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.

Recurring discoveries of abiotic methane in gas seeps and springs in ophiolites and peridotite massifs worldwide raised the question of where, in which rocks, methane was generated. Answers will impact the theories on life origin related to serpentinization of ultramafic rocks, and the origin of methane on rocky planets. Here we document, through molecular and isotopic analyses of gas liberated by rock crushing, that among the several mafic and ultramafic rocks composing classic ophiolites in Greece, i.e., serpentinite, peridotite, chromitite, gabbro, rodingite and basalt, only chromitites, characterized by high concentrations of chromium and ruthenium, host considerable amounts of C-13-enriched methane, hydrogen and heavier hydrocarbons with inverse isotopic trend, which is typical of abiotic gas origin. Raman analyses are consistent with methane being occluded in widespread microfractures and porous serpentine-or chlorite-filled veins. Chromium and ruthenium may be key metal catalysts for methane production via Sabatier reaction. Chromitites may represent source rocks of abiotic methane on Earth and, potentially, on Mars.

Laboratory simulations of Martian conditions are essential to develop quantitative models for the survival of organic biomarkers for future Mars exploration missions.

Confocal Raman Spectroscopy and Microscopy have attained a significant increase in recognition over the past two decades and the method is now well established as another instrument in the geoscientists' toolbox. Here we present and discuss the use and benefit of the method, considering aspects related to sample preparation, effects of the interaction of lasers on specific sample surfaces, as well as instrumental consideration to address these aspects. Further we present examples how confocal Raman microscopy can be applied in mineral phase and phase composition imaging as well as crystallographic orientation imaging in a variety of geological materials, including shocked minerals, carbonaceous materials and fluid inclusions.

Elemental sulfur (S-0) is produced and degraded by phylogenetically diverse groups of microorganisms. For Chlorobaculum tepidum, an anoxygenic phototroph, sulfide is oxidized to produce extracellular S-0 globules, which can be further oxidized to sulfate. While some sulfur-oxidizing bacteria (e.g., Allochromatium vinosum) are also capable of growth on commercial S-0 as an electron donor, C. tepidum is not. Even colloidal sulfur sols, which appear indistinguishable from biogenic globules, do not support the growth of C. tepidum. Here, we investigate the properties that make biogenic S-0 globules distinct from abiotic forms of S-0. We found that S-0 globules produced by C. tepidum and abiotic S-0 sols are quite similar in terms of mineralogy and material properties, but the two are distinguished primarily by the properties of their surfaces. C. tepidum's globules are enveloped by a layer of organics (protein and polysaccharides), which results in a surface that is fundamentally different from that of abiotic S-0 sols. The organic coating on the globules appears to slow the aging and crystallization of amorphous sulfur, perhaps providing an extended window of time for microbes in the environment to access the more labile forms of sulfur as needed. Overall, our results suggest that the surface of biogenic S-0 globules may be key to cell-sulfur interactions and the reactivity of biogenic S-0 in the environment.

Direct evidence of complex prebiotic chemistry from a water-rich world in the outer solar system is provided by the 4.5-billion-year-old halite crystals hosted in the Zag and Monahans (1998) meteorites. This study offers the first comprehensive organic analysis of the soluble and insoluble organic compounds found in the millimeter-sized halite crystals containing brine inclusions and sheds light on the nature and activity of aqueous fluids on a primitive parent body. Associated with these trapped brines are organic compounds exhibiting wide chemical variations representing organic precursors, intermediates, and reaction products that make up life's precursor molecules such as amino acids. The organic compounds also contain a mixture of C-, O-, and N-bearing macromolecular carbon materials exhibiting a wide range of structural order, as well as aromatic, ketone, imine, and/or imidazole compounds. The enrichment in N-15 is comparable to the organic matter in pristine Renazzo-type carbonaceous chondrites, which reflects the sources of interstellar N-15, such as ammonia and amino acids. The amino acid content of the Zag halite deviates from the meteorite matrix, supporting an exogenic origin of the halite, and therefore, the Zag meteorite contains organics synthesized on two distinct parent bodies. Our study suggests that the asteroidal parent body where the halite precipitated, potentially asteroid 1 Ceres, shows evidence for a complex combination of biologically and prebiologically relevant molecules.