(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.
Chemical composition affects virtually all aspects of astrobiology, from stellar astrophysics to molecular biology. We present a synopsis of the research results presented at the “Stellar Stoichiometry” Workshop Without Walls hosted at Arizona State University April 11–12, 2013, under the auspices of the NASA Astrobiology Institute. The results focus on the measurement of chemical abundances and the effects of composition on processes from stellar to planetary scales. Of particular interest were the scientific connections between processes in these normally disparate fields. Measuring the abundances of elements in stars and giant and terrestrial planets poses substantial difficulties in technique and interpretation. One of the motivations for this conference was the fact that determinations of the abundance of a given element in a single star by different groups can differ by more than their quoted errors.
The problems affecting the reliability of abundance estimations and their inherent limitations are discussed. When these problems are taken into consideration, self-consistent surveys of stellar abundances show that there is still substantial variation (factors of ∼2) in the ratios of common elements (e.g., C, O, Na, Al, Mg, Si, Ca) important in rock-forming minerals, atmospheres, and biology. We consider how abundance variations arise through injection of supernova nucleosynthesis products into star-forming material and through photoevaporation of protoplanetary disks. The effects of composition on stellar evolution are substantial, and coupled with planetary atmosphere models can result in predicted habitable zone extents that vary by many tens of percent. Variations in the bulk composition of planets can affect rates of radiogenic heating and substantially change the mineralogy of planetary interiors, affecting properties such as convection and energy transport.