop and rec, being that only in the reconstructed the formation of SO4-2 occurred. The temperature simulation induced breakage of the S-S bonds and formation of S-H bonds, whereas the hydration cycles leaded to the release of cysteine from the interlamellar space. These features present in LDHal_cys are, partially, also present for the LDHal_cyss. In general, LDHs are efficient in the intercalation of amino acids, stable in temperature and, in some cases, to UV-C radiation. In this manner, the LDHs may have been important minerals in the prebiotic Earth, being able to act in the retention of amino acids, resisting to some of the prevailing conditions and possibly releasing these biomolecules back into the environment, making them available for increasing chemical complexity

Esta tese se insere no contexto da química prebiótica, que estuda a evolução química que ocorreu antes do surgimento da vida na Terra. Tal área pertence ao ramo de pesquisa da Astrobiologia, que estuda o surgimento, a evolução, distribuição e futuro da vida na Terra ou em outro lugar do Universo. Dentre as várias hipóteses abordadas na química prebiótica, a hipótese mineral é foco de estudo deste trabalho, ou seja, se os minerais podem ter agido como preconcentradores ou protetores de moléculas biologicamente relevantes para a química prebiótica e como catalisadores de reações. A classe mineral de hidróxidos duplo lamelares (HDL) é estudada inicialmente considerando se sua síntese seria possível em um ambiente prebiótico. Desta forma, o HDL foi sintetizado por dois métodos de síntese (coprecipitação e reconstrução) e em quatro composições distintas de água do mar sintética, que mimetizam diferentes fases geológicas da Terra, os resultados mostraram a formação deste mineral em todas as composições de água do mar analisadas. Posteriormente, o estudo da interação de biomoléculas com HDL foi feito visando caracterizar se estas poderiam estar inseridas no espaço interlamelar deste mineral. O íon tiocianato, precursor de biomoléculas, e as bases nitrogenadas adenina, timina, e uracila mostraram-se presentes nas amostras de HDL sintetizadas pelos dois métodos, coprecipitação e reconstrução. As amostras foram caracterizadas por difratometria de raios X, análise termogravimétrica, análise elementar e por espectroscopia vibracional, Raman e no infravermelho. Embora os resultados iniciais indiquem que as biomoléculas possam estar interagindo com o mineral por adsorção e não necessariamente estejam intercaladas, estudos com lavagem das amostras com carbonato de sódio mostraram a troca iônica das biomoléculas pelo ânion inorgânico e sugerem que estas encontravam-se realmente no espaço interlamelar do mineral. Foram feitas então simulações de ambientes extremos nos sistemas HDL + biomoléculas para avaliar se a presença do mineral aumenta a estabilidade das biomoléculas frente a aquecimento, radiação UVC e radiação ionizante já que tais condições extremas estariam presentes na Terra primitiva / This thesis subject is related to prebiotic chemistry, which studies the chemical evolution that happened before the origin of life on Earth. This subject belongs to the Astrobiology research area, which studies the origin, evolution, distribution and future of life on Earth and elsewhere in the Universe. Among the many hypothesis that prebiotic chemistry encompass, the mineral hypothesis is the aim of this thesis, that is, if minerals could have had a role in preconcentrating and protecting molecules relevant to prebiotic chemistry, and also if they could have acted as catalists. The layered double hydroxide (LDH) minerals are studied and the first question is if they could have been synthetized in a prebiotic environment. Four different seawater compositions are analyzed, considering many geological periods of Earth, and two synthesis methods were studied: coprecipitation and reconstruction. The results showed that the LDHs are formed in all seawater types studied. Following these studies, we discuss whether biomolecules could be in the interlayer space of this mineral. Thiocyanate, a biomolecule precursor, and the nucleic acids adenine, thymine and uracil were present in the LDH samples synthetized either by coprecipitation and reconstruction, and they were characterized by X-Ray diffraction, thermogravimetric analysis, elemental analysis and by vibrational spectroscopy: IR and Raman. Although the preliminary results showed that the biomolecules are not necessarily intercalated, but may simply be adsorbed on the minerals, after washing with a sodium carbonate solution, the biomolecules were replaced by the inorganic anion, suggesting that the former was in fact intercalated in the mineral. Extreme conditions simulations were then performed on the LDH plus biomolecules systems to evaluate whether the mineral may act as a protector and stabilize the biomolecules when these were heated or irradiated with UV-C and ionizing radiation, since such scenarios would be common on early Earth

Entender como se originou a vida é um dos desafios propostos pela astrobiologia. Este trabalho busca compreender como argilas aniônicas do tipo hidróxidos duplos lamelares (LDH) interagem com alguns aminoácidos quando submetido a condições presentes no passado do nosso planeta. Para tanto, foi estudada a interação dos aminoácidos cisteína (cys), cistina (cyss) e ácido glutâmico (glu) com duas variações de LDHs: hidrotalcita, que consistem em um LDH de Mg e Al (LDHal), e as piroauritas, um LDH de Mg e Fe III (LDHfe). Os LDHs foram sintetizados com cada um dos três aminoácidos por coprecipitação (cop) e reconstrução (rec). Todos os compostos produzidos foram submetidos a irradiação com UV-C (254 nm), longa exposição à temperatura de 70 °C e ciclos de hidratação e dessecação a 70 °C, tentando simular condições próximas à Terra primitiva. Os resultados obtidos indicam que os aminoácidos estão presentes no espaço interlamelar dos LDHs. Sendo que os LDHfe e os LDHal_glu se mostraram mais inertes, não sofrendo variações significativas com as simulações prebióticas. Para os LDHal_cys ocorreu a formação de ligações do tipo S-S durante a síntese; a irradiação UV-C afetou de maneira distinta os LDHs cop e rec, sendo que apenas nos reconstruídos ocorreu a formação de SO4-2. A simulação de temperatura causou o rompimento das ligações S-S e a formação de ligações S-H, enquanto os ciclos de hidratação, ao que tudo indicam, acarretam a liberação da cisteína do meio interlamelar. Essas características presentes no LDHal_cys estão, em partes, também presentes para os LDHal_cyss. De maneira geral, os LDHs são eficientes na intercalação de aminoácidos e estáveis quanto à temperatura e, em alguns casos, a radiação UV-C. Desta forma os LDHs se mostram como um mineral que pode ter tido a sua importância na Terra prebiótica, sendo aptos a atuar na retenção de aminoácidos, resistência a algumas das condições presentes e com a possibilidade de liberar estas biomoléculas novamente no ambiente, tornando-as disponíveis para o aumento de complexidade química / Understanding how life originated is one of the challenges proposed by astrobiology. This work aims to understand how layered double hydroxides (LDH), a type of anionic clay, may interact with amino acids when submitted to conditions present in prebiotic Earth. It was studied the interaction between amino acids cysteine (cys), cystine (cyss) and glutamic acid (glu) with two LDHs variations: hydrotalcite, LDH of Mg and Al (LDHal), and pyroaurite, a LDH of Mg and Fe III (LDHfe). LDHs were synthesized with each of the three amino acids by coprecipitation (cop) and reconstruction (rec). All the LDHs produced were submitted to UV-C irradiation (254 nm), long exposure to the temperature of 70 °C and cycles of hydration and desiccation at 70 °C, trying to simulated the conditions presents in primordial Earth. The results indicate that amino acids are present in the interlayer region of LDHs. Since LDHfe and LDHal_glu were shown to be more inert, they did not undergo significant variations with the prebiotic simulations. For LDHal_cys the formation of S-S type bonds occurred during the synthesis; the UV-C irradiation differently affected the LDHs cop and rec, being that only in the reconstructed the formation of SO4-2 occurred. The temperature simulation induced breakage of the S-S bonds and formation of S-H bonds, whereas the hydration cycles leaded to the release of cysteine from the interlamellar space. These features present in LDHal_cys are, partially, also present for the LDHal_cyss. In general, LDHs are efficient in the intercalation of amino acids, stable in temperature and, in some cases, to UV-C radiation. In this manner, the LDHs may have been important minerals in the prebiotic Earth, being able to act in the retention of amino acids, resisting to some of the prevailing conditions and possibly releasing these biomolecules back into the environment, making them available for increasing chemical complexity

La sonde spatiale européenne Rosetta, après un voyage de dix années, a rejoint le 6 août 2014 son objet d’étude, la comète 67P/Churyumov-Gerasimenko (67P/C-G). Afin de l’étudier de manière intensive durant deux ans, un total de 21 instruments était embarqué sur l’orbiteur Rosetta et l’atterrisseur Philae. Le spectromètre de masse d’ions secondaires à temps de vol, COSIMA (COmetary Secondary Ions Mass Analyzer), était l’un des instruments de l’orbiteur et a été conçu pour analyser in situ la composition chimique des particules solides éjectées de la comète 67P/C-G. L’objectif de cette thèse est de caractériser la composante organique réfractaire contenue dans les poussières cométaires, à l’aide de l’instrument COSIMA. Dans le cadre de ces travaux, j’ai mis au point au point et appliqué une méthodologie pour analyser les spectres de masse cométaires, plus particulièrement dans le mode positif de l’instrument. A l’aide de cette méthodologie, cinq ions organiques d’origine cométaire ont été détectés et identifiés : C+ (m/z = 12,00), CH+ (m/z = 13,01), CH2+ (m/z = 14,02), CH3+ (m/z = 15,02) et C2H3+ (m/z = 27,02). La caractérisation de cette composante organique a été effectuée à l’aide de spectres de masse de calibration. Les composés de référence utilisés dans ces travaux de thèse incluent des molécules organiques pures et des analogues de la matière organique cométaire, tels que des échantillons naturels (des météorites carbonées, une micrométéorite ultracarbonée, de la matière organique insoluble extraite de météorites carbonées) et un échantillon synthétisé en laboratoire. La matière organique insoluble extraite des chondrites carbonées est, à ce jour, le meilleur analogue à la matière organique réfractaire contenue dans les particules de 67P/C-G. Ainsi, la matière organique cométaire serait de haut poids moléculaire et le carbone lié dans de grandes structures macromoléculaires. Le carbone est également l’un des éléments le plus abondant dans les particules avec un rapport C⁄Si = 5,5 (+1,4/-1,2). La comète 67P/C-G figure ainsi parmi les corps les plus riches en carbone du système solaire. Enfin, un composé spécifique a été recherché, le polyoxyméthylène. Cependant, les indicateurs développés et appliqués aux données cométaires ne permettent pas de conclure quant à sa présence dans les particules analysées par COSIMA / After a ten-year journey, the European spacecraft Rosetta arrived at comet 67P/Churyumov-Gersasimenko (67P/C-G) on August 6, 2014. In order to conduct intensive research for two years, a total of 21 instruments were on board the Rosetta orbiter and the Philae lander. The time-of-flight secondary ions mass spectrometer, COSIMA (COmetary Secondary Ions Mass Analyzer), was one of the orbiter instruments and was designed for in situ analysis of the chemical composition of cometary particles ejected from the comet 67P/C-G. This thesis aims to characterize the refractory organic component of the cometary dust, with the COSIMA instrument. As part of this work, I have developed and applied a methodology to analyze the cometary mass spectra, more specifically in the positive mode of the instrument. Using this methodology, five organic ions of cometary origin were detected and identified: C+ (m/z = 12.00), CH+ (m/z = 13.01), CH2+ (m/z = 14.02), CH3+ (m/z = 15.02) and C2H3+ (m/z = 27.02). The characterization of this organic component has been carried out with calibration mass spectra. The reference compounds used during this thesis include pure organic molecules and cometary organic matter analogs, such as natural samples (carbonaceous chondrites, ultracarbonaceous micrometeorite, insoluble organic matter extracted from carbonaceous chondrites) and one sample synthetized in the laboratory. The best analogue found so far to the refractory component of 67P/C-G particles is the insoluble organic matter extracted from carbonaceous chondrites. The cometary organic matter would be of high-molecular-weight and the carbon bounded in very large macromolecular compounds. Carbon is also one of the most abundant element in the dust particles with an elemental ratio of C⁄Si = 5.5 (+1.4/-1.2). Comet 67P/C-G is among the most carbon-rich bodies of the solar system. Finally, a specific compound was sought, the polyoxymethylene. However, indicators developed and applied to the cometary data do not allow to conclude on the presence of polyoxymethylene in the particles analyzed by COSIMA

abstract: The search for life on Mars is a major NASA priority. A Mars Sample Return (MSR) mission, Mars 2020, will be NASA's next step towards this goal, carrying an instrument suite that can identify samples containing potential biosignatures. Those samples will be later returned to Earth for detailed analysis. This dissertation is intended to inform strategies for fossil biosignature detection in Mars analog samples targeted for their high biosignature preservation potential (BPP) using in situ rover-based instruments. In chapter 2, I assessed the diagenesis and BPP of one relevant analog habitable Martian environment: a playa evaporite sequence within the Verde Formation, Arizona. Coupling outcrop-scale observations with laboratory analyses, results revealed four diagenetic pathways, each with distinct impacts on BPP. When MSR occurs, the sample mass returned will be restricted, highlighting the importance of developing instruments that can select the most promising samples for MSR. Raman spectroscopy is one favored technique for this purpose. Three Raman instruments will be sent onboard two upcoming Mars rover missions for the first time. In chapters 3-4, I investigated the challenges of Raman to identify samples for MSR. I examined two Raman systems, each optimized in a different way to mitigate a major problem commonly suffered by Raman instruments: background fluorescence. In Chapter 3, I focused on visible laser excitation wavelength (532 nm) gated (or time-resolved Raman, TRR) spectroscopy. Results showed occasional improvement over conventional Raman for mitigating fluorescence in samples. It was hypothesized that results were wavelength-dependent and that greater fluorescence reduction was possible with UV laser excitation. In Chapter 4, I tested this hypothesis with a time-resolved UV (266 nm) gated Raman and UV fluorescence spectroscopy capability. I acquired Raman and fluorescence data sets on samples and showed that the UV system enabled identifications of minerals and biosignatures in samples with high confidence. The results obtained in this dissertation may inform approaches for MSR by: (1) refining models for biosignature preservation in habitable Mars environments; (2) improving sample selection and caching strategies, which may increase the success of Earth-based biogenicity studies; and (3) informing the development of Raman instruments for upcoming rover-based missions. / Dissertation/Thesis / Doctoral Dissertation Geological Sciences 2016