In situ measurement of atmospheric krypton and xenon on Mars with Mars Science Laboratory

Mars Science Laboratory's Sample Analysis at Mars (SAM) investigation has measured all of the stable isotopes of the heavy noble gases krypton and xenon in the martian atmosphere, in situ, from the Curiosity Rover at Gale Crater, Mars. Previous knowledge of martian atmospheric krypton and xenon isotope ratios has been based upon a combination of the Viking mission's krypton and xenon detections and measurements of noble gas isotope ratios in martian meteorites. However, the meteorite measurements reveal an impure mixture of atmospheric, mantle, and spallation contributions. The xenon and krypton isotopic measurements reported here include the complete set of stable isotopes, unmeasured by Viking. The new results generally agree with Mars meteorite measurements but also provide a unique opportunity to identify various non-atmospheric heavy noble gas components in the meteorites. Kr isotopic measurements define a solar-like atmospheric composition, but deviating from the solar wind pattern at 80Kr and 82Kr in a manner consistent with contributions originating from neutron capture in Br. The Xe measurements suggest an intriguing possibility that isotopes lighter than 132Xe have been enriched to varying degrees by spallation and neutron capture products degassed to the atmosphere from the regolith, and a model is constructed to explore this possibility. Such a spallation component, however, is not apparent in atmospheric Xe trapped in the glassy phases of martian meteorites

Discordant K-Ar and Young Exposure Dates for the Windjana sandstone, Kimberley, Gale Crater, Mars

K-Ar and noble gas surface exposure age measurements were carried out on the Windjana sandstone, Kimberley region, Gale Crater, Mars, by using the Sample Analysis at Mars instrument on the Curiosity rover. The sandstone is unusually rich in sanidine, as determined by CheMin X-ray diffraction, contributing to the high K_2O concentration of 3.09 ± 0.20 wt % measured by Alpha-Particle X-ray Spectrometer analysis. A sandstone aliquot heated to ~915°C yielded a K-Ar age of 627 ± 50 Ma. Reheating this aliquot yielded no additional Ar. A second aliquot heated in the same way yielded a much higher K-Ar age of 1710 ± 110 Ma. These data suggest incomplete Ar extraction from a rock with a K-Ar age older than 1710 Ma. Incomplete extraction at ~900°C is not surprising for a rock with a large fraction of K carried by Ar-retentive K-feldspar. Likely, variability in the exact temperature achieved by the sample from run to run, uncertainties in sample mass estimation, and possible mineral fractionation during transport and storage prior to analysis may contribute to these discrepant data. Cosmic ray exposure ages from ^3He and ^(21)Ne in the two aliquots are minimum values given the possibility of incomplete extraction. However, the general similarity between the ^3He (57 ± 49 and 18 ± 32 Ma, mean 30 Ma) and ^(21)Ne (2 ± 32 and 83 ± 24 Ma, mean 54 Ma) exposure ages provides no evidence for underextraction. The implied erosion rate at the Kimberley location is similar to that reported at the nearby Yellowknife Bay outcrop

Young K-Ar gae of jarosite in the Mojave sample at Gale Crater, Mars.

By combining the Sample Analysis at Mars (SAM) instrument’s capabilities with those of the alpha particle X-ray spectrometer (APXS) on the Curiosity rover, radiometric K-Ar ages and 3He, 21Ne, and 36Ar exposure ages have been measured on two samples as of sol 1430. The Cumberland mudstone was found to have a K-Ar age of 4.21 ± 0.35 Ga (all uncertainties here are reported in 1σ), consistent with crater-counting estimates of the surrounding terrains. A second geochronology experiment was undertaken on the potassium-rich Windjana sandstone, which resulted in the unreasonably young and unrepeatable ages of 627 ± 50 Ma and 1710 ± 110 Ma on two different aliquots. These results were attributed to incomplete Ar extraction arising from the coarse grainsize and Ar-retentive characteristics of sanidine, the major K-bearing mineral in the sample.Recently, a drilled bedrock sample from the Murray mudstone formation (termed Mojave 2) was found by the CheMin instrument to contain approximately 3.1 wt% jarosite. Jarosite is precipitated from acidic, sulfate-rich waters and is a suitable mineral for KAr dating. On a large scale, jarosite has been thought to signal the aridification of Mars and a shift towards a cold, dry environment. The small amount of jarosite in this sample prohibits generalization to a larger Martian context. However, since jarosite forms strictly through interaction with water, the K-Ar age of the jarosite in Mojave 2 puts a maximum age constraint on the last time liquid water was present at the sample site. By extension, it could also indicate the time of the very final stages of evaporation from the lake in Gale Crater.A two-step heating experiment was designed to obtain the K-Ar age of the jarosite, which accounts for about 20% of the K2O in the sample. The remainder of the K2O exists in plagioclase, an amorphous component, and possibly a small amount in K-bearing phyllosilicates

Glen Torridon Mineralogy and the Sedimentary History of the Clay Mineral Bearing Unit

Clay minerals are common in ancient terrains on Mars and their presence at the surface alludes to aqueous processes in the Noachian to Early Hesperian (>3.5 Ga). Gale crater was selected as Curiositys landing site largely because of the identification of clay mineral rich strata from orbit. On Earth, the types of clay minerals (i.e., smectites) identified in Gale crater are typically juvenile weathering products that ultimately record the interaction between primary igneous minerals with the hydrosphere, atmosphere, and biosphere. Trioctahedral and dioctahedral smectite were identified by Curiosity in units stratigraphically below the Clay Mineral-Bearing Unit (CBU) identified from orbit. Compositional and sedimentological data suggest the smectite formed via authigenesis in a lake environment and may have been altered during early diagenesis. The CBU is stratigraphically equivalent to a hematite-rich unit to the north and stratigraphically underlies sulfate-rich units to the south, suggesting a dynamic environment and evolving history of water in the ancient Gale crater lake. Targeting these clay mineral rich areas on Mars with rover missions provides an opportunity to explore the aqueous and sedimentary history of the planet

Isotopes of nitrogen on Mars: Atmospheric measurements by Curiosity's mass spectrometer

Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/102173/1/wong_readme.pdfhttp://deepblue.lib.umich.edu/bitstream/2027.42/102173/2/wong2013_SM_v4b.pdfhttp://deepblue.lib.umich.edu/bitstream/2027.42/102173/3/grl51166.pd

Seasonal Variations in Atmospheric Composition as Measured in Gale Crater, Mars

All MSL data used in this manuscript (REMS and SAM) are freely available on NASA's Planetary Data System (PDS) Geosciences Node, from within 6 months after receipt on Earth (http://pds‐geosciences.wustl.edu/missions/msl/). The mixing ratios developed and presented in this paper are available at a publicly available archive (dataverse.org: doi.org/10.7910/DVN/CVUOWW) as cited within the manuscript. The successful operation of the Curiosity rover and the SAM instrument on Mars is due to the hard work and dedication of hundreds of scientists, engineers, and managers over more than a decade. Essential contributions to the successful operation of SAM on Mars and the acquisition of SAM data were provided by the SAM development, operations, and test bed teams. The authors gratefully thank the SAM and MSL teams that have contributed in numerous ways to obtain the data that enabled this scientific work. We also thank NASA for the support of the development of SAM, SAM data analysis, and the continued support of the Mars Science Laboratory mission. The contribution of F. Lefèvre was supported by the Programme National de Planétologie (PNP). R. Navarro‐Gonzalez acknowledges support from the Universidad Nacional Autónoma de México (PAPIIT IN111619). LPI is operated by USRA under a cooperative agreement with the Science Mission Directorate of the National Aeronautics and Space Administration. We thank members of the SAM and larger MSL team for insightful discussions and support. In particular, we thank R. Becker and R. O. Pepin for careful review of data analysis and interpretation. We thank M. D. Smith for discussion of CRISM CO measurements. We thank A. Brunner, M. Johnson, and M. Lefavor for their development of customized data analysis tools used here and in other SAM publications.Peer reviewedPublisher PD

Searching for Reduced Carbon on the Surface of Mars: The SAM Combustion Experiment

The search for reduced carbon has been a major focus of past and present missions to Mars. Thermal evolved gas analysis was used by the Viking and Phoenix landers and is currently in use by the Sample Analysis at Mars (SAM) instrument suite on the Mars Science Laboratory (MSL) to characterize volatiles evolved from solid samples, including those associated with reduced organic species. SAM has the additional capability to perform a combustion experiment, in which a sample of Mars regolith is heated in the presence of oxygen and the composition of the evolved gases is measured using quadrupole mass spectrometry (QMS) and tunable laser spectrometry (TLS) [1]. Organics detection on the Martian surface has been complicated by oxidation and destruction during heating by soil oxidants [2], including oxychlorine compounds, and terrestrial organics in the SAM background contributed by one of the SAM wet chemistry reagents MTBSTFA (N-Methyl-N-tertbutyldimethylsilyl- trifluoroacetamide) [3,4]. Thermal Evolved Gas Analysis (TEGA) results from Phoenix show a mid temperature CO2 release between 400 C - 680 C speculated to be carbonate, CO2 adsorbed to grains, or combustion of organics by soil oxidants [5]. Low temperature CO2 evolutions (approx. 200 C - 400 C) were also present at all three sites in Gale Crater where SAM Evolved Gas Analysis (EGA) was performed, and potential sources include combustion of terrestrial organics from SAM, as well as combustion and/or decarboxylation either indigenous martian or exogenous organic carbon [4,6]. By performing an experiment to intentionally combust all reduced materials in the sample, we hope to compare the bulk abundance of CO2 and other oxidized species evolved by combustion to that evolved during an EGA experiment to estimate how much CO2 could be contributed by reduced carbon sources. In addition, C, O, and H isotopic compositions of CO2 and H2O measured by TLS can contribute information regarding the potential sources of these volatiles

Martian Chlorobenzene Identified by Curiosity in Yellowknife Bay: Evidence for the Preservation of Organics in a Mudstone on Mars

The Sample Analysis at Mars (SAM) instrument on the Curiosity rover is designed to determine the inventory of organic and inorganic volatiles thermally evolved from solid samples using a combination of evolved gas analysis (EGA), gas chromatography mass spectrometry (GCMS), and tunable laser spectroscopy. The first sample analyzed by SAM at the Rocknest (RN) aeolian deposit revealed chlorohydrocarbons derived primarily from reactions between a martian oxychlorine phase (e.g. perchlorate) and terrestrial carbon from N-methyl-N-(tert-butyldimethylsilyl) trifluoroacetamide (MTBSTFA) vapor present in the SAM instrument background. No conclusive evidence for martian chlorohydrocarbons in the RN sand was found. After RN, Curiosity traveled to Yellowknife Bay and drilled two holes separated by 2.75 m designated John Klein (JK) and Cumberland (CB). Analyses of JK and CB by both SAM and the CheMin x-ray diffraction instrument revealed a mudstone (called Sheepbed) consisting of approx.20 wt% smectite clays, which on Earth are known to aid the concentration and preservation of organic matter. Last year at LPSC we reported elevated abundances of chlorobenzene (CBZ) and a more diverse suite of chlorinated hydrocarbons including dichloroalkanes in CB compared to RN, suggesting that martian or meteoritic organic compounds may be preserved in the mudstone. Here we present SAM data from additional analyses of the CB sample and of Confidence Hills (CH), another drill sample collected at the base of Mt. Sharp. This new SAM data along with supporting laboratory analog experiments indicate that most of the chlorobenzene detected in CB is derived from martian organic matter preserved in the mudstone

Mars methane detection and variability at Gale crater

Reports of plumes or patches of methane in the martian atmosphere that vary over monthly time scales have defied explanation to date. From in situ measurements made over a 20-month period by the tunable laser spectrometer of the Sample Analysis at Mars instrument suite on Curiosity at Gale crater, we report detection of background levels of atmospheric methane of mean value 0.69 ± 0.25 parts per billion by volume (ppbv) at the 95% confidence interval (CI). This abundance is lower than model estimates of ultraviolet degradation of accreted interplanetary dust particles or carbonaceous chondrite material. Additionally, in four sequential measurements spanning a 60-sol period (where 1 sol is a martian day), we observed elevated levels of methane of 7.2 ± 2.1 ppbv (95% CI), implying that Mars is episodically producing methane from an additional unknown source

The imprint of atmospheric evolution in the D/H of Hesperian clay minerals on Mars

The deuterium to hydrogen (D/H) ratio in strongly bound water or hydroxyl groups in ancient martian clays retains the imprint of the water of formation of these minerals. Curiosity’s Sample Analysis at Mars (SAM) experiment measured thermally evolved water and hydrogen gas released between 550°C and 950°C from samples of Hesperian era Gale crater smectite to determine this isotope ratio. The D/H value is 3.0 (±0.2) times the ratio in Standard Mean Ocean Water (SMOW). The D/H ratio in this ~3 billion year old mudstone that is half that of the present martian atmosphere but substantially higher than that expected in very early Mars indicates an extended history of hydrogen escape and desiccation of the planet