Organic carbon concentrations in 3.5-billion-year-old lacustrine mudstones of Mars.

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 µg C/g was released at low temperatures (with an isotopic composition of δ13C = +1.5 ± 3.8‰) representing a minimum of 431 µg C/g indigenous organic and inorganic Martian carbon components. Above 550 °C, 273 ± 30 µg C/g was evolved as CO2 and CO (with estimated δ13C = -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.

Fatty Acid Preservation in Modern and Relict Hot-Spring Deposits in Iceland, with Implications for Organics Detection on Mars.

Hydrothermal spring deposits host unique microbial ecosystems and have the capacity to preserve microbial communities as biosignatures within siliceous sinter layers. This quality makes terrestrial hot springs appealing natural laboratories to study the preservation of both organic and morphologic biosignatures. The discovery of hydrothermal deposits on Mars has called attention to these hot springs as Mars-analog environments, driving forward the study of biosignature preservation in these settings to help prepare future missions targeting the recovery of biosignatures from martian hot-spring deposits. This study quantifies the fatty acid load in three Icelandic hot-spring deposits ranging from modern and inactive to relict. Samples were collected from both the surface and 2-18 cm in depth to approximate the drilling capabilities of current and upcoming Mars rovers. To determine the preservation potential of organics in siliceous sinter deposits, fatty acid analyses were performed with pyrolysis-gas chromatography-mass spectrometry (GC-MS) utilizing thermochemolysis with tetramethylammonium hydroxide (TMAH). This technique is available on both current and upcoming Mars rovers. Results reveal that fatty acids are often degraded in the subsurface relative to surface samples but are preserved and detectable with the TMAH pyrolysis-GC-MS method. Hot-spring mid-to-distal aprons are often the best texturally and geomorphically definable feature in older, degraded terrestrial sinter systems and are therefore most readily detectable on Mars from orbital images. These findings have implications for the detection of organics in martian hydrothermal systems as they suggest that organics might be detectable on Mars in relatively recent hot-spring deposits, but preservation likely deteriorates over geological timescales. Rovers with thermochemolysis pyrolysis-GC-MS instrumentation may be able to detect fatty acids in hot-spring deposits if the organics are relatively young; therefore, martian landing site and sample selection are of paramount importance in the search for organics on Mars.

Organic matter preserved in 3-billion-year-old mudstones at Gale crater, Mars.

Establishing the presence and state of organic matter, including its possible biosignatures, in martian materials has been an elusive quest, despite limited reports of the existence of organic matter on Mars. We report the in situ detection of organic matter preserved in lacustrine mudstones at the base of the ~3.5-billion-year-old Murray formation at Pahrump Hills, Gale crater, by the Sample Analysis at Mars instrument suite onboard the Curiosity rover. Diverse pyrolysis products, including thiophenic, aromatic, and aliphatic compounds released at high temperatures (500° to 820°C), were directly detected by evolved gas analysis. Thiophenes were also observed by gas chromatography-mass spectrometry. Their presence suggests that sulfurization aided organic matter preservation. At least 50 nanomoles of organic carbon persists, probably as macromolecules containing 5% carbon as organic sulfur molecules.

Clay mineral diversity and abundance in sedimentary rocks of Gale crater, Mars.

Clay minerals provide indicators of the evolution of aqueous conditions and possible habitats for life on ancient Mars. Analyses by the Mars Science Laboratory rover Curiosity show that ~3.5-billion year (Ga) fluvio-lacustrine mudstones in Gale crater contain up to ~28 weight % (wt %) clay minerals. We demonstrate that the species of clay minerals deduced from x-ray diffraction and evolved gas analysis show a strong paleoenvironmental dependency. While perennial lake mudstones are characterized by Fe-saponite, we find that stratigraphic intervals associated with episodic lake drying contain Al-rich, Fe3+-bearing dioctahedral smectite, with minor (3 wt %) quantities of ferripyrophyllite, interpreted as wind-blown detritus, found in candidate aeolian deposits. Our results suggest that dioctahedral smectite formed via near-surface chemical weathering driven by fluctuations in lake level and atmospheric infiltration, a process leading to the redistribution of nutrients and potentially influencing the cycling of gases that help regulate climate.

Mineralogy, provenance, and diagenesis of a potassic basaltic sandstone on Mars: CheMin X-ray diffraction of the Windjana sample (Kimberley area, Gale Crater).

The Windjana drill sample, a sandstone of the Dillinger member (Kimberley formation, Gale Crater, Mars), was analyzed by CheMin X-ray diffraction (XRD) in the MSL Curiosity rover. From Rietveld refinements of its XRD pattern, Windjana contains the following: sanidine (21% weight, ~Or95); augite (20%); magnetite (12%); pigeonite; olivine; plagioclase; amorphous and smectitic material (~25%); and percent levels of others including ilmenite, fluorapatite, and bassanite. From mass balance on the Alpha Proton X-ray Spectrometer (APXS) chemical analysis, the amorphous material is Fe rich with nearly no other cations-like ferrihydrite. The Windjana sample shows little alteration and was likely cemented by its magnetite and ferrihydrite. From ChemCam Laser-Induced Breakdown Spectrometer (LIBS) chemical analyses, Windjana is representative of the Dillinger and Mount Remarkable members of the Kimberley formation. LIBS data suggest that the Kimberley sediments include at least three chemical components. The most K-rich targets have 5.6% K2O, ~1.8 times that of Windjana, implying a sediment component with >40% sanidine, e.g., a trachyte. A second component is rich in mafic minerals, with little feldspar (like a shergottite). A third component is richer in plagioclase and in Na2O, and is likely to be basaltic. The K-rich sediment component is consistent with APXS and ChemCam observations of K-rich rocks elsewhere in Gale Crater. The source of this sediment component was likely volcanic. The presence of sediment from many igneous sources, in concert with Curiosity's identifications of other igneous materials (e.g., mugearite), implies that the northern rim of Gale Crater exposes a diverse igneous complex, at least as diverse as that found in similar-age terranes on Earth.

Evidence for indigenous nitrogen in sedimentary and aeolian deposits from the Curiosity rover investigations at Gale crater, Mars.

The Sample Analysis at Mars (SAM) investigation on the Mars Science Laboratory (MSL) Curiosity rover has detected oxidized nitrogen-bearing compounds during pyrolysis of scooped aeolian sediments and drilled sedimentary deposits within Gale crater. Total N concentrations ranged from 20 to 250 nmol N per sample. After subtraction of known N sources in SAM, our results support the equivalent of 110-300 ppm of nitrate in the Rocknest (RN) aeolian samples, and 70-260 and 330-1,100 ppm nitrate in John Klein (JK) and Cumberland (CB) mudstone deposits, respectively. Discovery of indigenous martian nitrogen in Mars surface materials has important implications for habitability and, specifically, for the potential evolution of a nitrogen cycle at some point in martian history. The detection of nitrate in both wind-drifted fines (RN) and in mudstone (JK, CB) is likely a result of N2 fixation to nitrate generated by thermal shock from impact or volcanic plume lightning on ancient Mars. Fixed nitrogen could have facilitated the development of a primitive nitrogen cycle on the surface of ancient Mars, potentially providing a biochemically accessible source of nitrogen.

The origin and implications of clay minerals from Yellowknife Bay, Gale crater, Mars.

The Mars Science Laboratory (MSL) rover Curiosity has documented a section of fluvio-lacustrine strata at Yellowknife Bay (YKB), an embayment on the floor of Gale crater, approximately 500 m east of the Bradbury landing site. X-ray diffraction (XRD) data and evolved gas analysis (EGA) data from the CheMin and SAM instruments show that two powdered mudstone samples (named John Klein and Cumberland) drilled from the Sheepbed member of this succession contain up to ~20 wt% clay minerals. A trioctahedral smectite, likely a ferrian saponite, is the only clay mineral phase detected in these samples. Smectites of the two samples exhibit different 001 spacing under the low partial pressures of H2O inside the CheMin instrument (relative humidity <1%). Smectite interlayers in John Klein collapsed sometime between clay mineral formation and the time of analysis to a basal spacing of 10 Å, but largely remain open in the Cumberland sample with a basal spacing of ~13.2 Å. Partial intercalation of Cumberland smectites by metal-hydroxyl groups, a common process in certain pedogenic and lacustrine settings on Earth, is our favored explanation for these differences. The relatively low abundances of olivine and enriched levels of magnetite in the Sheepbed mudstone, when compared with regional basalt compositions derived from orbital data, suggest that clay minerals formed with magnetite in situ via aqueous alteration of olivine. Mass-balance calculations are permissive of such a reaction. Moreover, the Sheepbed mudstone mineral assemblage is consistent with minimal inputs of detrital clay minerals from the crater walls and rim. Early diagenetic fabrics suggest clay mineral formation prior to lithification. Thermodynamic modeling indicates that the production of authigenic magnetite and saponite at surficial temperatures requires a moderate supply of oxidants, allowing circum-neutral pH. The kinetics of olivine alteration suggest the presence of fluids for thousands to hundreds of thousands of years. Mineralogical evidence of the persistence of benign aqueous conditions at YKB for extended periods indicates a potentially habitable environment where life could establish itself. Mediated oxidation of Fe2+ in olivine to Fe3+ in magnetite, and perhaps in smectites provided a potential energy source for organisms.