The search for organic biosignatures on Mars will depend on finding material protected from the destructive ambient radiation. Solar ultraviolet can induce photochemical degradation of organic compounds, but certain clays have been shown to preserve organic material. We examine how the SHERLOC instrument on the upcoming Mars 2020 mission will use deep-ultraviolet (UV) (248.6nm) Raman and fluorescence spectroscopy to detect a plausible biosignature of adenosine 5'-monophosphate (AMP) adsorbed onto Ca-montmorillonite clay. We found that the spectral signature of AMP is not altered by adsorption in the clay matrix but does change with prolonged exposure to the UV laser over dosages equivalent to 0.2-6 sols of ambient martian UV. For pure AMP, UV exposure leads to breaking of the aromatic adenine unit, but in the presence of clay the degradation is limited to minor alteration with new Raman peaks and increased fluorescence consistent with formation of 2-hydroxyadenosine, while 1wt % Mg perchlorate increases the rate of degradation. Our results confirm that clays are effective preservers of organic material and should be considered high-value targets, but that pristine biosignatures may be altered within 1 sol of martian UV exposure, with implications for Mars 2020 science operations and sample caching.

The search for organic biosignatures on Mars will depend on finding material protected from the destructive ambient radiation. Solar ultraviolet can induce photochemical degradation of organic compounds, but certain clays have been shown to preserve organic material. We examine how the SHERLOC instrument on the upcoming Mars 2020 mission will use deep-ultraviolet (UV) (248.6 nm) Raman and fluorescence spectroscopy to detect a plausible biosignature of adenosine 5 '-monophosphate (AMP) adsorbed onto Ca-montmorillonite clay. We found that the spectral signature of AMP is not altered by adsorption in the clay matrix but does change with prolonged exposure to the UV laser over dosages equivalent to 0.2-6 sols of ambient martian UV. For pure AMP, UV exposure leads to breaking of the aromatic adenine unit, but in the presence of clay the degradation is limited to minor alteration with new Raman peaks and increased fluorescence consistent with formation of 2-hydroxyadenosine, while 1 wt % Mg perchlorate increases the rate of degradation. Our results confirm that clays are effective preservers of organic material and should be considered high-value targets, but that pristine biosignatures may be altered within 1 sol of martian UV exposure, with implications for Mars 2020 science operations and sample caching.

Although the habitability of early Mars is now well established, its suitability for conditions favorable to an independent origin of life (OoL) has been less certain. With continued exploration, evidence has mounted for a widespread diversity of physical and chemical conditions on Mars that mimic those variously hypothesized as settings in which life first arose on Earth. Mars has also provided water, energy sources, CHNOPS elements, critical catalytic transition metal elements, as well as B, Mg, Ca, Na and K, all of which are elements associated with life as we know it. With its highly favorable sulfur abundance and land/ocean ratio, early wet Mars remains a prime candidate for its own OoL, in many respects superior to Earth. The relatively well-preserved ancient surface of planet Mars helps inform the range of possible analogous conditions during the now-obliterated history of early Earth. Continued exploration of Mars also contributes to the understanding of the opportunities for settings enabling an OoL on exoplanets. Favoring geochemical sediment samples for eventual return to Earth will enhance assessments of the likelihood of a Martian OoL.

Nanoscale graphene morphologies are reported in the Allende and QUE 94366 CV3-type carbonaceous chondrites via Confocal Raman Imaging Spectroscopy. These morphologies are found embedded in the refractory calcium-aluminum-rich inclusion (CAI) rims in Allende and within a chondrule inclusion in QUE 94366. Earlier investigation already revealed graphite whiskers (GWs) presence in both these meteorites. Further inspection of the meteoritic sections, coupled with advancements in the knowledge of carbon materials, reveal a re-interpretation of Raman features of a subset of the reported GWs and newer analyzed features as graphene. This meteoritic graphene perhaps originated from the same protosolar carbon reservoir that synthesized the GWs. The graphene was most likely synthesized concurrent to the inclusions and CAIs, in a high-temperature zone near the proto-Sun and during the solar system's earliest eon. However, in the case of Allende we cannot totally rule out synthesis during later aqueous alteration of the original mineral CAI assemblage.

Combined UV Raman and laser-induced fluorescence (LIF) spectroscopy instruments will soon be launched onboard missions to planetary surfaces, including Mars, to search for biosignatures. However, the rare earth element Ce3+, found in many common and Mars-relevant minerals, can produce fluorescence features within the spectral window usually attributed to organic compounds in a LIF spectrum. This study explored the detection of Ce3+ as a biosignature mimicker using UV Raman-LIF mission instruments. We assessed how LIF spectra of a suite of synthetic CePO4 samples compare with those of organics, how varying concentrations of both Ce3+ and organics in Martian regolith simulant affect this comparison, and whether two additional data sets obtainable by combined UV Raman-LIF instruments, including time-resolved fluorescence decay lifetimes and Raman spectra, can distinguish Ce3+-containing samples from organics. Results showed that the dominant LIF features of Ce3+ (320 and 338 nm) are similar to those of the aromatic amino acid tryptophan (325 and 340 nm), even when Ce3+ samples were mixed in a Martian regolith simulant at a range of concentrations. Lifetimes were revealed to be 2-9 ns in Ce3+-containing samples, typical for organic fluomphores. These results support the erroneous interpretation that LIF spectra and lifetime values obtained on these samples constitute potential organic signatures. Raman spectroscopy results suggested that with UV laser excitation, Raman is unlikely to identify Ce-bearing samples due to strong absorption of Raman scattered energy by Ce3+. We conclude that biosignature searches using UV LIF and Raman spectroscopy instrumentation may encounter challenges with unambiguously distinguishing spectra of organic compounds from Ce-bearing compounds.

Carbonate rocks record the oldest forms of life on Earth, and their geologic reconstruction requires multiple methods to determine physical and chemical processes before conclusions of ancient biosignatures are made. Since crystal orientation within rock fabric may be used to infer geologic settings, we present here a complementary Raman method to study the orientation of calcite (CaCO3) and dolomite [CaMg (CO3)(2)] minerals. The relative peak intensity ratio of the carbonate lattice E-g modes T and L reveals the crystallographic orientation of calcite and dolomite with respect to the incident light polarization. Our results for calcite show that when the incident laser light propagates down the crystallographic a/b axis: (1) the L mode is always greater in intensity than the T mode (I-T < I-L), and (2) the spectra are most intense at 45 degrees and least intense at 90 degrees polarization angles measured from around the c axis. Our results for dolomite show that (1) I-T > I-L when the incident light propagation is down the crystallographic c axis and (2) I-T < I-L when the incident light propagation is down the crystallographic a/b axis. This study reveals mineral orientation variation related to deposition and paragenesis within limestone and dolostone samples. The method presented yields information related to growth and deformation during diagenetic and metamorphic alteration and may be used in research seeking to identify the fabric parameters of any calcite or dolomite containing rock. The compositional and structural data obtained from Raman mapping is useful in structural geology, materials science, and biosignature research.

Obtaining carbon isotopic information for organic carbon from Martian sediments has long been a goal of planetary science, as it has the potential to elucidate the origin of such carbon and aspects of Martian carbon cycling. Carbon isotopic values (813CVPDB) of the methane released during pyrolysis of 24 powder samples at Gale crater, Mars, show a high degree of variation (-137 +/- 8%o to +22 +/- 10%o) when measured by the tunable laser spectrometer portion of the Sample Analysis at Mars instrument suite during evolved gas analysis. Included in these data are 10 measured 813C values less than -70%o found for six different sampling locations, all potentially associated with a possible paleosurface. There are multiple plausible explanations for the anomalously depleted 13C observed in evolved methane, but no single explanation can be accepted without further research. Three possible explanations are the photolysis of biological methane released from the subsurface, photoreduction of atmospheric CO2, and deposition of cosmic dust during passage through a galactic molecular cloud. All three of these scenarios are unconventional, unlike processes common on Earth.

The Philae lander of the Rosetta space mission made a non-nominal landing on comet 67P/Churyumov-Gerasimenko on November 12, 2014. Shortly after, using the limited power available from Philae's batteries, the COSAC instrument performed a single 18-minutes gas chromatogram, which has remained unpublished until now due to the lack of identifiable elution. This work shows that, despite the unsuccessful drilling of the comet and deposition of surface material in the SD2 ovens, the measurements from the COSAC instrument were executed nominally. We describe an automated search for extremely small deviations from noise and discuss the possibility of a signal from ethylene glycol at m/z 31. Arguments for and against this detection are listed, but the results remain inconclusive. Still, the successful operations of an analytical chemistry laboratory on a cometary nucleus gives great hope for the future of space exploration.

The Sample Analysis at Mars instrument stepped combustion experiment on a Yellowknife Bay mudstone at Gale crater, Mars revealed the presence of organic carbon of Martian and meteoritic origins. The combustion experiment was designed to access refractory organic carbon in Mars surface sediments by heating samples in the presence of oxygen to combust carbon to CO2. Four steps were performed, two at low temperatures (less than 550°C) and two at high temperatures (up to 870°C). More than 950 mug C/g was released at low temperatures (with an isotopic composition of delta13C = +1.5 ± 3.8) representing a minimum of 431 mug C/g indigenous organic and inorganic Martian carbon components. Above 550°C, 273 ± 30 mug C/g was evolved as CO2 and CO (with estimated delta13C = -32.9 to -10.1 for organic carbon). The source of high temperature organic carbon cannot be definitively confirmed by isotopic composition, which is consistent with macromolecular organic carbon of igneous origin, meteoritic infall, or diagenetically altered biomass, or a combination of these. If from allochthonous deposition, organic carbon could have supported both prebiotic organic chemistry and heterotrophic metabolism at Gale crater, Mars, at 3.5 Ga.