In 2018 ESA and NASA plan to send the ExoMars rover to the Martian surface. This rover is planned to have a suite of analytical equipment that includes a Raman spectrometer. In this context, an evaluation of Raman spectroscopy as an analytical tool for interplanetary studies is investigated. The preparation techniques for appropriate inorganic and organic mixtures are interrogated. Methods are investigated to optimize the homogeneity of over 50 samples involving mineral phases; calcite, gypsum and goethite and selected organic biomolecular systems; anthracene, naphthalene and beta-carotene. From mixtures produced of these organic and inorganic materials differences between homogeneity of the samples is observed. Different mixing techniques are investigated to reduce this, however all the samples display variation on a micron scale. To resolve this issue a grid system of 9 points is implemented on solid samples and solutions are used to produce standards. The standards are devised using a range of instrument validation parameters for comparison between commercially available spectrometers and the prototype instrument. From these standards a prototype instrument is optimized for data acquisition and an evaluation procedure for instrument performance is established. The prototype Raman spectrometer is evaluated to match the specifications of the spectrometer on board ExoMars rover. A range of astrobiological relevant samples are interrogated; geological samples, biomarkers, cellular systems and bio-geological inclusions. From these samples detection of organics is observed to be only possible, with Raman spectroscopy where organics are localised in high concentrations, upon grinding and mixing geological inclusions Raman spectroscopy is unable to detect the organic components. / Appendices 3 and 4 are full text of the articles which are referenced in the text, but the published copy is not allowed to be displayed under copyright restrictions and are not included with this online thesis.

Modern microbialites provide the opportunity to explore the influences of biology on microbialite formation and understand how biosignatures can be preserved in these structures. In this study, we compared δ13Ccarb values from nodule and surface biofilm carbonates on microbialite structures across depths and locations throughout Pavilion Lake to evaluate whether variable light exposure produced limitations to biosignature formation. At depths below 21 m, vertical profiling of δ13Ccarb across colour transitions of surface biofilm on microbialite structures was performed to identify spatial arrangement of autotrophic and heterotrophic biosignatures. Finally, preservation of the photosynthetic biosignature over time was investigated by collecting carbonates beneath the microbialite surface. These investigations were performed in order to better characterize the factors controlling biosignature formation, distribution, and preservation within Pavilion Lake.Decreasing trends of δ13Ccarb with depth across study sites indicated that attenuated sunlight in the water column is likely the primary control on biosignature formation. Below 21 m, photosynthetic enrichments representing biosignatures on microbialite surfaces were reduced and recorded δ13Ccarb values that fell within the predicted equilibrium range. Biosignature loss is suggested to result from the relative proportions of autotrophic and heterotrophic processes changing at depths and producing average δ13Ccarb values. Variability of where biosignatures are lost on the microbialite surface indicated that the spatial extent of photosynthetic communities producing enrichments is potentially influenced by variable incidences of light at these depths. Although no definitive biosignatures of heterotrophy were identified, several interfaces were identified where the balancing proportions of autotrophic and heterotrophic processes influenced by light variability potentially mediate biosignature loss. Decreasing trends of δ13Ccarb beneath the microbialite surface and estimates of past microbialite growth rates indicated that surface biosignatures are lost within 100 – 400 years. It is suggested that infilling processes overprint enrichments and deplete δ13Ccarb values due to heterotrophic abundance below the microbialite surface. This is supported by an isotopic mass balance that predicts smaller inputs of heterotrophically-depleted DIC are required to sufficiently overprint δ13Ccarb enrichments. These results concluded that the photosynthetic biosignature identified in Pavilion Lake is short-lived and mitigated by biological processes. / Thesis / Master of Science (MSc)

Analyzing the constituents of meteorites has played an important role in forming the contemporary theories of solar system evolution, planets formation, and stellar evolution. Meteorites are often a complex mixture of common rock forming silicates, such as olivines and pyroxenes, with a range of exotic species including hydrated silicates, and in some cases organic compounds. We used Micro-Raman spectroscopy to analyze the compositions of three carbonaceous chondrites: NWA852, Murchison and Allende. Raman spectra were measured using laser sources with different excitation wavelengths: HeNe 633 nm and Nd:YAG 532 nm. We were able to detect 9 minerals in NWA852, 3 minerals in Murchison and 4 minerals in Allende. Some of these minerals like pyrite in NWA852 and magnetite in NWA852 and Murchison provide evidence for potential previous organic life. Other minerals like ringwoodite in Allende and lizardite in NWA852 reveal information about previous astrophysical and geological events experienced by the meteorites. The detection of graphite in the Murchison and Allende reveals information about the microstructure of these meteorites.

This thesis investigates how increased global mean temperatures on Earth, induced by the increase in the luminosity of the Sun as it ages, change the types of habitable environments on the planet at local scales over the next 3 Gyr. Rising temperatures enhance silicate weathering rates, reducing atmospheric CO₂ levels to below the threshold for photosynthesis, while simultaneously pushing environments past the temperature tolerances of plant and animal species. This leads to the end of all plant life and animal life (due to reduced food, O₂ and H₂O availability, as well as higher temperatures) within the next 1 Gyr. The reduction in the extent of the remaining microbial biosphere due to increasing temperatures and rapid ocean evaporation is then modelled, incorporating orbital parameter changes until all known types of life become extinct; a maximum of 2.8 Gyr from the present. The biosignatures associated with these changes are determined and the analysis extended to Earth-like extrasolar planets nearing the end of their habitable lifetimes. In particular, the stages in the main sequence evolutions of Sun-like stars within 10 pc are evaluated and used to extrapolate the stage that an Earth-analogue planet would be at in its habitable evolution, to determine the best candidate systems for a far-future Earth-analogue biosphere, highlighting the Beta Canum Venaticorum system as a good target. One of the most promising biosignatures for a microbial biosphere on the far-future Earth (and similar planets) may be CH₄, which could reach levels in the atmosphere that make it more readily detectable than it is for a present-day Earth-like atmosphere. Determining these biosignatures will help expand the search for life to the wider range of environments that will be found as the habitable exoplanet inventory grows and planets are found at different stages in their habitable evolution.

Raman spectroscopy has been used to characterise both organic and geological samples in order to build a database for the future characterization of biomarker molecules that are of astrobiological relevance. Characteristic geological features and hydrated minerals recently found on the surface of Mars by the NASA planetary rovers Spirit and Opportunity suggest that a possible biosphere could have once existed there. Analytical instrumentation protocols for the unequivocal detection of biomarkers in suitable geological matrices are critical for future unmanned explorations, including the forthcoming ESA ExoMars mission scheduled for 2018. Several geological features found on the surface of Mars by planetary rovers suggest that a possible extinct biosphere could exist based on similar sources of energy as occurred on Earth. For this reason, analytical instrumental protocols for the detection of isolated biomarkers preserved in suitable geological matrices unequivocally and non-destructively have to be evaluated for future unmanned missions. Raman spectroscopy is currently part of the Pasteur instrumentation suite of the ExoMars mission for the remote detection of extant or extinct life signatures in the Martian surface and subsurface. Terrestrial analogues of Martian sites have been identified and the biogeological modifications resulting from extremophilic survival activity have been studied. Here we present the Raman spectral characterization of several examples of organic compounds which have been recorded using 785 nm, 633 nm and 514 nm laser excitation -polycyclic aromatic hydrocarbons (PAHs), organic acids, chlorophyll and carotenoids. Experimental mixtures of ß-carotene in usnic acid, PAHs in usnic acid and PAHs in mineral matrices have also been investigated. Organic compounds and PAHs located under crystalline minerals samples were identified using a 5x objective lens and 785 nm III excitation. The pure compounds and compound mixtures were also analysed using X-ray powder diffraction and scanning electron microscopy (SEM). The results of this study indicate that near infrared laser at 785 nm provided the clearest and the most informative spectra due to the reduction of fluorescence emission. Higher energy lasers operating in the visible region have resulted in the emission of significant background fluorescence. Few samples fluoresce even with the use of 785 nm excitation and FT-Raman spectroscopy remains the instrument of choice for the analysis of these samples.

The Life Marker Chip instrument, which has been selected to fly as part of the 2018 ExoMars rover mission payload, aims to detect up to 25 organic molecules in martian rocks and regolith, as markers of extant life, extinct life, meteoritic in-fall and spacecraft contamination. Martian samples will be extracted with a solvent and the resulting liquid extracts will be analysed using multiplexed microarray-format immunoassays. The LMC is under development by an international consortium led by the University of Leicester and the work described within this thesis was carried out at Cranfield University as part of the consortium’s broader program of work preparing the LMC instrument for flight in 2018. Within this thesis four specific areas of LMC instrument development are addressed: the investigation of immunoassay compatible liquid extraction solvents, the study of likely interactions of martian sample matrix with immunoassays, the development of antibodies for the detection of markers of extinct life and demonstration of solvent extraction and immunoassay detection in a flight representative format. Cont/d.

The aim of the research documented in this thesis was to explore issues associated with the development of instrumentation for life detection and characterisation in a planetary exploration context. Within this aim, the following objectives had to be achieved: 1. To consider current and near-future single molecule detection (ultra-low lower limit of detection) analytical techniques that would be compatible with development into a Space qualifiable in situ analytical instrument for the detection of biomarkers in a planetary exploration context. 2. To practically consider the consequences of Planetary Protection and Contamination Control on the development of a sample return instrumentation in a planetary exploration context. 3. To consider the implications of flying an in situ instrument on-board a stratospheric balloon platform in order to apply them into a specific planetary exploration mission: In order to achieve the objectives described above, the following work was pursued:  A desk-based European Space Agency (ESA) study was carried out which entailed producing a literature review on single molecule detection technologies that had to be validated by the expert community. This was done by organising an International Workshop on Single Molecule Detection Technologies for Space Applications in March 2009 at Cranfield University, UK. The approved technologies then had to be analysed with standard analytical techniques (i.e., tradeoffs) in order to propose a specific technology for development and present its breadboard implementation and test plans at the end of the study.  A sample return experiment implementing PP&CC constraints and protocols was designed, built, tested and flown on-board the ESA, Swedish Space Corporation (SSC), Swedish National Space Board (SNSB) and German Space Agency (DLR) BEXUS stratospheric balloon platform. The biological and engineering results obtained from the sample return flight were then analysed and lessons learnt obtained for future flights.  Another desk-based study was performed to research future stratospheric balloon platforms for the exploration of Venus’ cloud layer. The in situ instrument previously proposed for the detection of biomarkers for planetary exploration missions was then put forward as a possible payload for a Venusian stratospheric balloon platform and approved by experts during the Venus Exploration Analysis Group (VEXAG) conference held in August 2011 in Washington D.C, USA. The first part of the research involved studying ultra-low lower limit of detection technologies as these have the potential to impact significantly on the technological and scientific requirements of future Space missions. Two systems were proposed: one based on Tandem Mass Spectrometry (with Cylindrical Ion Trap analysers) followed by Surface Enhanced Raman Scattering spectroscopy to create an MS/MS-SERS instrument for the detection of astrobiology biomarkers in Martian regolith, Europan ice and samples from Titan’s hydrocarbon lakes; and a second one as a Stand-Alone SERS system for the detection of biomarkers in Enceladean plumes, Venusian clouds and cometary coma. The second part of the research practically explored the design of instrumentation for stratospheric balloon platforms. CASS•E, the Cranfield Astrobiological Stratospheric Sampling Experiment, was a life detection experiment that aimed to be capable of detecting stratospheric microorganisms. The experiment consisted of a pump which drew air from the Stratosphere through a 0.2 μm collection filter which retained any microorganisms and >0.2 μm particulates present in the pumped air. Due to the expected rarity of microbes in the Stratosphere compared to the known levels of contamination at ground level, Planetary Protection and Contamination Control (PP&CC)constraints were introduced. Therefore PP&CC protocols were followed to implement Space qualified cleaning and sterilisation techniques; biobarrier technology was implemented to prevent re-contamination of the instrument after sterilisation; and cleanliness and contamination was monitored throughout assembly, integration and testing. The third part of the research demonstrated how an instrument from the first part of the study could be proposed as a payload on-board a stratospheric balloon platform with a focused mission context, i.e., a life detection mission for Venus. Therefore, the research concluded with the proposal of a payload for a Venus mission based on SERS technology on-board a stratospheric balloon platform to search for life above or in the mid Venusian cloud cover.

The recent detections of two transit events attributed to the super-Earth candidate K2-18b have provided the unprecedented prospect of spectroscopically studying a habitable-zone planet outside the solar system. Orbiting a nearby M2.5 dwarf and receiving virtually the same stellar insolation as Earth, K2-18b would be a prime candidate for the first detailed atmospheric characterization of a habitable-zone exoplanet using the Hubble Space Telescope (HST) and James Webb Space Telescope (JWST). Here, we report the detection of a third transit of K2-18b near the predicted transit time using the Spitzer Space Telescope. The Spitzer detection demonstrates the periodic nature of the two transit events discovered by K2, confirming that K2-18 is indeed orbited by a super-Earth in a 33 day orbit, ruling out the alternative scenario of two similarly sized, long-period planets transiting only once within the 75 day Kepler Space Telescope (K2) observation. We also find, however, that the transit event detected by Spitzer occurred 1.85 hr (7 sigma) before the predicted transit time. Our joint analysis of the Spitzer and K2 photometry reveals that this early occurrence of the transit is not caused by transit timing variations, but the result of an inaccurate ephemeris due to a previously undetected data anomaly in the K2 photometry. We refit the ephemeris and find that K2-18b would have been lost for future atmospheric characterizations with HST and JWST if we had not secured its ephemeris shortly after the discovery. We caution that immediate follow-up observations as presented here will also be critical for confirming and securing future planets discovered by the Transiting Exoplanet Survey Satellite (TESS), in particular if only two transit events are covered by the relatively short 27-day TESS campaigns.

This dissertation is focused on the design of the Open Data Repository's Data Publisher (ODR), a web-based central repository for scientific data, primarily focused on mineralogical properties, but also applicable to other data types, including for instance, morphological, textural and contextual images, chemical, biochemical, isotopic, and sequencing information. Using simple web-based tools, the goal of ODR is to lower the cost and training barrier so that any researcher can easily publish their data, ensure that it is archived for posterity, and comply with the mandates for data sharing. There are only a few databases in the mineralogical community, including RRUFF (http://rruff.info) for professionals, and mindat.org (http://www.mindat.org) for amateurs. These databases contain certain specific mineral information, but none, however, provide the ability to include, in the same platform, any of the many datatypes that characterize the properties of minerals. The ODR framework provides the flexibility required to include unforeseen data without the need for additional software programming. Once ODR is completed, the RRUFF database will be migrated into ODR and populated with additional data using other analytical techniques, such as Mössbauer data from Dr. Richard Morris and NVIR data from Dr. Ralf Milliken. The current ODR pilot studies are also described here, including 1) a database of the XRD analysis performed by the CheMin instrument on the Mars Science Laboratory rover Curiosity, 2) the NASA-AMES Astrobiology Habitable Environments Database (AHED), which aims to provide a central, high quality, long-term data repository for relevant astrobiology information, 3) the University of Arizona Mineral Museum (UAMM), with over 21,000 records of minerals and fossils from the museum collection, and 4) the Mineral Evolution Database (MED), that uses the ages of mineral species and their localities to correlate the diversification of mineral species through time with Earth's physical, chemical and biological processes. A good database design requires understanding the fundamentals of its content, so part of this thesis is also focused on developing my skills in mineral analysis and characterization, through the study of the crystal-chemistry of diverse minerals using X-ray diffraction, Raman spectroscopy and microprobe analysis, as principal techniques.

In 2018 ESA and NASA plan to send the ExoMars rover to the Martian surface. This rover is planned to have a suite of analytical equipment that includes a Raman spectrometer. In this context, an evaluation of Raman spectroscopy as an analytical tool for interplanetary studies is investigated. The preparation techniques for appropriate inorganic and organic mixtures are interrogated. Methods are investigated to optimize the homogeneity of over 50 samples involving mineral phases; calcite, gypsum and goethite and selected organic biomolecular systems; anthracene, naphthalene and beta-carotene. From mixtures produced of these organic and inorganic materials differences between homogeneity of the samples is observed. Different mixing techniques are investigated to reduce this, however all the samples display variation on a micron scale. To resolve this issue a grid system of 9 points is implemented on solid samples and solutions are used to produce standards. The standards are devised using a range of instrument validation parameters for comparison between commercially available spectrometers and the prototype instrument. From these standards a prototype instrument is optimized for data acquisition and an evaluation procedure for instrument performance is established. The prototype Raman spectrometer is evaluated to match the specifications of the spectrometer on board ExoMars rover. A range of astrobiological relevant samples are interrogated; geological samples, biomarkers, cellular systems and bio-geological inclusions. From these samples detection of organics is observed to be only possible, with Raman spectroscopy where organics are localised in high concentrations, upon grinding and mixing geological inclusions Raman spectroscopy is unable to detect the organic components.