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Stern, J. C.

Publications and source records attributed to Stern, J. C..

At least 19 records

Mineralogical and Geochemical Trends of the Murray Mudstones, Gale Crater: A Combined Sample Analysis at Mars-Evolved Gas Analyzer and Chemistry and Mineralogy Instrument Assessment

The Murray formation is predominantly composed of lacustrine mudstone that forms the basal layer of Aeolis Mons (informally Mt. Sharp) in Gale Crater, Mars. The Murray formation has distinct iron and sulfur mineralogical variation within its stratigraphy detectable by the Chemistry Mineralogy (Che-Min) instrument consisting of magnetite/hematite in the lower Murray and higher hematite, CaSO4, and smectite content in the upper Murray. The objectives of this work were to evaluate the Sample Analysis at Mars Evolved Gas Analyzer (SAM-EGA) data to 1) Determine what SAM-EGA-detectable phases correlate or do not correlate with the Murray mineralogical composition detected by CheMin and 2) Utilize CheMin/SAM results to propose possible formation scenarios for the observed Murray mudstone mineralogy.

Sutter, B.↗

Evolved Gas Analyses of Mudstones from the Vera Rubin Ridge

The Sample Analysis at Mars (SAM) instrument suite on the Mars Science Laboratory (MSL) rover has been essential in understanding volatile-bearing phases in Gale Crater materials. SAM’s evolved gas analysis mass spectrometry (EGA-MS) has detected H2O, CO2, O2, H2, SO2, H2S, HCl, NO, and other trace gases, including organic fragments, in many samples. The identity and evolution temperature of evolved gases can support CheMin instrument mineral detection and place constraints on trace volatile-bearing phases or phases difficult to characterize with X-ray diffraction (e.g., amorphous phases). For the past ~500 sols, MSL has been exploring the Vera Rubin Ridge (VRR), which exhibits a striking hematite signature in orbital remote sensing data, in order to understand the depositional and diagenetic history recorded in the rocks and how it relates to the underlying Murray Formation. Four rock samples were drilled, one from the Blunts Point Member (Duluth, DU), one from the Pettegrrove Point Member (Stoer, ST), and two from the Jura Member. The Jura Member displays differences in color, summarized as grey and red, and a key goal was to constrain the cause of this color difference and the associated implications for depositional or post-depositional conditions. To investigate, a grey (Highfield, HF) and a red (Rock Hall, RH) Jura sample were drilled. Here we will give an overview of results from SAM EGA-MS analyses of VRR materials, with some comparisons to analyses of samples of the underlying Murray.

McAdam, A. C.↗

NH4-Smectite, a Potential Source of N Compounds (NO) in SAM Analyses

Recent detection of nitrate by Curiosity's Sample Analysis at Mars (SAM) instrument suite in Gale Crater sediments on Mars at abundances up to ~600 mg/kg indicates that nitrogen fixation processes occurred in early Martian history. But little is known about other possible N reservoirs on Mars, including those that may contain reduced forms of fixed N (i.e., NH3, NH4+) in the mantle, crust and sediments. Specifically, fixed nitrogen (i.e. NH3, NH4+, NOx or N that is chemically bound to either inorganic or organic molecules and can be released by hydrolysis to form NH3 or NH4+) is useful to terrestrial living organisms Therefore, understanding whether reduced N compounds such as NH4+ are present in surface materials is important to assess habitability in the Martian environment. While these species generally have short photochemical lifetimes, nitrogen in this form may be sequestered and stabilized in the soil by inclusion of NH4+ in certain phyllosilicates.

Andrejkovičová, S.↗

Stable Isotope Fractionation in Titan Aerosol Formation

Stable isotope ratio measurements are a powerful tool used to understand both ancient and modern planetary processes. Instruments on the Cassini- Huygens spacecraft along with ground-based observations have measured several isotope pairs, including C-13/C-12 and N-15/N-14, in Titan's atmosphere. This includes isotopic measurements of the major atmospheric species, CH4 and N2, along with HCN, HC3N, C2H2. C2H6 and C4H2. However, the isotopic fractionation of Titan's organic aerosol has not conclusively been measured and therefore the effect of aerosol formation as an isotopic fractionation pathway in Titan's atmosphere has not been considered. Laboratory studies have measured the carbon and/or nitrogen isotopic fractionation of Titan aerosol analogs. [18] found that the carbon fractionation of photochemical organic aerosol analogs are more enriched in C-13. This enrichment in the aerosol analogs is opposite of what is predicted for photochemical products by the kinetic isotope effect. Additionally, both [16] and [18] found that the nitrogen fractionation in the organic aerosol analogs are opposite of what is observed in Titan's atmospheric N2 and HCN, with the aerosol analogs being a light nitrogen sink. Here we monitor the gas phase during photochemical aerosol analog production as a function of reaction time. In a recirculation experiment, the isotopic fractionation of carbon within the gas-phase products is measured as the CH4 reservoir is depleted. This allows us to monitor the isotopic fractionation pathway during photochemical aerosol analog formation.

Ugelow, M. S.↗

Large Sulphur Isotope Fractionations in Martian Sediments at Gale Crater

Variability in the sulfur isotopic composition in sediments can reflect atmospheric, geologic and biological processes. Evidence for ancient fluvio-lacustrine environments at Gale crater on Mars and a lack of efficient crustal recycling mechanisms on the planet suggests a surface environment that was once warm enough to allow the presence of liquid water, at least for discrete periods of time, and implies a greenhouse effect that may have been influenced by sulfur-bearing volcanic gases. Here we report in situ analyses of the sulfur isotopic compositions of SO2 volatilized from ten sediment samples acquired by NASA's Curiosity rover along a 13 km traverse of Gale crater. We find large variations in sulfur isotopic composition that exceed those measured for Martian meteorites and show both depletion and enrichment in S-34. Measured values of δS-34 range from -47 +/- 14% to 28 +/- 7%, similar to the range typical of terrestrial environments. Although limited geochronological constraints on the stratigraphy traversed by Curiosity are available, we propose that the observed sulfur isotopic signatures at Gale crater can be explained by equilibrium fractionation between sulfate and sulfide in an impact-driven hydrothermal system and atmospheric processing of sulfur-bearing gases during transient warm periods.

Curiosity↗

Evolved Gas Analyses of Sedimentary Rocks and Eolian Sediment in Gale Crater, Mars: Results of the Curiosity Rover's Sample Analysis at Mars Instrument from Yellowknife Bay to the Namib Dune

The sample analysis at Mars instrument evolved gas analyzer (SAM-EGA) has detected evolved water, H2, SO2, H2S, NO, CO2, CO, O2, 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 CO2 (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 CO2 at temperatures consistent with carbonate (0.32 +/- 0.05-0.70 +/- 0.1 wt % CO3). Evolved NO amounts to 0.002 +/- 0.007-0.06 +/- 0.03 wt % NO3. Evolution of O2 suggests that oxychlorine phases (chlorate/perchlorate) (0.05 +/- 0.025-1.05 +/- 0.44 wt % ClO4) are present, while SO2 evolution indicates the presence of crystalline and/or poorly crystalline Fe and Mg sulfate and possibly sulfide. Evolved H2O (0.9 +/- 0.3-2.5 +/- 1.6 wt % H2O) is consistent with the presence of adsorbed water, hydrated salts, interlayer/structural water from phyllosilicates, and possible inclusion water in mineral/amorphous phases. Evolved H2 and H2S 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.

Sutter, B.↗

Evolved Gas Analyses of the Murray Formation in Gale Crater, Mars: Results of the Curiosity Rover's Sample Analysis at Mars (SAM) Instrument

The Sample Analysis at Mars (SAM) instrument aboard the Mars Science Laboratory rover has analyzed 13 samples from Gale Crater. All SAM-evolved gas analyses have yielded a multitude of volatiles (e.g., H2O, SO2, H2S, CO2, CO, NO, O2, HCl) [1- 6]. The objectives of this work are to 1) Characterize recent evolved SO2, CO2, O2, and NO gas traces of the Murray formation mudstone, 2) Constrain sediment mineralogy/composition based on SAM evolved gas analysis (SAM-EGA), and 3) Discuss the implications of these results relative to understanding the geological history of Gale Crater.

Sutter, B.↗

Nitrogen on Mars: Insights from Curiosity

Recent detection of nitrate on Mars indicates that nitrogen fixation processes occurred in early martian history. Data collected by the Sample Analysis at Mars (SAM) instrument on the Curiosity Rover can be integrated with Mars analog work in order to better understand the fixation and mobility of nitrogen on Mars, and thus its availability to putative biology. In particular, the relationship between nitrate and other soluble salts may help reveal the timing of nitrogen fixation and post-depositional behavior of nitrate on Mars. In addition, in situ measurements of nitrogen abundance and isotopic composition may be used to model atmospheric conditions on early Mars.

Stern, J. C.↗

Microbial Habitability in Gale Crater: Sample Analysis at Mars (SAM) Instrument Detection of Microbial Essential Carbon and Nitrogen

Chemical analyses of Mars soils and sediments from previous landed missions have demonstrated that Mars surface materials possessed major (e.g., P, K, Ca, Mg, S) and minor (e.g., Fe, Mn, Zn, Ni, Cl) elements essential to support microbial life. However, the detection of microbial essential organic-carbon (C) and nitrate have been more elusive until the Mars Science Laboratory (MSL) rover mission. Nitrate and organic-C in Gale Crater, Mars have been detected by the Sample Analysis at Mars (SAM) instrument onboard the MSL Curiosity rover. Eolian fines and drilled sedimentary rock samples were heated in the SAM oven from approximately 30 to 860 degrees Centigrade where evolved gases (e.g., nitrous oxide (NO) and CO2) were released and analyzed by SAM’s quadrupole mass spectrometer (MS). The temperatures of evolved NO was assigned to nitrate while evolved CO2 was assigned to organic-C and carbonate. The CO2 releases in several samples occurred below 450 degrees Centigrade suggesting organic-C dominated in those samples. As much as 7 micromoles NO3-N per gram and 200 micromoles CO2-C per gram have been detected in the Gale Crater materials. These N and C levels coupled with assumed microbial biomass (9 x 10 (sup -7) micrograms per cell) C (0.5 micrograms C per micrograms cell) and N (0.14 micrograms N per micrograms cell) requirements, suggests that less than 1 percent and less than 10 percent of Gale Crater C and N, respectively, would be required if available, to accommodate biomass requirements of 1 by 10 (sup 5) cells per gram sediment. While nitrogen is the limiting nutrient, the potential exists that sufficient N and organic-C were present to support limited heterotrophic microbial populations that may have existed on ancient Mars.

Sutter, B.↗

Oxychlorine Detections on Mars: Implications for Cl Cycling

The Sample Analysis at Mars (SAM) instrument has detected evolved O2 and HCl indicating the presence of perchlorate and/or chlorate (oxychlorine) in all 11 sediments analyzed to date. The hyperarid martian climate is believed to have allowed accumulation of oxychlorine and assumed chloride contents similar to those in hyperarid terrestrial settings. The linear correlation of oxychlorine and chloride of Gale Crater sediments is low (r (sup 2) equals 0.64). Correlations present in hyperarid Antarctica and the Atacama Desert are attributed to unaltered atmospheric source coupled with minimal redox cycling by biological activity. Terrestrial semi-arid to arid settings have low correlations similar to Gale Crater and are attributed to additional inputs of Cl minus from sea salt, dust, and/or proximal playa settings, and possible reduction of oxychlorine phases during wetter periods. While microbiological processes could contribute to low oxychlorine/chloride correlations on Mars, several abiotic mechanisms are more likely, such as changing oxychlorine production rates with time and/or post-depositional geochemical redox processes that altered the Gale Crater oxychlorine and chloride contents.

Sutter, B.↗

Evolved Gas Analyses of Sedimentary Materials in Gale Crater, Mars: Results of the Curiosity Rover's Sample Analysis at Mars (SAM) Instrument from Yellowknife Bay to the Stimson Formation

The Sample Analysis at Mars (SAM) instrument aboard the Mars Science Laboratory rover has analyzed 10 samples from Gale Crater. All SAM evolved gas analyses have yielded a multitude of volatiles (e.g, H2O, SO2, H2S, CO2, CO, NO, O2, HC1). The objectives of this work are to 1) Characterize the evolved H2O, SO2, CO2, and O2 gas traces of sediments analyzed by SAM through sol 1178, 2) Constrain sediment mineralogy/composition based on SAM evolved gas analysis (SAM-EGA), and 3) Discuss the implications of these results releative to understanding the geochemical history of Gale Crater.

Sutter, B.↗

Iron-Rich Carbonates as the Potential Source of Evolved CO2 Detected by the Sample Analysis at Mars (SAM) Instrument in Gale Crater

The Sample Analysis at Mars (SAM) instrument detected at least 4 distinct CO2 release during the pyrolysis of a sample scooped from the Rocknest (RN) eolian deposit. The highest peak CO2 release temperature (478-502 C) has been attributed to either a Fe-rich carbonate or nano-phase Mg-carbonate. The objective of this experimental study was to evaluate the thermal evolved gas analysis (T/EGA) characteristics of a series of terrestrial Fe-rich carbonates under analog SAM operating conditions to compare with the RN CO2 releases. Natural Fe-rich carbonates (<53 microns) with varying Fe amounts (Fe(0.66)X(0.34)- to Fe(0.99)X(0.01)-CO3, where X refers to Mg and/or Mn) were selected for T/EGA. The carbonates were heated from 25 to 715 C (35 C/min) and evolved CO2 was measured as a function of temperature. The highest Fe containing carbonates (e.g., Fe(0.99)X(0.01)-CO3) yielded CO2 peak temperatures between 466-487 C, which is consistent with the high temperature RN CO2 release. The lower Fe-bearing carbonates (e.g., Fe(0.66)X(0.34)CO3) did not have peak CO2 release temperatures that matched the RN peak CO2 temperatures; however, their entire CO2 releases did occur within RN temperature range of the high temperature CO2 release. Results from this laboratory analog analysis demonstrate that the high temperature RN CO2 release is consistent with Fe-rich carbonate (approx.0.7 to 1 wt.% FeCO3). The similar RN geochemistry with other materials in Gale Crater and elsewhere on Mars (e.g., Gusev Crater, Meridiani) suggests that up to 1 wt. % Fe-rich carbonate may occur throughout the Gale Crater region and could be widespread on Mars. The Rocknest Fe-carbonate may have formed from the interaction of reduced Fe phases (e.g., Fe2+ bearing olivine) with atmospheric CO2 and transient water. Alternatively, the Rocknest Fe-carbonate could be derived by eolian processes that have eroded distally exposed deep crustal material that possesses Fe-carbonate that may have formed through metamorphic and/or metasomatic processes.

Sutter, B.↗

The Investigation of Perchlorate/Iron Phase Mixtures as A Possible Source of Oxygen Detected by the Sample Analysis at Mars (SAM) Instrument in Gale Crater, Mars

The Sample Analysis at Mars (SAM) instrument onboard the Curiosity rover detected O2 and HCl gas releases from the Rocknest (RN) eolian bedform and the John Klein (JK) and Cumberland (CB) drill hole materials in Gale Crater. Chlorinated hydrocarbons have also been detected by the SAM quadrupole mass spectrometer (QMS) and gas chromatography/mass spectrometer (GCMS). These detections along with the detection of perchlorate (ClO4-) by the Mars Phoenix Lander's Wet Chemistry Laboratory (WCL) suggesting perchlorate is a possible candidate for evolved O2 and chlorine species. Laboratory thermal analysis of individual per-chlorates has yet to provide an unequivocal temperature match to the SAM O2 and HCl release data. These detections along with the detection of perchlorate (ClO4-) by the Mars Phoenix Lander's Wet Chemistry Laboratory suggested perchlorate is a possible candidate for evolved O2 and chlorine species. Laboratory thermal analysis of pure perchlorates has yet to provide an unequivocal temperature match to the SAM O2 and HCl release data. Analog laboratory analysis of iron mineralogy detected in Gale materials that was physically mixed with Ca- and Mg-perchlorate has been shown to catalyze lower O2 release temperatures and approach some SAM O2 release data. Instead of physical mixtures used in previous work, the work presented here utilized perchlorate solutions added to Fe phases. This technique allowed for perchlorate to come in closer contact with the Fe-phase and may more closely mimic Mars conditions where humidity can increase enough to cause deliquescence of the highly hygroscopic perchlorate phases. The objective of this work is to: 1) Utilize a laboratory SAM analog instrument to evaluate the O2 release temperatures from Mg- and Ca-perchlorates solutions applied to Fephases detetected in Gale Crate; and 2) Determine if perchlorate solutions can provide improved matches with the SAM O2 temperature release profiles.

Sutter, B.↗

The Nitrate/Perchlorate Ratio on Mars as an Indicator for Habitability

Discovery of indigenous martian nitrogen in Mars surface materials has important implications for habitability and the potential development of a nitrogen cycle at some point in martian history. The Sample Analysis at Mars (SAM) instrument suite on the Mars Science Laboratory (MSL) Curiosity Rover detected evolved nitric oxide (NO) gas during pyrolysis of scooped aeolian sediments and drilled mudstone acquired in Gale Crater. The detection of NO suggests an indigenous source of fixed N, and may indicate a mineralogical sink for atmospheric N2 in the form of nitrate. The ratio of nitrate to oxychlorine species (e.g. perchlorate) may provide insight into the extent of development of a nitrogen cycle on Mars.

Stern, J. C.↗

Major Volatiles from MSL SAM Evolved Gas Analyses: Yellowknife Bay Through Lower Mount Sharp

The Sample Analysis at Mars (SAM) and Chemistry and Mineralogy (CheMin) instruments on the Mars Science Laboratory (MSL) analysed several subsamples of <150 μm fines from five sites at Gale Crater. Three were in Yellowknife Bay: the Rocknest aeolian bedform ("RN") and drilled Sheepbed mudstone from sites John Klein ("JK") and Cumberland ("CB"). One was drilled from the Windjana ("WJ") site on a sandstone of the Kimberly formation investigated on route to Mount Sharp. Another was drilled from the Confidence Hills ("CH") site on a sandstone of the Murray Formation at the base of Mt. Sharp (Pahrump Hills). Outcrops are sedimentary rocks that are largely of fluvial or lacustrine origin, with minor aeolian deposits.. SAM's evolved gas analysis (EGA) mass spectrometry detected H2O, CO2, O2, H2, SO2, H2S, HCl, NO, and other trace gases, including organic fragments. The identity and evolution temperature (T) of evolved gases can support CheMin mineral detection and place constraints on trace volatile-bearing phases or phases difficult to characterize with XRD (e.g., X-ray amorphous phases). They can also give constraints on sample organic chemistry. Here, we discuss trends in major evolved volatiles from SAM EGA analyses to date.

McAdam, A. C.↗

The Nitrate/Perchlorate Ratio on Mars as an Indicator for Habitability

Discovery of indigenous martian nitrogen in Mars surface materials has important implications for habitability and the potential development of a nitrogen cycle at some point in martian history. The Sample Analysis at Mars (SAM) instrument suite on the Mars Science Laboratory (MSL) Curiosity Rover detected evolved nitric oxide (NO) gas during pyrolysis of scooped aeolian sediments and drilled mudstone acquired in Gale Crater. The detection of NO suggests an indigenous source of fixed N, and may indicate a mineralogical sink for atmospheric N2 in the form of nitrate. The ratio of nitrate to oxychlorine species (e.g. perchlorate) may provide insight into the extent of development of a nitrogen cycle on Mars.

Mars↗

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 degrees Centigrade and 950 degrees Centigrade from samples of Hesperian-era Gale crater smectite to determine this isotope ratio. The D/H value is 3.0 (plus or minus 0.2) times the ratio in standard mean ocean water. The D/H ratio in this approximately 3-billion-year-old mudstone, which 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.

Deuterium↗

The Investigation of Magnesium Perchlorate/Iron Phase-mineral Mixtures as a Possible Source of Oxygen and Chlorine Detected by the Sample Analysis at Mars (SAM) Instrument in Gale Crater, Mars

The Sample Analysis at Mars (SAM) instrument onboard the Curiosity rover detect-ed O2 and HCl gas releases from the Rocknest (RN) eolian bedform and the John Klein (JK) and Cumber-land (CB) drill hole materials in Gale Crater (Fig. 1) [1,2]. Chlorinated hydrocarbons have also been detect-ed by the SAM quadrupole mass spectrometer (QMS) and gas chromatography/mass spectrometer (GCMS) [1,2,3,4]. These detections along with the detection of perchlorate (ClO4(-)) by the Mars Phoenix Lander's Wet Chemistry Laboratory (WCL) [5] suggesting perchlo-rate is a possible candidate for evolved O2 and chlorine species. Laboratory thermal analysis of individual per-chlorates has yet to provide an unequivocal tempera-ture match to the SAM O2 and HCl release data [1,2]. Catalytic reactions of Fe phases in the Gale Crater ma-terial with perchlorates can potentially reduce the de-composition temperatures of these otherwise pure per-chlorate/chlorate phases [e.g., 6,7]. Iron mineralogy found in the Rocknest materials when mixed with Ca-perchlorate was found to cause O2 release temperatures to be closer match to the SAM O2 release data and enhance HCl gas releases. Exact matches to the SAM data has unfortnunately not been achieved with Ca-perchlorate-Fe-phase mixtures [8]. The effects of Fe-phases on magnesium perchlorate thermal decomposi-tion release of O2 and HCl have not been evaluated and may provide improved matches to the SAM O2 and HCl release data. This work will evaluate the thermal decomposition of magnesium perchlorate mixed with fayalite/magnetite phase and a Mauna Kea palagonite (HWMK 919). The objectives are to 1) summarize O2 and HCl releases from the Gale Crater materials, and 2) evaluate the O2 and HCl releases from the Mg-perchlorate + Fe phase mixtures to determine if Mg-perchlorate mixed with Fe-phases can explain the Gale Crater O2 and HCl releases.

Sutter, B.↗