Table of Contents

An interesting characteristic of the pyroclastic glass bead deposits, select impact produced lithologies such as the "rusty rock" 66095, and unique lunar soils from the Apollo 16 landing site, is their unusual enrichments in Pb-204, Cd, Bi, Br, I, Ge, Sb, Tl, Zn, and Cl which indicates that portions of these sample contain a substantial volatile component. Sample 66095, a fine-grained, subophitic to ophitic polymict melt breccia, also hosts a pervasive low-temperature, volatile-rich, oxy-hydrated mineral assemblage. The volatile element enrichments in these assorted lunar lithologies have been attributed to a variety of extra-lunar and lunar processes, whereas the oxyhydration in 66095 has long been thought to represent either terrestrial alteration of lunar chlorides and Fe-Ni metal to beta FeO(OH,Cl) or indigenous lunar processes. In 66095, Cl is accommodated in FeO(OH,Cl), phosphates, and chlorides and is heterogeneously distributed. The low-temperature alteration occurs as rims around Fe-Ni metal and sulfide grains, and as dispersed grains in the adjacent matrix. Micro-Raman and transmission electron microscope (TEM) imaging indicate that akaganeite (beta FeO(OH,Cl)) is the dominant Fe0(OH) polymorph and is intergrown with goethite (alpha FeO(OH)) and hematite (alpha Fe2O3). TEM observations indicate a well-defined "nanometer-scale" stratigraphy" to the alteration. For example, kamacite (body centered cubic) --> face-centered cubic (fcc) Fe-Ni alloy --> lawrencite (FeCl2) --> akaganeite. The lunar lawrencite (Fe,Ni)Cl-2 in 66095 does not react directly to akaganeite on Earth. Rather, lawrencite exposed to terrestrial conditions reacts to form an amorphous Fe- and Cl-bearing phase, nano-crystalline goethite, and hematite. The morphology of these terrestrial alteration products is significantly different than that of the akaganeite occurring in 66095. The chlorine isotopic compositions of these volatile-rich samples are enriched in heavy Cl. For 66095, the delta Cl-32 ranges from +14.0 parts per thousand to +15.6 parts per thousand, whereas the delta Cl-32 for the volatile-rich A16 soils ranges from +5.6 parts per thousand to +15.7 parts per thousand. Based on these data it appears likely that the volatile element enrichments and the Cl isotopic fractionation observed in 66095 and the Apollo 16 soils did not result from extra-lunar additions, but are most likely indigenous to the Moon. Lawrencite was deposited on mineral surfaces at approximately 650 degrees C to 570 degrees C from a metal-chloride-bearing, H-poor gas phase. This gas phase was also responsible for the transport of other metals (e.g. Zn, Cu, Pb, Fe). The fractionation of Cl isotopes in the rusty rock can be attributed to fumarole processes in a low-H system. The origin and formation of the akaganeite is more enigmatic. The Cl-isotopes are consistent with it replacing lawrencite. However, numerous nanometer-scale observations are not consistent with a terrestrial origin and indicate multiple episodes of oxyhydration. (C) 2014 Elsevier Ltd. All rights reserved.

The Cometary Sampling and Composition (COSAC) experiment onboard the Philae lander is a combined Gas Chromatograph-Mass Spectrometer targeted to determine the organic composition of the nucleus of comet 67P/Churyumov-Gerasimenko. The COSAC flight-model mass spectrometer (FM-MS) was scheduled to sample volatile organic species from 67P's coma prior to Philae's detachment from the Rosetta orbiter in November 2014. It was again scheduled to sample subsequent to Philae's touchdown but prior to drilling operations, thereby retrieving measurements of volatiles from the surface of an unperturbed nucleus. This article evaluates the competence of COSAC mass spectrometers in identifying volatile organic species in both cometary and laboratory-simulated environments. The evaluation was conducted on an operationally optimized COSAC flight spare model mass spectrometer (FS-MS) maintained in ultra-high vacuum. The FS-MS obtained analytical measurements by "sniffing" several organic molecule mixtures of diverse chemical functional groups and molecules with broader molecular masses introduced into the vacuum vessel housing the instrument. The results demonstrate that COSAC produces mass fragmentation patterns of organic species similar to those in calibration standard mass spectra; it is able to identify various organic species within mixtures present at low concentrations (100 ppm); and it can identify fragmentation patterns of non-introduced unknown species and those with high molecular masses within organic mixtures. These observations successfully substantiate the potential of the FM-MS to make qualitative measurements of organic species both in the rarefied environment of the coma and in the relatively enriched nucleus surface. (C) 2014 Elsevier Ltd. All rights reserved.

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.