Abstract. The Curiosity rover discovered fine--grained sedimentary rocks, inferred to represent an ancient lake, preserve evidence of an environment that would have been suited to support a Martian biosphere founded on chemolithoautotrophy. This aqueous environment was characterized by neutral pH, low salinity, and variable redox states of both iron and sulfur species. C, H, O, S, N, and P were measured directly as key biogenic elements, and by inference N and P are assumed to have been available. The environment likely had a minimum duration of hundreds to tens of thousands of years. These results highlight the biological viability of fluvial--lacustrine environments in the post--Noachian history of Mars.
X-ray diffraction analysis of the Rocknest scoop sample is described in (23); similar analyses were performed for John Klein and Cumberland. John Klein and Cumberland were the first two drill samples collected by Curiosity. All scooped or drilled samples pass through the Collection and Handling for In situ Martian Rock Analysis (CHIMRA) sample collection and processing system (10). All powders for X-ray diffraction are processed through a 150-m sieve before delivering a portion to the CheMin inlet funnel.The sieved drill powders were placed into sample cells with 6 μm thick Mylar® windows. Mylar® contributes a minor, broad scattering signature in diffraction patterns that is generally "swamped" by diffraction from the loaded sample. In addition, an aluminized light shield also contributes "peaks" to the observed diffraction patterns. Only ~10 mm 3 of material is required to fill the active volume of the sample cell, which is a disc-shaped volume 8 mm in diameter and 175 m thick. A collimated ∼70 μm diameter X-ray beam illuminates the center of the sample cell. A piezoelectric vibration system on each cell pair shakes the material during analysis, causing grains in the cell to pass through the X-ray beam in random orientations.CheMin measures XRD and XRF data simultaneously using Co radiation in transmission geometry (11). The instrument operates in single-photon counting mode so that between each readout the majority of CCD pixels are struck by either a single X-ray photon or by no photons. In this way, the system can determine both the energy of the photons striking the CCD (XRF) and the two-dimensional (2-D) position of each photon (XRD). The energy and positional information of detected photons in each frame are summed over repeated 10-sec measurements into a "minor frame" of 30 min of data (180 frames). The 2-D distribution of Co K X-ray intensity represents the XRD pattern of the sample. Circumferential integration of these rings, corrected for arc length, produces a conventional 1-D XRD pattern. For conversion of the 2-D CCD pattern to a 1-D pattern we have used FilmScan © software from Materials Data, Inc.CheMin generally operates for only a few hours each night, when the CCD can be cooled to its lowest temperature, collecting as many minor frames as possible for the available analysis time, usually five to seven per night. XRD data were acquired over multiple nights for the John Klein and Cumberland drill samples to provide acceptable counting statistics. Total data collection times were 33.9 hr for John Klein and 20.2 hr for Cumberland. The data for individual minor frames and for each night's analysis were examined separately, and there was no evidence of any changes in instrumental parameters as a function of time over the duration of these analyses. Before sample delivery and analysis, the empty cell was analyzed to confirm that it was indeed empty before receiving the sample. The flight instrument was calibrated on the ground before flight using a quartz-beryl standard, and measurement of this st...
The sample analysis at Mars instrument evolved gas analyzer (SAM-EGA) has detected evolved water, H 2 , SO 2 , H 2 S, NO, CO 2 , 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 CO 2 (160 ± 248-2373 ± 820 μgC (CO2) /g) and CO (11 ± 3-320 ± 130 μgC (CO) /g) suggest that organic C is present in Gale Crater materials. Five samples evolved CO 2 at temperatures consistent with carbonate (0.32 ± 0.05-0.70 ± 0.1 wt % CO 3 ). Evolved NO amounts to 0.002 ± 0.007-0.06 ± 0.03 wt % NO 3 . Evolution of O 2 suggests that oxychlorine phases (chlorate/perchlorate) (0.05 ± 0.025-1.05 ± 0.44 wt % ClO 4 ) are present, while SO 2 evolution indicates the presence of crystalline and/or poorly crystalline Fe and Mg sulfate and possibly sulfide. Evolved H 2 O (0.9 ± 0.3-2.5 ± 1.6 wt % H 2 O) 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 H 2 S 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.
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 C2 to C4 dichloroalkanes (up to 70 ppbw) 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.Key PointsFirst in situ evidence of nonterrestrial organics in Martian surface sediments Chlorinated hydrocarbons identified in the Sheepbed mudstone by SAM Organics preserved in sample exposed to ionizing radiation and oxidative condition
All terrestrial organisms depend on nucleic acids (RNA and DNA), which use pyrimidine and purine nucleobases to encode genetic information. Carbon-rich meteorites may have been important sources of organic compounds required for the emergence of life on the early Earth; however, the origin and formation of nucleobases in meteorites has been debated for over 50 y. So far, the few nucleobases reported in meteorites are biologically common and lacked the structural diversity typical of other indigenous meteoritic organics. Here, we investigated the abundance and distribution of nucleobases and nucleobase analogs in formic acid extracts of 12 different meteorites by liquid chromatography-mass spectrometry. The Murchison and Lonewolf Nunataks 94102 meteorites contained a diverse suite of nucleobases, which included three unusual and terrestrially rare nucleobase analogs: purine, 2,6-diaminopurine, and 6,8-diaminopurine. In a parallel experiment, we found an identical suite of nucleobases and nucleobase analogs generated in reactions of ammonium cyanide. Additionally, these nucleobase analogs were not detected above our parts-per-billion detection limits in any of the procedural blanks, control samples, a terrestrial soil sample, and an Antarctic ice sample. Our results demonstrate that the purines detected in meteorites are consistent with products of ammonium cyanide chemistry, which provides a plausible mechanism for their synthesis in the asteroid parent bodies, and strongly supports an extraterrestrial origin. The discovery of new nucleobase analogs in meteorites also expands the prebiotic molecular inventory available for constructing the first genetic molecules.
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