The Sample Analysis at Mars (SAM) instrument on board the Mars Science Laboratory Curiosity rover is designed to conduct inorganic and organic chemical analyses of the atmosphere and the surface regolith and rocks to help evaluate the past and present habitability potential of Mars at Gale Crater. Central to this task is the development of an inventory of any organic molecules present to elucidate processes associated with their origin, diagenesis, concentration, and long-term preservation. This will guide the future search for biosignatures. Here we report the definitive identification of chlorobenzene (150-300 parts per billion by weight (ppbw)) and C-2 to C-4 dichloroalkanes (up to 70ppbw) with the SAM gas chromatograph mass spectrometer (GCMS) and detection of chlorobenzene in the direct evolved gas analysis (EGA) mode, in multiple portions of the fines from the Cumberland drill hole in the Sheepbed mudstone at Yellowknife Bay. When combined with GCMS and EGA data from multiple scooped and drilled samples, blank runs, and supporting laboratory analog studies, the elevated levels of chlorobenzene and the dichloroalkanes cannot be solely explained by instrument background sources known to be present in SAM. We conclude that these chlorinated hydrocarbons are the reaction products of Martian chlorine and organic carbon derived from Martian sources (e.g., igneous, hydrothermal, atmospheric, or biological) or exogenous sources such as meteorites, comets, or interplanetary dust particles.

Comets harbor the most pristine material in our solar system in the form of ice, dust, silicates, and refractory organic material with some interstellar heritage. The evolved gas analyzer Cometary Sampling and Composition (COSAC) experiment aboard Rosetta's Philae lander was designed for in situ analysis of organic molecules on comet 67P/Churyumov-Gerasimenko. Twenty-five minutes after Philae's initial comet touchdown, the COSAC mass spectrometer took a spectrum in sniffing mode, which displayed a suite of 16 organic compounds, including many nitrogen-bearing species but no sulfur-bearing species, and four compounds-methyl isocyanate, acetone, propionaldehyde, and acetamide-that had not previously been reported in comets.

Changes in composition during the transition from sediment to rock are usually attributed to long, complicated histories and atmospheric influences, while the contribution of benthic mat-building cyanobacteria is not typically considered. Here the goal is to understand the influence of cyanobacterial mats on mineral weathering in postdepositional settings of sandy, shallow subaquatic environments. Laboratory incubation experiments were done using ilmenite sands and ilmenite-enriched quartz sands colonized by cyanobacterial mats for five months at three temperatures: 25 degrees C and 37 degrees C, representative of postdepositional weathering regimes, and 70 degrees C corresponding to early diagenesis. As a comparative control to represent abiotic processes, ilmenite sands and ilmenite-enriched quartz sands were also subjected to the same conditions without cyanobacterial colonization. The precipitation of minerals on cyanobacterial cells and extracellular polymeric substances (EPS) as well as the phase changes in natural ilmenites (FeTiO3) were documented to determine if cyanobacteria influence mineral reaction pathways. The precipitates, ilmenite grains, and permineralized cells were analyzed using complementary techniques of scanning electron microscopy (SEM), X-ray diffraction (XRD), and micro-Raman spectroscopy. The results of this study show that a variety of pure and mixed mineral phases precipitate under postdepositional conditions (T <= 70 degrees C) in wet, sandy environments with or without cyanobacteria. Akaganeite, anatase, ankerite, lepidocrocite, gibbsite, kaolinite, and natrojarosite formed exclusively in the samples incubated with cyanobacteria. In the samples incubated with cyanobacteria, more mineral phases formed at 37 degrees C, suggesting that cyanobacteria play a greater role in weathering than in early diagenesis. Sulfate phases that formed in the presence of cyanobacteria differed in chemical composition from the abiotic precipitates as Na, Al, Mg, and Si were incorporated into the structures of newly formed biotic phases. Understanding the possible fate of these precursor mineral phases will help redefine geochemical biosignatures that can be used for the detection of ancient microbial life in sedimentary rocks on Earth as well as for future missions exploring life on other planets.

Methane has been reported repeatedly in the martian atmosphere but its origin remains an obstinate mystery. Possible sources include aqueous alteration of igneous rocks, release from ancient deposits of methane/water ice clathrates, infall from exogenous sources such as background interplanetary dust, or biological activity. All of these sources are problematic, however. We hypothesise that delivery of cometary material includes meteor outbursts, commonly known as "meteor showers", may explain martian methane plumes. Correlations exist between the appearance of methane and near-approaches between Mars and cometary orbits. Additional correlations are seen between these interactions and the appearance of high-altitude dust clouds on Mars, showing that large amounts of material may be deposited on Mars during these encounters. Methane is released by UV breakdown of delivered cometary material. This hypothesis is testable in future Mars/cometary encounters. A cometary origin for methane would reveal formation of methane through processes that are separate from any geological or biological processes on Mars.

The utility of nondestructive laser Raman for testing the biogenicity of microfossil-like structures in ancient rocks is promising, yet results from deposits like the similar to 3.46 Ga Apex chert remain contentious. The essence of the debate is that associated microstructures, which are not purported to be microfossils, also contain reduced carbon that displays Raman D- and G-band peaks similar to those seen in the purported microfossils. This has led to the hypothesis that all features including reported microfossils are due to compression of nonfossil carbon during crystal growth around quartz spherulites or more angular crystals. In this scenario, the precursor to this macromolecular carbon may or may not have been of biogenic origin, while the arcuate and linear features described would be pseudofossils. To test this hypothesis, we have undertaken 2-D micro-Raman imaging of the Eoleptonema apex holotype and associated features using instrumentation with a high spatial and spectral resolution. In addition to this, we utilized the ratio of two Raman active quartz mode intensities (I-129/I-461) to assess quartz grain orientation and grain-splitting artifacts. These data lead us to conclude that the holotype of Eoleptonema apex is a sheet-shaped pseudofossil that appears to be a carbon infilled intragranular crack; therefore other holotypes should be carefully reexamined for syngenicity. Key Words: Micro-Raman spectroscopy-Microfossils-Life detection-Archean-Apex chert. Astrobiology 16, 169-180.

Purple sulfur bacteria (PSB) are known to couple the carbon, nitrogen, and sulfur cycling in euxinic environments. This is the first study with multiple strains and species of okenone-producing PSB to examine the carbon (C), nitrogen (N), and sulfur (S) metabolisms and isotopic signatures in controlled laboratory conditions, investigating what isotopic fractionations might be recorded in modern environments and the geologic record. PSB play an integral role in the ecology of euxinic environments and produce the unique molecular fossil okenane, derived from the diagenetic alteration of the carotenoid pigment okenone. Cultures of Marichromatium purpuratum 1591 (Mpurp1591) were observed to have carbon isotope fractionations ((13)epsilon(biomass -) (CO2)), via RuBisCO, ranging from -16.1 to -23.2 parts per thousand during exponential and stationary phases of growth. Cultures of Thiocapsa marina 5653 (Tmar5653) and Mpurp1591 had a nitrogen isotope fractionation ((15)epsilon(biomass -) (NH4)) of -15 parts per thousand, via glutamate dehydrogenase, measured and recorded for the first time in PSB. The S-34(VCDT) values and amount of stored elemental sulfur for Mpurp1591 cells grown autotrophically and photoheterotrophically were dependent upon their carbon metabolic pathways. We show that PSB may contribute to the isotopic enrichments observed in modern and ancient anoxic basins. In a photoheterotrophic culture of Mpurp1591 that switched to autotrophy once the organic substrate was consumed, there were bulk biomass C-13 values that span a broader range than recorded across the Late Devonian, Permian-Triassic, Triassic-Jurassic, and OAE2 mass extinction boundaries. This finding stresses the complexities in interpreting and assigning C-13 values to bulk organic matter preserved in the geologic record.

Okenone is a carotenoid pigment unique to certain members of Chromatiaceae, the dominant family of purple sulfur bacteria (PSB) found in euxinic photic zones. Diagenetic alteration of okenone produces okenane, the only recognized molecular fossil unique to PSB. The in vivo concentrations of okenone and bacteriochlorophyll a (Bchl a) on a per cell basis were monitored and quantified as a function of light intensity in continuous cultures of the purple sulfur bacterium Marichromatium purpuratum (Mpurp1591). We show that okenone-producing PSB have constant bacteriochlorophyll to carotenoid ratios in light-harvesting antenna complexes. The in vivo concentrations of Bchl a, 0.151 +/- 0.012fmolcell(-1), and okenone, 0.103 +/- 0.012fmolcell(-1), were not dependent on average light intensity (10-225Lux) at both steady and non-steady states. This observation revealed that in autotrophic continuous cultures of Mpurp1591, there was a constant ratio for okenone to Bchl a of 1:1.5. Okenone was therefore constitutively produced in planktonic cultures of PSB, regardless of light intensity. This confirms the legitimacy of okenone as a signature for autotrophic planktonic PSB and by extrapolation water column euxinia. We measured the C-13, N-15, and S-34 bulk biomass values from cells collected daily and determined the isotopic fractionations of Mpurp1591. There was no statistical relationship in the bulk isotope measurements or stable isotope fractionations to light intensity or cell density under steady and non-steady-state conditions. The carbon isotope fractionation between okenone and Bchl a with respect to overall bulk biomass ((13)epsilon(pigment-biomass)) was 2.2 +/- 0.4 parts per thousand and -4.1 +/- 0.9 parts per thousand, respectively. The carbon isotopic fractionation ((13)epsilon(pigment - CO2)) for the production of pigments in PSB is more variable than previously thought with our reported values for okenone at -15.5 +/- 1.2 parts per thousand and -21.8 +/- 1.7 parts per thousand for Bchl a.

An increasing number of observations have shown that gaseous debris discs are not an exception. However, until now, we only knew of cases around A stars. Here we present the first detection of (CO)-C-12 (2-1) disc emission around an F star, HD 181327, obtained with the Atacama Large Millimeter/submillimeter Array (ALMA) observations at 1.3 mm. The continuum and CO emission are resolved into an axisymmetric disc with ring-like morphology. Using a Markov chain Monte Carlo method coupled with radiative transfer calculations, we study the dust and CO mass distribution. We find the dust is distributed in a ring with a radius of 86.0 +/- 0.4 au and a radial width of 23.2 +/- 1.0 au. At this frequency, the ring radius is smaller than in the optical, revealing grain size segregation expected due to radiation pressure. We also report on the detection of low-level continuum emission beyond the main ring out to similar to 200 au. We model the CO emission in the non-local thermodynamic equilibrium regime and we find that the CO is co-located with the dust, with a total CO gas mass ranging between 1.2 x 10(-6) M-aS center dot and 2.9 x 10(-6) M-aS center dot, depending on the gas kinetic temperature and collisional partners densities. The CO densities and location suggest a secondary origin, i.e. released from icy planetesimals in the ring. We derive a CO+CO2 cometary composition that is consistent with Solar system comets. Due to the low gas densities, it is unlikely that the gas is shaping the dust distribution.