Isotopic and geochemical investigation of two distinct Mars analog environments using evolved gas techniques in Svalbard, Norway

Stern, J. C.; McAdam, A. C.; Kate, I. L. ten; Bish, David L.; Blake, D. F.; Morris, R. V.; Bowden, R.; Fogel, Marilyn L.; Glamoclija, M.; Mahaffy, P. R.; Steele, A.; Amundsen, H. E. F.

doi:10.1016/j.icarus.2012.07.010

Cited by 10 publications

(4 citation statements)

References 75 publications

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“…The subsequent decomposition of these secondary products caused the SO 2 releases at ~490 and 700 °C. Furthermore, crystalline and amorphous ferric sulfates show SO 2 releases from ~500-800 °C (McAdam et al 2014;Ming et al 2014), consistent with the two higher-temperature m/z 64 releases in sulfate-chemisorbed ferrihydrite, and other common sulfate minerals (e.g., Ca-, Mg-, and Al-sulfates) decompose at temperatures >500 °C (e.g., Lombardi 1984;Archer et al 2013;Stern et al 2013;McAdam et al 2014;Ming et al 2014). Thus, a m/z 64 release at 400 °C in SAM data would distinguish sulfate chemisorbed onto ferrihydrite from discrete crystalline and amorphous ferric sulfates; however, this release has not been detected in SAM to date (McAdam et al 2014(McAdam et al , 2015Ming et al 2014).…”

Section: Implications For Martian Orbital and In-situ Analysessupporting

confidence: 63%

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Recognizing sulfate and phosphate complexes chemisorbed onto nanophase weathering products on Mars using in-situ and remote observationsk

Rampe

Morris

Archer

et al. 2016

American Mineralogist

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Orbital and in-situ data from the surface of Mars indicate that nanophase weathering products are important constituents of martian rocks and soils. Nanophase minerals have the capacity to chemisorb anions like sulfate and phosphate onto their surfaces, but it is not known whether chemisorption is an important or even detectable process via orbital and in-situ observations. The detection of chemisorbed sulfate and phosphate anions on nanophase minerals would constrain the speciation of these anions and past aqueous environmental conditions. Here, we synthesized two nanophase weathering products that are common in terrestrial volcanic soils and have been identified on the martian surface: allophane and nanophase ferric oxide as represented by ferrihydrite. We specifically adsorbed sulfate and phosphate separately onto the nanophase mineral surfaces (4.5 and 1.6 wt% SO 4 2-, and 6.7 and 8.9 wt% PO 4 3-on allophane and ferrihydrite, respectively) and analyzed the untreated and chemisorbed materials using instruments similar to those on orbital and landed Mars missions (including X-ray diffraction, evolved gas analysis, Mössbauer spectroscopy, and VNIR and thermal-IR spectroscopy). Evolved gas analysis is the optimum method to detect chemisorbed sulfate, with SO 2(g) being released at >900 °C for allophane and 400-800 °C for ferrihydrite. Chemisorbed sulfate and phosphate anions affect the thermal-IR spectra of allophane and ferrihydrite in the S-O and P-O stretching region when present in abundances of only a few weight percent; S-O and P-O stretching bands are apparent as short-wavelength shoulders on Si-O stretching bands. Sulfate and phosphate anions chemisorbed to allophane have small but measurable effects on the position of the OH-H 2 O bands at 1.4 and 1.9 mm in near-IR spectra. Chemisorbed sulfate and phosphate anions did not affect the X-ray diffraction patterns, Mössbauer spectra, and visible/near-IR spectra of ferrihydrite. These data suggest that sulfate chemisorbed onto the surfaces of nanophase minerals can be detected with the Sample Analysis at Mars (SAM) instrument on the Mars science laboratory Curiosity rover, and subtle signatures of chemisorbed sulfate and phosphate may be detectable by IR spectrometers on landed missions. The combined use of SAM, the Chemistry and Mineralogy (CheMin) instrument, and the Alpha Particle X-ray Spectrometer (APXS) on Curiosity allows for the most detailed characterization to date of nanophase minerals in martian rocks and soils and the potential presence of chemisorbed anionic complexes.

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Section: Implications For Martian Orbital and In-situ Analysessupporting

confidence: 63%

“…In addition, SO 2 evolution from some Mg-or Ca-sulfate minerals may overwhelm the EGA signature of sulfate-adsorbed allophane if present in higher abundances. For example, epsomite undergoes sulfate decomposition at 970 °C under SAM-like experimental conditions (Archer et al 2013;Stern et al 2013).…”

Section: Implications For Martian Orbital and In-situ Analysesmentioning

confidence: 99%

Recognizing sulfate and phosphate complexes chemisorbed onto nanophase weathering products on Mars using in-situ and remote observationsk

Rampe

Morris

Archer

et al. 2016

American Mineralogist

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“…SO 2 from sulfates results from sulfate decomposition. Sulfides alone, counterintuitively, consistently evolve SO 2 in EGA experiments (McAdam et al, 2014; Stern et al, 2013) with minor O 2 or H 2 O likely serving as oxidants. The decomposition of other compounds, such as oxychlorines, can also provide oxygen for sulfide oxidation.…”

Section: Resultsmentioning

confidence: 99%

Detection of Reduced Sulfur on Vera Rubin Ridge by Quadratic Discriminant Analysis of Volatiles Observed During Evolved Gas Analysis

et al. 2020

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The Mars Science Laboratory mission investigated Vera Rubin ridge, which bears spectral indications of elevated amounts of hematite and has been hypothesized as having a complex diagenetic history. Martian samples, including three drilled samples from the ridge, were analyzed by the Sample Analysis at Mars instrument suite via evolved gas analysis‐mass spectrometry (EGA‐MS). Here, we report new EGA‐MS data from Martian samples and describe laboratory analogue experiments. Analyses of laboratory analogues help determine the presence of reduced sulfur in Martian solid samples, which could have supported potential microbial life. We used evolved carbonyl sulfide (COS) and carbon disulfide (CS2) to identify Martian samples likely to contain reduced sulfur by applying a quadratic discriminant analysis. While we report results for 24 Martian samples, we focus on Vera Rubin ridge samples and select others for comparison. Our results suggest the presence of reduced sulfur in the Jura member of Vera Rubin ridge, which can support various diagenetic history models, including, as discussed in this work, diagenetic alteration initiated by a mildly reducing, sulfite‐containing groundwater.

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“…Results by XRF also contributed to a paper by Stivaletta et al, 20 whose interest was in the identication of minerals in terrestrial evaporites relevant to the exploration of environments suitable for supporting microbial life on the surface of Mars. Two distinct Mars analogue environments were identied by Stern et al 21 in Svalbard, Norway, for evaluating methodologies and techniques to be used on the Mars Science Lander. An XRD/XRF instrument was deployed as part of the eld campaign at these sites, although the main focus of this investigation was an evaluation of evolved-gas techniques including a Hiden evolved gas analysis-mass spectrometer and a Picarro cavity ring down spectrometer.…”

Section: Hand-held Mobile On-line Xrf Techniques and Planetary Explor...mentioning

confidence: 99%

2014 Atomic Spectrometry Update – a review of advances in X-ray fluorescence spectrometry

West

Ellis

Potts

et al. 2014

J. Anal. At. Spectrom.

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Isotopic and geochemical investigation of two distinct Mars analog environments using evolved gas techniques in Svalbard, Norway

Cited by 10 publications

References 75 publications

Recognizing sulfate and phosphate complexes chemisorbed onto nanophase weathering products on Mars using in-situ and remote observationsk

Recognizing sulfate and phosphate complexes chemisorbed onto nanophase weathering products on Mars using in-situ and remote observationsk

Detection of Reduced Sulfur on Vera Rubin Ridge by Quadratic Discriminant Analysis of Volatiles Observed During Evolved Gas Analysis

2014 Atomic Spectrometry Update – a review of advances in X-ray fluorescence spectrometry

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