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Possible Detection of Perchlorates by the Sample Analysis at Mars (SAM) Instrument: Comparison with Previous Missions

The first chemical analysis of soluble salts in the soil was carried out by the Phoenix Lander in the Martian Arctic [1]. Surprisingly, chlorine was present as magnesium or calcium perchlorate at 0.4 to 0.6 percent. Additional support for the identification of perchlorate came from the evolved gas analysis which detected the release of molecular oxygen at 350-550C [1]. When Mars-like soils from the Atacama Desert were spiked with magnesium perchlorate (1 percent) and heated using the Viking GC-MS protocol, nearly all the organics were combusted but a small amount was chlorinated, forming chloromethane and dichloromethane [2]. These chlorohydrocarbons were detected by the Viking GC-MS experiments when the Martian soil was analyzed but they were considered to be terrestrial contaminants [3]. Reinterpretation of the Viking results suggests <0.1 percent perchlorate and ppm levels of organic carbon at landing site 1 and 2 [2]. The suggestion of perchlorate in the Viking sites [2] has been challenged on the grounds that the detected compounds (CH3Cl and CH2Cl2) were carried from Earth [4]. Recently the Sample Analysis at Mars (SAM) instrument on board the Mars Science Laboratory (MSL) ran four samples from an aeolian bedform named Rocknest. The samples analyzed were portioned from the fifth scoop at this location. The samples were heated to 835C at 35C/min with a He flow. The SAM QMS detected a major oxygen release (300-500C) [5], coupled with the release of chlorinated hydrocarbons (chloromethane, dichloromethane, trichloromethane, and chloromethylpropene) detected both by SAM QMS and GC-MS derived from known Earth organic contaminants in the instrument [6]. Calcium perchlorate appears to be the best candidate for evolved O2 in the Rocknest samples at this time but other Cl species (e.g., chlorates) are possible and must be evaluated. The potential detection of perchlorates in Rocknest material adds weight to the argument that both Viking Landers measured signatures of perchlorates. Even if the source of the organic carbon detected is still unknown, the chlorine source was likely Martian. Two mechanisms have been hypothesized for the formation of soil perchlorate: (1) Atmospheric oxidation of chlorine; and (2) UV photooxidation of chlorides catalyzed by mineral catalysts [7]. The presence of soil perchlorates in the Martian surface has important implications for the detection of organics [2], carbonates [8] and nitrates [9] by SAM.

Navarro-Gonzalex, Rafael

Diverse organic molecules on Mars revealed by the first SAM TMAH experiment

The search for organic matter on Mars has rapidly evolved in the past decade with simple aromatic, S-heterocycles, and aliphatic organic molecules detected in Gale crater. We report the in situ detection of >20 organic molecules from clay-bearing sandstones in the ~3.5-billion-year-old Knockfarrill Hill member of Glen Torridon, Gale crater, by the Sample Analysis at Mars instrument suite onboard the Curiosity rover. These molecules were liberated by the onboard tetramethylammonium hydroxide wet chemistry experiment. Diverse thermochemolysis products, including benzothiophene, methyl benzoate, and single and dicyclic aromatic molecules were released and detected by evolved gas analysis and gas chromatography-mass spectrometry. Results indicate the experiment successfully released molecules preserved in ancient macromolecular or free organic matter within Martian bedrock despite ~3.5 billion years of diagenesis and radiation exposure.

Amy J Williams

Detection of Reduced Nitrogen Compounds at Rocknest Using the Sample Analysis At Mars (SAM) Instrument on the Mars Science Laboratory (MSL)

The Sample Analysis at Mars (SAM) instrument suite on the Mars Science Laboratory (MSL) Curiosity Rover detected nitrogen-bearing compounds during the pyrolysis of Rocknest material at Gale Crater. Hydrogen cyanide and acetonitrile were identified by the quadrupole mass spectrometer (QMS) both in direct evolved gas analysis (EGA). SAM carried out four separate analyses from Rocknest Scoop 5. A significant low temperature release was present in Rocknest runs 1-4, while a smaller high temperature release was also seen in Rocknest runs 1-3. Here we evaluate whether these compounds are indigenous to Mars or a pyrolysis product resulting from known terrestrial materials that are part of the SAM derivatization.

Sample Analysis at Mars

The Search for Organic Compounds of Martian Origin in Gale Crater by the Sample Analysis at Mars (SAM) Instrument on Curiosity

One of the key objectives of the Mars Science Laboratory rover and the Sample Analysis at Mars (SAM) instrument suite is to determine the inventory of organic and inorganic volatiles in the atmosphere and surface regolith and rocks to help assess the habitability potential of Gale Crater. The SAM instrument on the Curiosity rover can detect volatile organic compounds thermally evolved from solid samples using a combination of evolved gas analysis (EGA) and gas chromatography mass spectrometry (GCMS) (Mahaffy et al. 2012). The first solid samples analyzed by SAM, a scoop of windblown dust and sand at Rocknest, revealed several chloromethanes and a C4-chlorinated hydrocarbon derived primarily from reactions between a martian oxychlorine phase (e.g. perchlorate) and terrestrial carbon from N-methyl-N-(tertbutyldimethylsilyl)- trifluoroacetamide (MTBSTFA) vapor present in the SAM instrument background (Glavin et al. 2013). After the analyses at Rocknest, Curiosity traveled to Yellowknife Bay and drilled two separate holes in a fluvio-lacustrine sediment (the Sheepbed unit) designated John Klein and Cumberland. Analyses of the drilled materials by both SAM and the CheMin X-Ray Diffraction instrument revealed a mudstone consisting of ~20 wt% smectite clays (Ming et al. 2013; Vaniman et al. 2013), which on Earth are known to aid the concentration and preservation of organic matter. Oxychlorine compounds were also detected in the Sheepbed mudstone during pyrolysis; however, in contrast to Rocknest, much higher levels of chloromethanes were released from the Sheepbed materials, suggesting an additional, possibly martian source of organic carbon (Ming et al. 2013). In addition, elevated abundances of chlorobenzene and a more diverse suite of chlorinated alkanes including dichloropropane and dichlorobutane detected in Cumberland compared to Rocknest suggest that martian or meteoritic organic carbon sources may be preserved in the mudstone (Freissinet et al. 2013). Chloromethane and dichloromethane were also identified after thermal volatilization of the surface soils by the GCMS instruments at the Viking landing sites, although no other chlorinated hydrocarbons were reported (Biemann et al. 1977). Here we focus on the origin of the chlorinated hydrocarbons detected in the Sheepbed mudstone by SAM and the implications for the preservation of organic matter in near-surface materials on Mars.

Mars Curiosity Rover

Evidence for Smectite Clays from MSL SAM Analyses of Mudstone at Yellowknife Bay, Gale Crater, Mars

Drilled samples of mudstone from the Sheepbed unit at Yellowknife Bay were analyzed by MSL instruments including the Sample Analysis at Mars (SAM) and Chemistry and Mineralogy (CheMin) instruments in MSL's Analytical Laboratory. CheMin analyses revealed the first in situ X-ray diffraction based evidence of clay minerals on Mars, which are likely trioctahedral smectites (e.g., saponite) and comprise approx 20% of the mudstone sample (e.g., Bristow et al., this meeting). SAM analyses, which heated the mudstone samples to 1000 C and monitored volatiles evolved to perform in situ evolved gas analysis mass spectrometry (EGA-MS), resulted in a H2O trace exhibiting a wide evolution at temperatures < 500 C, and an evolution peak at higher temperatures near approx 750 C. The low temperature H2O evolution has many potential contributors, including adsorbed H2O, smectite interlayer H2O, and structural H2O/OH from bassanite and akaganeite (identified by CheMin) and H2O/OH from amorphous phases in the sample. The high temperature H2O is consistent with the evolution of H2O from the dehydroxylation of the smectite clay mineral. Comparison to EGA-MS data collected under SAM-like conditions on a variety of clay mineral reference materials indicate that a trioctahedral smectite, such as saponite, is most consistent with the high temperature H2O evolution observed. There may also be SAM EGA-MS evidence for a small high temperature H2O evolution from scoop samples from the Yellowknife Bay Rocknest sand shadow bedform. As in the mudstone samples, this evolution may indicate the detection of smectite clays, and the idea that minor clays may be present in Rocknest materials that could be expected to be at least partially derived from local sources is reasonable. But, because smectite clays were not definitively observed in CheMin analyses of Rocknest materials, they must be present at much lower abundances than the approx 20% observed in the mudstone samples. This potential detection underscores the complementary nature of the MSL CheMin and SAM instruments for investigations of martian sample mineralogy. Information on the nature of Yellowknife Bay clay minerals may also be available from the detection of H2 evolved during SAM EGA-MS at high temperature. A likely source of at least some of this H2 is H2O evolved from the smectite clays at high temperature, and it is possible these evolutions can be used in a similar fashion to high temperature H2O releases to provide constraints on the clay minerals in a sample. In addition, the D/H of this high temperature H2, as well as the H2O, can be derived from SAM MS and Tunable Laser Spectrometer (TLS) data, respectively. These D/H values may help to inform the provenance of high and low temperature water evolved from martian samples

McAdam, Amy

Effect of Solution pH and Chloride Concentration on Akaganeite Precipitation: Implications for Akaganeite Formation on Mars

Akaganeite (Beta-FeOOH, chloride-containing Fe(III) (hydr)oxide) has been recently discovered on the surface of Mars by the Mars Science Laboratory Curiosity rover in Yellowknife Bay, Gale Crater, Mars [1] and from orbit by the Mars Reconnaissance Orbiter in Robert Sharp crater and Antoniadi basin [2]. However, the mechanism and aqueous environmental conditions of akaganeite formation (e.g., pH and chloride concentration) remain unknown. We have investigated formation of akaganeite through Fe(III) hydrolysis at variable initial pH and chloride concentrations. The formed Fe(III) precipitates were characterized by instruments similar to instruments on Mars robotic spacecraft. Syntheses were performed through hydrolysis of Fe(III) perchlorate with addition of Na cloride (Fe/Cl ratio between 0.5 and 5) and at initial pH of 1.5, 2, 4, 6 and 8 at 90degC. X-ray diffraction analysis revealed formation of akaganeite alone or in mixture with goethite, hematite and ferrihydrite at all initial pHs and Fe/Cl ratio between 0.5 and 2 while akaganeite precipitated only at pH 1.5 and Fe/Cl greater than2. Chloride content of akaganeite was affected by initial pH and decreased from 20-60 mg/g at pH 1.5 to less than 0.1 mg/g at pH 8. The synthesized akaganeite samples were also characterized by Mössbauer and infrared spectroscopy and volatiles were analysed by thermal and evolved gas analysis. The obtained characterization data will be compared to published data from rover and orbital missions [1-3] to determine martian akaganeite composition, crystallinity and formation conditions.

Peretyazhko, T. A.

X-Ray Diffraction and Reflectance Spectroscopy of Murchison Powders (CM2) After Thermal Analysis Under Reducing Conditions to Final Temperatures Between 300 and 1300°c

The asteroids Ryugu and Bennu have spectral characteristics in common with CI/CM type carbonaceous chondrites and are target bodies for JAXA’s Hayabusa2 and NASA’s OSIRIS-Rex missions, respectively. Analog studies, based primarily on the Murchison CM2 chondrite, provide a pathway to separate spectral properties resulting space weathering from those inherent to parent-body, mineralogy, chemistry, and processes. Ryugu shares spectral properties with thermally metamorphosed and partly dehydrated CI/CM chondrites. We have undertaken a multidisciplinary study of the thermal decomposition of Murchison powder samples as an analog to metamorphic process that may have occurred on Ryugu. Bulk analyses include thermal And evolved gas analysis, X-ray diffraction (XRD), and VIS-NIR and Mössbauer spectroscopy; micro- to nanoscale analyses included scanning and transmission electron microscopy and electron probe micro analysisWe report here XRD and VIS-NIR analyses of pre- and post-heated Murchison powders, and in a companion paper report results from multiple electron beam techniques.

Morris, R. V.

Tandem pyrolysis evolved gas–gas chromatography–mass spectrometry

Analysis of byproducts from thermal degradation of polymer materials provides a wealth of information about a materials’ composition, thermal stability, degradation mechanisms, and kinetics. However, regardless of the instrumentation used, only limited information is obtainable from a single experiment. Microfurnace technology, when interfaced to a gas chromatography-mass spectrometry (GC-MS), can be used to obtain both thermal and chemical information via evolved gas analysis-MS (EGA-MS) and GC-MS analysis modes. While both EGA-MS and Py-GC-MS are valuable when characterizing polymer materials, at least two experiments on distinct samples are required, which can be a liability for clear interpretation of results from inhomogeneous samples. Here, we seek to overcome this limitation by combining EGA-MS and Py-GC-MS modes in a single experimental setup. Further, this was done by developing new gas line modifications to allow for tandem Pyrolysis Evolved Gas-Gas Chromatography-Mass Spectrometry (Py/EG-GC-MS) analysis. Verification of Py/EG-GC-MS analysis was performed using a polystyrene standard. Results demonstrate successful Py/EG-GC-MS analysis for the first-time showing the potential of these modifications for application in areas where sample is limited or direct correlation of products to the thermal profile is desirable such as in forensics or product-specific kinetics.

36 MATERIALS SCIENCE

Carbon Limited Soils of Iceland: Analogs for Identifying Carbon-Mineral Interactions in Gale Crater, Mars Surface Materials

The Mars Science Laboratory’s Curiosity rover mission to Gale Crater, Mars has a goal to search for organic carbon and corresponding evidence of ancient microbiology preserved in clay mineral-rich sedimentary deposits [1]. No clear correlation of clay mineral (smectite) abundances with the Sample Analysis at Mars (SAM) carbon detections (up to 2000 ppm C) [2] has been established, suggesting other phases may preserve organic C in martian sediments. Terrestrial volcanic glass soils can accumulate C due to the C-complexing abilities of poorly crystalline Al- and Fe-oxyhydroxides [3]. The Xray amorphous component (20 to 73 wt. %) in Gale Crater materials [4,5] has received little consideration regarding organic C preservation in Gale Crater. The objectives of this work are to 1) Evaluate C content and level of soil development of basaltic glass-bearing Icelandic soils to determine the role that poorly crystalline phases have in complexing organic C in carbon limited soils and 2) Determine if evolved gas analysis (EGA) of well-characterized Mars analog basaltic materials from Iceland can be used to interpret SAM data to understand the nature of organic-C mineral/geochemical associations in Gale materials.

B. Sutter

Light Isotopes and Trace Organics Analysis of Mars Samples with Mass Spectrometry

Precision measurement of light isotopes in Mars surface minerals and comparison of this isotopic composition with atmospheric gas and other, well-mixed reservoirs such as surface dust are necessary to understand the history of atmospheric evolution from a possibly warmer and wetter Martian surface to the present state. Atmospheric sources and sinks that set these ratios are volcanism, solar wind sputtering, photochemical processes, and weathering. Measurement of a range of trace organic species with a particular focus on species such as amino acids that are the building blocks of terrestrial life are likewise important to address the questions of prebiotic and present or past biological activity on Mars. The workshop topics "isotopic mineralogy" and "biology and pre-biotic chemistry" will be addressed from the point of view of the capabilities and limitations of insitu mass spectrometry (MS) techniques such as thermally evolved gas analysis (TEGA) and gas chromatography (GC) surface experiments using MS, in both cases, as a final chemical and isotopic composition detector. Insitu experiments using straightforward adaptations of existing space proven hardware can provide a substantial improvement in the precision and accuracy of our present knowledge of isotopic composition both in molecular and atomic species in the atmosphere and those chemically bound in rocks and soils. Likewise, detection of trace organic species with greatly improved sensitivity from the Viking GCMS experiment is possible using gas enrichment techniques. The limits to precision and accuracy of presently feasible insitu techniques compared to laboratory analysis of returned samples will be explored. The insitu techniques are sufficiently powerful that they can provide a high fidelity method of screening samples obtained from a diverse set of surface locations such as the subsurface or the interior of rocks for selection of those that are the most interesting for return to Earth.

Mahaffy, P.

The Combustion Experiment on the Sample Analysis at Mars (SAM) Instrument Suite on the Curiosity Rover

The combustion experiment on the Sample Analysis at Mars (SAM) suite on Curiosity will heat a sample of Mars regolith in the presence of oxygen and measure composition of the evolved gases using quadrupole mass spectrometry (QMS) and tunable laser spectrometry (TLS). QMS will enable detection of combustion products such as CO, CO2, NO, and other oxidized species, while TLS will enable precise measurements of the abundance and carbon isotopic composition (delta(sup 13)C) of the evolved CO2 and hydrogen isotopic composition (deltaD) of H2O. SAM will perform a two-step combustion to isolate combustible materials below approx.550 C and above approx.550 C. The combustion experiment on SAM, if properly designed and executed, has the potential to answer multiple questions regarding the origins of volatiles seen thus far in SAM evolved gas analysis (EGA) on Mars. Constraints imposed by SAM and MSL time and power resources, as well as SAM consumables (oxygen gas), will limit the number of SAM combustion experiments, so it is imperative to design an experiment targeting the most pressing science questions. Low temperature combustion experiments will primarily target the quantification of carbon (and nitrogen) contributed by SAM wet chemistry reagants MTBSTFA (N-Methyl-N-tert-butyldimethylsilyltrifluoroacetamide) and DMF (Dimethylformamide), which have been identified in the background of blank and sample runs and may adsorb to the sample while the cup is in the Sample Manipulation System (SMS). In addition, differences between the sample and "blank" may yield information regarding abundance and delta(sup 13)C of bulk (both organic and inorganic) martian carbon. High temperature combustion experiments primarily aim to detect refractory organic matter, if present in Cumberland fines, as well as address the question of quantification and deltaD value of water evolution associated with hydroxyl hydrogen in clay minerals.

Mars

Thermal and evolved gas analyzer

The Thermal and Evolved Gas Analyzer (TEGA) instrument will perform calorimetry and evolved gas analysis on soil samples collected from the Martian surface. TEGA is one of three instruments, along with a robotic arm, that form the Mars Volatile and Climate Survey (MVACS) payload. The other instruments are a stereo surface imager, built by Peter Smith of the University of Arizona and a meteorological station, built by JPL. The MVACS lander will investigate a Martian landing site at approximately 70 deg south latitude. Launch will take place from Kennedy Space Center in January, 1999. The TEGA project started in February, 1996. In the intervening 24 months, a flight instrument concept has been designed, prototyped, built as an engineering model and flight model, and tested. The instrument performs laboratory-quality differential-scanning calorimetry (DSC) over the temperature range of Mars ambient to 1400K. Low-temperature volatiles (water and carbon dioxide ices) and the carbonates will be analyzed in this temperature range. Carbonates melt and evolve carbon dioxide at temperatures above 600 C. Evolved oxygen (down to a concentration of 1 ppm) is detected, and C02 and water vapor and the isotopic variations of C02 and water vapor are detected and their concentrations measured. The isotopic composition provides important tests of the theory of solar system formation.

Williams, M. S.

Oxychlorine Species on Mars: The Gale Crater Story

Comparing data from the Alpha- Particle X-Ray Spectrometer (APXS) and the Sample Analysis at Mars (SAM) instruments on MSL reveals a strong linear correlation between chlorine and oxygen, further demonstrating the presence of oxychlorine species in Gale Crater and, very likely, globally on Mars. Perchlorate was first discovered on Mars by the Microscopy, Electrochemistry, and Conductivity Analyzer (MECA) instrument on the Phoenix lander in 2008. Current hypotheses suggest that the formation of oxychlorine species such as perchlorate or chlorate is a global process and that these species should be globally distributed on Mars [e.g. 2-4]. To date, the SAM and Chemistry and Mineralogy (CheMin) instruments on MSL have analyzed one scooped sample of aeolian material (Rocknest [RN]), and four drilled samples (John Klein [JK], Cumberland [CB], Windjana [WJ], and Confidence Hills [CH]). The APXS instrument has also investigated the same or very similar samples. Although not definitively identified, oxychlorine species have been proposed to explain releases of O2, HCl, and chlorinated hydrocarbon species detected by evolved gas analysis (EGA) with the SAM instrument. We report a strong linear correlation between wt. % Cl detected by APXS and moles O2 detected by SAM during pyrolysis, indicating the presence of oxychlorine species in Gale Crater.

Archer, P. D., Jr.

Evidence for Partially Chloritized Smectite in Gale Crater, Mars, and Implications for Diagenesis

Phyllosilicates are an important mineral group found in ancient (~3.5-4.1 Gyr old) martian terrains because they are a marker of water-rock interactions and can help constrain aqueous conditions (e.g., pH, salinity, temperature) and, thus, identify habitable environments. Orbital visible/short-wave infrared (VSWIR) data demonstrate that smectite is the most abundant type of phyllosilicate on Mars, followed by chlorite [e.g., 1]. The geologic settings in which phyllosilicates are found provide important clues into their formation. Smectite has been identified in abundances of up to ~30 wt.% in early Hesperian-aged fluvial-lacustrine sedimentary rocks in Gale crater using the CheMin X-ray diffractometer on the Mars Science Laboratory Curiosity rover [e.g., 2-6]. CheMin XRD patterns and evolved water measured by the Sample Analysis at Mars (SAM) instrument suite show the structure of smectite changes from trioctahedral Fe(II)-bearing smectite at the base of the section to dioctahedral nontronite and montmorillonite ~400 m up section in the Glen Torridon valley where orbital VSWIR show evidence of Fe/Mg smectite. Most of the smectite identified by CheMin is collapsed (i.e., lacking substantial interlayer H2O) based on basal spacings at 10 Å. Fe(II) saponite found in two drill targets at the base of the section in Yellowknife Bay, however, suggest the smectite is expanded. The XRD pattern of the “Cumberland” drill target has a peak at 13.5 Å, whereas the “John Klein” drill target has a peak at 10 Å and a shoulder extending to higher d-spacings (Fig. 1) [2]. A possible explanation for this expanded structure is partial chloritization of the interlayer site caused by the precipitation of small domains of brucite-like sheets [e.g., 7,8]. Here, we synthesize smectite with different degrees of chloritization and analyze the products via XRD, evolved gas analysis (EGA), and VSWIR to determine whether chloritized smectite on Mars can be recognized with these techniques.

E B Rampe

Examining Weathering of Magnesite in an Arid Environment: Implications For Jezero Crater

Introduction:Orbiter data indicatethe presence of carbonates in severallocations on the surface of Mars[1],but Jezero crater, landing site of the Perseverancerover,is the only known location where carbonatesap-pear coincident with evidence of fluvialand lacustrineactivity [2].On Earth, carbonates in close proximity to these paleoenvironments mayindicatethe presence of past microbial life,like stromatolites[3], that could re-sult inbiosignatures [2]. However,in other cases,car-bonates can also form throughthe alteration of mafic materialwiththe introductionof carbonic acid[4].Hy-drated magnesites have also been found in evaporative environments along lake shores, and in playas[5,6,7].Correctly interpreting past carbonates on Mars is there-fore critical in the search for past signs of life. In Jezero crater,both thenorthernand western fans haveMg-rich carbonates intermixed with olivine-rich material[8].According to CRISM data, magnesite(MgCO3), along with hydromagnesite(Mg5(CO3)4(OH)2•4H2O), arepotential candidatesfor these Mg-carbonates [2]. Considering the spatial con-text with olivine,there aremultiplepotential explana-tions for the presence ofMg-carbonatesin this locationincludingin-situformation via alterationof olivine-rich materialwith carbonic acid,transportationfrom farther up in the watershed, or precipitation of lacustrine car-bonates[2]. The formation of hydromagnesite rather than magnesite is favored when Mg2+saturated solutions have a high CO32-/HCO3-ratio, which, on Earth, is thought to be caused byinflow of groundwater [4]. Additionally, Mg-carbonates tend to precipitate under high pH condi-tions and are unstable at lower pH conditions [5]. Hy-dromagnesite is stable at atmospheric CO2pressure and temperature conditions common to most Earth surface environments [9]. However, it is subject to transfor-mation to magnesite after dehydration and concomitant brucite formation or dissolution and reprecipitation [10].Previousresearch suggests that hydrated car-bonates, including hydromagnesite, can formas weath-ering productsof mafic minerals in the presenceof H2O and CO2in subfreezing temperatures and would not de-hydrate under Martian atmospheric conditions [11,12].It is critical to understand the formation conditions of Mg-carbonatesbecause of the different implications for the past history of Martian environments. Therefore, in this work we are investigating the weathering of Mg-carbonatesin arid environments to helpbetter understand Mg-carbonates in Jezero crater. Study Area:The Ala-Mar Mines(East and West)near Ely, NVare the site ofmultiple magnesitedepositsfound within a calcareous tuff formationthat overlies Tertiary aged volcanic rocks.Here,magnesiteis formed via the alteration of the calcareous tuff and occurs innodules, veins,and lenses[13]. Previous work suggests magnesite deposits are associated with faults [13]. Within the West Mine, magnesite can be found in two maincontexts: (1) relatively circular zones of cauli-flower-like material found within (2) a more massivelensthat is heavily fractured on the surface.Methods.Samplesof both the cauliflower texture and more massive materialwere collectedat Ala Mar West Mine. Both samples were thenpowdered, sieved and analyzed with an inXitu Terra Portable XRD. The program QualX was used to identify potential mineral phases [14].Both samples were also optically inspected using 10x and 20x hand lenses.Figure 1. XRD patterns for the cauliflower magnesite (top) and massive magnesite (bottom). Ongoing and future work on the samples discussed above includes scanning electron microscopy (SEM), electron microprobe analysis (EMPA), and near-infra-red spectroscopy to determine whether hydromagnesite is present. Separation and analysis of the clay-size frac-tionby XRD will helpto better identify any phyllosili-cate phases present. Results and Discussion:Both textures are a white to light tan with a porcelain luster on weathered sur-faces, along with minor iron staining in some areas. Likewise, both textures are white with a porcelain luster on fresh surfaces. When broken apart, the massive mag-nesite shows macroscopic crystals, unlike the cauli-flower magnesite. XRD analysis shows that both samples have high concentrationsof magnesite with lesser amounts of thecarbonatemineral huntite(Mg3Ca(CO3)4; Figure1).The more massive samplecontainsa serpentine-groupmineral,with lizardite being apotential candidate. The cauliflower sample has several minor peaks that may correspond to hydromagnesite(Figure 1), although more work is needed to confirm this.Additionally, thecauliflower deposits closely resemble hydromagnesite deposits found in southwestern Turkey, formed via mi-crobialites[15].As such, it is likely that moreaqueous alterationor weatheringis occurring at the locations where the cauliflower magnesite is present. However, additional field work will need to be conducted to con-firm this hypothesis. Conclusions and Future Work:Future work will include field mapping of fault locations andadditional samplingof the different magnesite types as well as of the calcareous tuffmaterial.We will also look specifi-cally for potential weathering products of magnesite in this arid location, which may yield important insight into the Mg-carbonates located in Jezero crater. XRD analyses on aPANalytical XRDusing non-ambient stages will be used to investigate the stability of hydro-magnesiteat different humiditiesand temperatures, which has implications for samples to bereturned to Earth in the future. Additionally, thermal and evolved gas analysis of magnesite and hydromagnesite will be compared to results from Gale Craterto help interpret the mineralogy inthat location[16]. The results of this research will further ourunderstanding of carbonate for-mationin volcanic settingsandtheirweathering pro-cessesin arid environments. Acknowledgments:We acknowledge funding for this research from Jacobs Technology at the Johnson Space Center.We would also like to thank Ngoc Luu, Christopher Adcock, Richard Allanson, and the rest of the UNLV Soil Science Teamfor their continued sup-portwith troubleshooting and otherlab work. References:[1] Ehlmann, B.L., and Edwards, C.S. (2014) Annual Review of Earth and Planetary Sci., 42, 291–315. [2] Horgan, B.H.N., et al. (2020) Icarus, 339, 113526. [3] Bosak, T., et al. (2013) Annual Review of Earth and Planetary Sci, 41, 21–44. [4] Pohl, W.L. (1989) Gebriider Borntraege, 28, 1-13. [5] Müller, G., et al. (1972) Die Naturwissenschaften, 59, 158–164. [6] Walter, M.R., et al. (1973) Journal of Sedimentary Pe-trology, 43, 1021–1030. [7] Braithwaite, C.J.R., and Zedef, V. (1994) Sedimentary Geology, 92, 1–5. [8] Goudge, T.A., et al. (2015) JGR: Planets, 120, 775–808. [9] Langmuir, D. (1965) Journal of Geology, 73, 730–754. [10] Zhang, P., et al. (2000) Applied Geo-chem., 286, 1748–1753. [11] Calvin, W.M., et al. (1994) JGR, 99, 14659-14675. [12]Russell, M.J., et al. (1999) Journal of the Geological Society of London, v. 156, p. 869–888. [13] Faust, G.T., and Callaghan, E. (1948) GSA Bulletin, 59, 11–74. [14] Altomare, A., et al. (2015) J. of Applied Crystallography, 48, 598–603. [15] Zedef, V.,et al. (2000) Economic Geology, 95, 429–445. [16] Leshin, L.A. et al., (2013) Science, 341, 1–9

A W Provow

Investigation of the Glen Torridon Clay-Bearing Unit and Overlying Greenheugh Pediment by the Sample Analysis at Mars Instrument Suite

Exploring the Glen Torridon (GT) clay-bearing unit in Gale crater has long been a prime goal for the Mars Science Laboratory (MSL) because of spectral signatures of smectite identified from orbit. Smectite clay minerals can indicate habitable environments [1,2] and possibly facilitate the preservation of organic compounds [e.g., 3-7].Also, sulfate-bearing layers overlie GT and this sequence may record a large-scale change in aqueous conditions overtime [8].The Sample Analysis at Mars (SAM) instrument suitehas been essential in understanding volatile-bearing phases in Gale crater materials. SAM EGA has detected H2O, CO2, O2, H2, SO2, H2S, HCl, NO, and other trace gases, including organic fragments, evolved from many samples on heating. The identity and evolution temperature of evolved gases can support mineral detection by CheMin instrument X-ray diffraction (XRD)and place constraints on trace volatile-bearing phases, clay mineral compositions, and X-ray amorphous materials. In GT, SAM analyzed the sample Kilmarie (KM) from the Jura member, Glen Etive (GE), Mary Anning (MA) and Groken (GR)from the Knockfarril Hill member (KHm), Glasgow (GG) and Hutton (HU) from the fractured Intermediate Unit (fIU), and Edinburgh (EB) from the Stimson formation rocks of the Greenheugh Pediment (GP). The Jura, KHm and fIU are all members of the Murray formation. HU was sampled near the basal Siccar Point group (SPg) unconformity between the fIU and GP, in an area that exhibits a brighter tone and differences in geochemistry compared to Murray materials down-section [9,10]. CheMin XRD of most samples (except for HU and EB)showed large abundances of smectite clay minerals (~25-35%) and all samples showed X-ray amorphous materials and relatively low amounts of well-crystalline hematite[11]. SAM evaluated mineralogy through evolved gas analysis mass spectrometry (EGA) while detailed organic chemistry of several samples was examined by pyrolysis gas chromatography mass spectrometry and wet chemistry experiments [12,13].Here we discuss data and interpretations from SAM EGA analyses.

Mars

Calibration and Sequence Development Status for the Sample Analysis at Mars Investigation on the Mars Science Laboratory

The measurement goals of the Sample Analysis at Mars (SAM) instrument suite on the "Curiosity" Rover of the Mars Science Laboratory (MSL) include chemical and isotopic analysis of organic and inorganic volatiles for both atmospheric and solid samples [1,2]. SAM directly supports the ambitious goals of the MSL mission to provide a quantitative assessment of habitability and preservation in Gale crater by means of a range of chemical and geological measurements [3]. The SAM FM combined calibration and environmental testing took place primarily in 2010 with a limited set of tests implemented after integration into the rover in January 2011. The scope of SAM FM testing was limited both to preserve SAM consumables such as life time of its electromechanical elements and to minimize the level of terrestrial contamination in the SAM instrument. A more comprehensive calibration of a SAM-like suite of instruments will be implemented in 2012 with calibration runs planned for the SAM testbed. The SAM Testbed is nearly identical to the SAM FM and operates in a ambient pressure chamber. The SAM Instrument Suite: SAM's instruments are a Quadrupole Mass Spectrometer (QMS), a 6-column Gas Chromatograph (GC), and a 2-channel Tunable Laser Spectrometer (TLS). Gas Chromatography Mass Spectrometry is designed for identification of even trace organic compounds. The TLS [5] secures the C, H, and O isotopic composition in carbon dioxide, water, and methane. Sieved materials are delivered from the MSL sample acquisition and processing system to one of68 cups of the Sample Manipulation System (SMS). 59 of these cups are fabricated from inert quartz. After sample delivery, a cup is inserted into one of 2 ovens for evolved gas analysis (EGA ambient to >9500C) by the QMS and TLS. A portion of the gas released can be trapped and subsequently analyzed by GCMS. Nine sealed cups contain liquid solvents and chemical derivatization or thermochemolysis agents to extract and transform polar molecules such as amino acids, nucleobases, and carboxylic acids into compounds that are sufficiently volatile to transmit through the GC columns. The remaining 6 cups contain calibrants. SAM FM Calibration Overview: The SAM FM calibration in the Mars chamber employed a variety of pure gases, gas mixtures, and solid materials. Isotope calibration runs for the TLS utilized 13C enriched C02 standards and 0 enriched CH4. A variety of fluorocarbon compounds that spanned the entire mass range of the QMS as well as C3-C6 hydrocarbons were utilized for calibration of the GCMS. Solid samples consisting of a mixture of calcite, melanterite, and inert silica glass either doped or not with fluorocarbons were introduced into the SAM FM cups through the SAM inlet funnel/tube system.

Mahaffy, Paul R.

Probing thermodynamics of radiogenic helium and defects in $δ$-plutonium alloys and interactions with adsorbed environmental gases

Differential scanning calorimetry coupled with simultaneous evolved gas analysis (DSC-EGA) on aged δ-Pu samples shows that most radiogenic helium remains trapped within the Pu matrix at temperatures very close to, or slightly above, the melting temperature. Our results indicate that helium release from 50-year-old δ-Pu occurs as a burst just below the melting temperature (>0.994 T m ), with subsequent pressure oscillations as temperature increases. Subordinate quantities of H 2 were also released along with helium. Here, the helium emission tails off and ceases above ~720 – 750°C. In a δ-Pu alloy aged 6 years, the initial helium burst occurs slightly above melting (~1.015 – 1.042 T m ), with a discrete, larger helium spike occurring between 670 and 686°C. The proximity of helium release to the liquidus transition presented challenges in the deconvolution of overlapping process enthalpies, the liquidus endotherm, and the exotherm resulting from bubble collapse, annealing and gas expulsion. Helium’s strong affinity for vacancy binding in a 2He-vac configuration is predicted by Density Functional Theory (DFT) modeling. The measured stored energy associated with the He release events in a 50-year-old δ alloy is on the order of ~ 10–11 J/g, which is significantly higher than stored energies measured in the sub-solidus regimes (~2 J/g) that are related to the solid-state annealing of processing- and radiation-induced defects. This implies that aged δ Pu alloys have a remarkable resilience to accommodate the lattice strain produced by the internal pressure of the helium bubbles and provides further insight into the thermodynamic behavior of aged δ Pu.

36 MATERIALS SCIENCE