Evidence for Adsorption of Chlorine Species on Iron(III) (hydr)oxides in the Sheepbed Mudstone, Gale Crater, Mars

Chlorine is a widespread element on Mars present in dust, soils and rocks, including the Sheepbed mudstone at Yellowknife Bay, Gale crater. Combined elemental and volatile analyses of two drilled samples, Cumberland and John Klein, indicated that chloride (Cl-) and perchlorate (ClO4 -) are likely present in the mudstone. The nature of chlorine species in Sheepbed mudstone is still not well constrained. It has been proposed that both are present as amorphous or crystalline salts physically mixed with mudstone minerals. We alternatively hypothesize that adsorbed perchlorate and chloride exist in the mudstone and adsorption could occur, in particular, on Fe(III) (hydr)oxide phases as supported by laboratory observations on terrestrial materials. Mineralogical and compositional analyses of the drilled Cumberland mudstone sample revealed the presence of ~30 wt% of a Fe-rich X-ray amorphous phase. Ferrihydrite has been proposed as a component of the Fe-rich X-ray amorphous material. The objectives of this work were to determine adsorption of perchlorate and chloride on ferrihydrite and to enable data comparison by characterizing adsorbed chloride and perchlorate with thermal and evolved gas analysis run under operating conditions similar to the SAM instrument onboard the Curiosity rover

Phyllosilicate Transitions in Ferromagnesian Soils: Short-Range Order Materials and Smectites Dominate Secondary Phases

Analyses of X-ray diffraction (XRD) patterns taken by the CheMin instrument on the Curiosity Rover in Gale crater have documented the presence of clay minerals interpreted as smectites and a suite of amorphous to short-range order materials termed X-ray amorphous materials. These X-ray amorphous materials are commonly ironrich and aluminum poor and likely some of them are weathering products rather than primary glasses due to the presence of volatiles. Outstanding questions remain regarding the chemical composition and mineral structure of these X-ray amorphous materials and the smectites present at Gale crater and what they indicate about environmental conditions during their formation. To gain a better understanding of the mineral transitions that occur within ferromagnesian parent materials, we have investigated the development of secondary clay minerals and shortrange order materials in two soil chronosequences with varying climates developing on ultramafic bedrock. Field Sites: We investigated soil weathering within two field locations, the Klamath Mountains of Northern California, and the Tablelands of Newfoundland, Canada. Both sites possess age dated or correlated recently deglaciated soils and undated but substantially older soils. In the Klamath mountains the Trinity Ultramafic Body was deglaciated roughly 15,000 years bp while in the Tablelands a moraine was dated to about 17,600 years bp. The Klamath Mountains feature a seasonally wet and dry climate while the Tablelands are wet year-round with saturated soil conditions observed during sampling and standing water observed within 3 of 4 soil pit sampling locations

Formation of Fe/mg Smectite Under Acidic Conditions from Synthetic Adirondack Basaltic Glass: an Analog to Fe/mg Smectite Formation on Mars

Smectite has been detected as layered material hundreds of meters thick, in intracrater depositional fans, in plains sediments, and deposits at depth on Mars. If early Mars hosted a dense CO2 atmosphere, then extensive carbonate should have formed in the neutral/alkaline conditions expected for smectite formation. However, large carbonate deposits on Mars have not been discovered. Instead of neutral to moderately alkaline conditions, early Mars may have experienced mildly acidic conditions that allowed for Fe/Mg smectite formation but prevented widespread carbonate formation. The objective of this work is to demonstrate that Fe(II)/Mg saponite and nontronite can form in mildly acidic solutions (e.g., pH 4). Synthetic basaltic glass (< 53 microns) of Adirondack rock class composition was exposed to pH 4 (acetic acid buffer) and N2 purged (anoxic) solutions amended with 0 and 10 mM Mg or Fe(II). Basaltic glass in these solutions was heated to 200 C in batch reactors for 1, 7, and 14 days. X-ray diffraction analysis of reacted materials detected the presence of phyllosilicates as indicated by a approx. 15.03-15.23Angstroms (001) peak. Smectite was confirmed as the phyllosilicate after treatments with glycerol and KCl and heating to 550 C. Trioctahedral saponite was confirmed by the presence of a 4.58 to 4.63 Angstroms (02l) and 1.54Angstroms (060) peaks. Saponite concentration was highest, as indicated by XRD peak intensity, in the 10 mM Mg treatment followed by the 0 mM and then 10 mM Fe(II) treatments. This order of sapontite concentration suggests that Fe(II) additions may have a role in slowing the kinetics of saponite formation relative to the other treatments. Nontronite synthesis was attempted by exposing Adirondack basaltic glass to pH 4 oxic solutions (without N2 purge) at 200 C for 14 days. X-ray diffraction analysis indicated that mixtures of trioctahedral (saponite) and dioctahedral (nontronite) may have formed in these experiments based on the 02l and 060 peaks. Moessbauer analysis coupled with future experiments are planned to verify if nontronite can be formed under mildly acidic and oxic conditions. Results of this work demonstrate that acidic conditions could have occurred on an early Mars, which allowed for smectite formation but inhibited carbonate formation

Interpreting Aqueous Alteration in the Murray Formation Using Reactive Transport Modeling

Abundant evidence for liquid water exists at Gale crater, Mars. However, the characteristics of past water remain an area of active research. The first exposures of the Murray formation in Gale crater, Mars (Fig. 1) were studied with four samples analyzed using CheMin: Buckskin, Telegraph Peak, Mojave, and Confidence Hills. Analyses indicate differences in mineralogy and chemistry between the samples which have been attributed to changes in pH and oxidation state of depositional and diagenetic environments. Recent work also suggests that hydrothermal fluids may have been present based on the presence of Se, Zn, Pb, and other elements

Reaction of Akaganeite with Mars-Relevant Anions

Akaganeite has been identified by the Chemistry and Mineralogy (CheMin) and Sample Analysis at Mars (SAM) instruments onboard the Curiosity rover in Yellowknife Bay, Gale Crater, Mars. Akaganeite was also detected by the Compact Reconnaissance Imaging Spectrometer for Mars (CRISM) instrument on the Mars Reconnaissance Orbiter (MRO) in Robert Sharp Crater and Antoniadi basin. Akaganeite is an iron(III) hydroxide with a hollandite-like tunnel structure with tunnels usually occupied by Cl-. Chloride in tunnels is not immobile and can be replaced by other anions in solution. Identification of tunnel composition with Mars-like instruments can help to characterize composition of ancient aqueous environments where akaganeite is present on Mars

Effect of Sulfur Concentration and PH Conditions on Akaganeite Formation: Understanding Akaganeite Formation Conditions in Yellowknife Bay, Gale Crater, Mars

The Chemistry and Mineralogy Instrument (CHEMIN) on board the Mars Science Laboratory (MSL) Curiosity Rover identified minor amounts of akaganeite (beta-FeOOH) at Yellowknife Bay, Mars. There is also evidence for akaganeite at other localities on Mars from the Compact Reconnaissance Imaging Spectrometer for Mars (CRISM). Akaganeite is an iron(III) hydroxide with a hollandite- like structure and Cl in its tunnels. Terrestrial akaganeite usually forms in Cl-rich environments under acidic, oxidizing conditions. Previous studies of akaganeite have revealed that akaganeite formation is affected by the presence of sulfate (hereafter denoted as S. The prediction of circumneutral pH coupled with the detection of S at Yellowknife Bay dictate that work is needed to determine how S and pH together affect akaganeite formation. The goal of this work is to study how changes in both S concentration and pH influence akaganeite precipitation. Akaganeite formation was investigated at S/Cl molar ratios of 0, 0.017, 0.083, 0.17 and 0.33 at pH 1.5, 2, and 4. Results are anticipated to provide combined S concentration and pH constraints on akaganeite formation in Yellowknife Bay and elsewhere on Mars. Knowledge of solution pH and S concentrations can be utilized in understanding microbial habitability potential on the Martian surface

Smectite Formation from Basaltic Glass Under Acidic Conditions on Mars

Massive deposits of phyllosilicates of the smectite group, including Mg/Fe-smectite, have been identified in Mars's ancient Noachian terrain. The observed smectite is hypothesized to form through aqueous alteration of basaltic crust under neutral to alkaline pH conditions. These pH conditions and the presence of a CO2-rich atmosphere suggested for ancient Mars were favorable for the formation of large carbonate deposits. However, the detection of large-scale carbonate deposits is limited on Mars. We hypothesized that smectite deposits may have formed under acidic conditions that prevented carbonate precipitation. In this work we investigated formation of saponite at a pH of approximately 4 from Mars-analogue synthetic Adirondack basaltic glass of composition similar to Adirondack class rocks located at Gusev crater. Hydrothermal (200 Centigrade) 14 day experiments were performed with and without 10 millimoles Fe(II) or Mg under anoxic condition [hereafter denoted as anoxic_Fe, anoxic_Mg and anoxic (no addition of Fe(II) or Mg)] and under oxic condition [hereafter denoted as oxic (no addition of Fe(II) or Mg)]. Characterization and formation conditions of the synthesized saponite provided insight into the possible geochemical conditions required for saponite formation on Mars

Smectite Formation in Acid Sulfate Environments on Mars

Phyllosilicates of the smectite group detected in Noachian and early Hesperian terrains on Mars were hypothesized to form under aqueous conditions that were globally neutral to alkaline. These pH conditions and the presence of a CO2-rich atmosphere should have been favorable for the formation of large carbonate deposits. However, large-scale carbonate deposits have not been detected on Mars. We hypothesized that smectite deposits are consistent with perhaps widespread acidic aqueous conditions that prevented carbonate precipitation. The objective of our work was to investigate smectite formation under acid sulfate conditions in order to provide insight into the possible geochemical conditions required for smectite formation on Mars. Hydrothermal batch incubation experiments were performed with Mars-analogue, glass-rich, basalt simulant in the presence of sulfuric acid of variable concentration

Synthesis of Akaganeite in the Presence of Sulfate: Implications for Akaganeite Formation in Yellowknife Bay, Gale Crater, Mars

Akaganeite (beta-FeOOH) is an Fe(III) (hydr)oxide with a tunnel structure usually occupied by chloride. Akaganeite has been recently discovered in a mudstone on the surface of Mars by the Chemistry and Mineralogy (CheMin) and Sample Analysis at Mars (SAM) instruments onboard the Mars Science Laboratory (MSL) Curiosity Rover in Gale crater [1, 2]. Akaganeite was detected together with sulfate minerals [anhydrite (CaSO4) and basanite (2CaSO42H2O)] in the drilled Cumberland and John Clein mudstone samples at Yellowknife Bay [2]. Discovery of akaganeite and sulfates in the same samples suggests that sulfate ions could be present in aqueous solution during akaganeite formation. However, mechanism and aqueous environmental conditions of akaganeite formation (e.g., pH and range of sulfate concentration) in Yellowknife Bay remain unknown. The objective of our work was to perform synthesis of akaganeite without or with sulfate addition at variable pHs in order to constrain formation conditions of akaganeite in Yellowknife Bay, Gale crater on Mars

Smectite Formation in the Presence of Sulfuric Acid: Implications for Acidic Smectite Formation on Early Mars

The excess of orbital detection of smectite deposits compared to carbonate deposits on the martian surface presents an enigma because smectite and carbonate formations are both favored alteration products of basalt under neutral to alkaline conditions. We propose that Mars experienced acidic events caused by sulfuric acid (H2SO4) that permitted phyllosilicate, but inhibited carbonate, formation. To experimentally verify this hypothesis, we report the first synthesis of smectite from Mars-analogue glass-rich basalt simulant (66 wt% glass, 32 wt% olivine, 2 wt% chromite) in the presence of H2SO4 under hydrothermal conditions (approximately 200 degC). Smectites were analyzed by X-ray diffraction, Mossbauer spectroscopy, visible and near-infrared reflectance spectroscopy and electron microprobe to characterize mineralogy and chemical composition. Solution chemistry was determined by Inductively Coupled Plasma Mass Spectrometry. Basalt simulant suspensions in 11-42 mM H2SO4 were acidic with pH less than or equal to 2 at the beginning of incubation and varied from acidic (pH 1.8) to mildly alkaline (pH 8.4) at the end of incubation. Alteration of glass phase during reaction of the basalt simulant with H2SO4 led to formation of the dioctahedral smectite at final pH approximately 3 and trioctahedral smectite saponite at final pH approximately 4 and higher. Anhydrite and hematite formed in the final pH range from 1.8 to 8.4 while natroalunite was detected at pH 1.8. Hematite was precipitated as a result of oxidative dissolution of olivine present in Adirondack basalt simulant. Formation of secondary phases, including smectite, resulted in release of variable amounts of Si, Mg, Na and Ca while solubilization of Al and Fe was low. Comparison of mineralogical and solution chemistry data indicated that the type of smectite (i.e., dioctahedral vs trioctahedral) was likely controlled by Mg leaching from altering basalt and substantial Mg loss created favorable conditions for formation of dioctahedral smectite. We present a model for global-scale smectite formation on Mars via acid-sulfate conditions created by the volcanic outgassing of SO2 in the Noachian and early Hesperian