Variability in the sulfur isotopic composition in sediments can reflect atmospheric, geologic and biological processes. Evidence for ancient fluvio-lacustrine environments at Gale crater on Mars and a lack of efficient crustal recycling mechanisms on the planet suggests a surface environment that was once warm enough to allow the presence of liquid water, at least for discrete periods of time, and implies a greenhouse effect that may have been influenced by sulfur-bearing volcanic gases. Here we report in situ analyses of the sulfur isotopic compositions of SO2 volatilized from ten sediment samples acquired by NASA's Curiosity rover along a 13 km traverse of Gale crater. We find large variations in sulfur isotopic composition that exceed those measured for Martian meteorites and show both depletion and enrichment in S-34. Measured values of delta S-34 range from -47 +/- 14 parts per thousand to 28 +/- 7 parts per thousand h, similar to the range typical of terrestrial environments. Although limited geochronological constraints on the stratigraphy traversed by Curiosity are available, we propose that the observed sulfur isotopic signatures at Gale crater can be explained by equilibrium fractionation between sulfate and sulfide in an impact-driven hydrothermal system and atmospheric processing of sulfur-bearing gases during transient warm periods.

Cyanobacteria are ubiquitous in a variety of modern habitats, and siliciclastic sediments in particular are home to a wide diversity of microbial communities. Benthic microbial mats, typically established by cyanobacteria on modern Earth, were likely prevalent on Archean Earth, yet explicit traces of their ancestors in Archean siliciclastic rocks are difficult to detect. To understand the taphonomy of benthic microbial mats in sandy, subaquatic environments, cyanobacterial mats were incubated for five months under a range of temperatures representative of ambient (25 degrees C) and eogenetic conditions (37 degrees C, 70 degrees C, and 100 degrees C). Cyanobacterial materials including trichomes, sheaths, and extracellular polymeric substances (EPS) were analyzed using scanning electron microscopy-energy dispersive X-ray spectroscopy (SEM-EDS) and micro Raman spectroscopy. Textures were permineralized in all temperature regimes with phases that included mixed silicates, Na-carbonate, clays, gypsum-anhydrite, pyrrhotite, anatase, akaganeite, magnetite, natrojarosite, and ankerite. Pigments including chlorophyll, beta-carotene, and scytonemin were identified in the lower temperature regimes, but were not easily detected in the samples incubated at 100 degrees C. The morphological characteristics of trichomes and sheaths were maintained to some degree in all temperature regimes, but there was a higher relative abundance of EPS as temperatures increased. The profusion of EPS obscured the absolute differentiation between individual trichomes and sheaths at higher temperatures. The results indicate that over time, morphological, mineralogical, and carbonaceous features that formed at the end of these incubation experiments could collectively create the laminations characteristic of fossilized microbial mats found in sandstones throughout the geologic record. In Archean sandstones, where very little is preserved, these collective features may prove to be especially important in the detection of ancient life.

We describe the current state of the search for direct, surviving samples of early, inner Solar System fluids-fluid inclusions in meteorites. Meteoritic aqueous fluid inclusions are not rare, but they are very tiny and their characterization is at the state of the art for most analytical techniques. Meteoritic fluid inclusions offer us a unique opportunity to study early Solar System brines in the laboratory. Inclusion-by-inclusion analyses of the trapped fluids in carefully selected samples will, in the immediate future, provide us detailed information on the evolution of fluids as they interacted with anhydrous solid materials. Thus, real data can replace calculated fluid compositions in thermochemical calculations of the evolution of water and aqueous reactions in comets, asteroids, moons and the terrestrial planets.

The sample analysis at Mars instrument evolved gas analyzer (SAM-EGA) has detected evolved water, H-2, SO2, H2S, NO, CO2, CO, O-2, and HCl from two eolian sediments and nine sedimentary rocks from Gale Crater, Mars. These evolved gas detections indicate nitrates, organics, oxychlorine phase, and sulfates are widespread with phyllosilicates and carbonates occurring in select Gale Crater materials. Coevolved CO2 (160248-2373820gC((CO2))/g) and CO (113-320130 gC((CO))/g) suggest that organic C is present in Gale Crater materials. Five samples evolved CO2 at temperatures consistent with carbonate (0.32 +/- 0.05-0.70 +/- 0.1wt% CO3). Evolved NO amounts to 0.002 +/- 0.007-0.06 +/- 0.03wt% NO3. Evolution of O-2 suggests that oxychlorine phases (chlorate/perchlorate) (0.05 +/- 0.025-1.05 +/- 0.44wt% ClO4) are present, while SO2 evolution indicates the presence of crystalline and/or poorly crystalline Fe and Mg sulfate and possibly sulfide. Evolved H2O (0.9 +/- 0.3-2.5 +/- 1.6wt% H2O) is consistent with the presence of adsorbed water, hydrated salts, interlayer/structural water from phyllosilicates, and possible inclusion water in mineral/amorphous phases. Evolved H-2 and H2S suggest that reduced phases occur despite the presence of oxidized phases (nitrate, oxychlorine, sulfate, and carbonate). SAM results coupled with CheMin mineralogical and Alpha-Particle X-ray Spectrometer elemental analyses indicate that Gale Crater sedimentary rocks have experienced a complex authigenetic/diagenetic history involving fluids with varying pH, redox, and salt composition. The inferred geochemical conditions were favorable for microbial habitability and if life ever existed, there was likely sufficient organic C to support a small microbial population.

Bobdownsite, IMA number 2008-037, was approved as a new mineral by the Commission on New Minerals, Nomenclature and Classification (CNMNC) as the fluorine end-member of the mineral whitlockite. The type locality of bobdownsite is in Big Fish River, Yukon, Canada, and bobdownsite was reported to be the first mineral with essential monofluorophosphate (PO3F2-). The type specimen of bobdownsite has been reinvestigated by electron probe microanalysis (EPMA), and our data indicate that fluorine abundances are below detection in the mineral. In addition, we conducted detailed analysis of bobdownsite from the type locality by gas chromatography isotope ratio mass spectrometry, Raman spectroscopy, EPMA, and NMR spectroscopy. These data were compared with previously published data on synthetic monofluorophosphate salts. Collectively, these data indicate that bobdownsite is indistinguishable from whitlockite with a composition along the whitlockite-merrillite solid solution. Bobdownsite is therefore discredited as a valid mineral species. An additional mineral, krasnoite, has been purported to have monofluorophosphate components in its structure, but reexamination of those data indicate that F-in krasnoite forms bonds with Al, similar to OH-bonded to Al in perhamite. Consequently, krasnoite also lacks monofluorophosphate groups, and there are currently no valid mineral species with monofluorophosphate in their structure. We recommend that any future reports of new minerals that contain essential monofluorophosphate anions be vetted by abundance measurements of fluorine, vibrational spectroscopy (both Raman and FTIR), and where paramagnetic components are permissibly low, NMR spectroscopy. Furthermore, we emphasize the importance of using synthetic compounds containing monofluorophosphate anions as a point of comparison in the identification of minerals with essential monofluorophosphate. Structural data that yield satisfactory P-F bond lengths determined by X-ray crystallography, coupled with direct chemical analyses of fluorine in a material do not constitute sufficient evidence alone to identify a new mineral with essential monofluorophosphate.

Lake Lucero is a gypsum-rich, hypersaline, ephemeral playa located on the southern part of the Alkali Flat at the White Sands National Monument (WSNM), New Mexico, USA. This modern playa setting provides a dynamic extreme environment that changes from a freshwater lake to a hypersaline dry desert during the year. We investigated the microbial diversity (bacteria, archaea, and microbial eukaryotes) of the Lake Lucero sediments using 16S- and 18S-based amplicon sequencing approach and explored the diversity patterns in different geochemical microenvironments. Our results indicated that similar microbial communities, in particular bacterial communities colonized, were remarkably consistent across our depth profiles. Therefore, these communities show a first-order relevance on the environmental conditions (moisture content, oxygen content, and mineral composition). We found that Proteobacteria, Actinobacteria, Bacteroidetes, Firmicutes, and Gemmatimonadetes were the major bacterial phyla, while Cyanobacteria were present in relatively low abundances and appeared only at the surface. Genus level assessment reflected that Truepera, Delftia, and Pseudomonas were the predominant bacterial genera across all samples. Euryarchaeota was the major archaeal phylum in all the samples, while Candidatus Halobonum and Candidatus Nitrososphaera were the main genera. Diatoms were the dominant eukaryotic group in surface samples and Fungi, Ciliophora, Metazoa, and Nematodes were the other major groups. As expected, metabolic inference indicated that aerobic microbial communities were near surface colonizers, with anaerobic communities dominating with increasing depth. We demonstrated that these microbial communities could be used to characterize unique geochemical microenvironments enabling us to extrapolate these results into other terrestrial and possibly extraterrestrial environments with comparable geochemical characteristics.

The sources and nature of organic carbon on Mars have been a subject of intense research. Steele et al. (2012) showed that 10 martian meteorites contain macromolecular carbon phases contained within pyroxene-and olivine-hosted melt inclusions. Here, we show that martian meteorites Tissint, Nakhla, and NWA 1950 have an inventory of organic carbon species associated with fluid-mineral reactions that are remarkably consistent with those detected by the Mars Science Laboratory (MSL) mission. We advance the hypothesis that interactions among spinel-group minerals, sulfides, and a brine enable the electrochemical reduction of aqueous CO2 to organic molecules. Although documented here in martian samples, a similar process likely occurs wherever igneous rocks containing spinel-group minerals and/or sulfides encounter brines.

Variable levels of methane in the martian atmosphere have eluded explanation partly because the measurements are not repeatable in time or location. We report in situ measurements at Gale crater made over a 5-year period by the Tunable Laser Spectrometer on the Curiosity rover. The background levels of methane have a mean value 0.41 +/- 0.16 parts per billion by volume (ppbv) (95% confidence interval) and exhibit a strong, repeatable seasonal variation (0.24 to 0.65 ppbv). This variation is greater than that predicted from either ultraviolet degradation of impact-delivered organics on the surface or from the annual surface pressure cycle. The large seasonal variation in the background and occurrences of higher temporary spikes (similar to 7 ppbv) are consistent with small localized sources of methane released from martian surface or subsurface reservoirs.

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 similar to 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 degrees 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.