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NASA NTRS2011

Formation of Jarosite in the Marwrth Vallis Region of Mars by Weathering Within Paleo-Ice Deposits

Here we report new detections of jarosite in the Mawrth Vallis region of Mars. These newly recognized deposits expand the known occurrences of sulfates [1-2] in the region and further expand the already considerable geologic-mineralogic diversity of the Mawrth Vallis area [3-6]. The occurrence of sulfates such as jarosite in geologic contact with thick deposits of phyllosilicates in the Mawrth Vallis area is a relatively rare case on Mars where the enigmatic transition from an early phyllosilicateforming era to a younger sulfate-forming era [7] can be explored. We propose an ice-weathering model which can potentially explain the formation of jarosite-silicakaolinite within acidic ice deposits.

Michalski, J. R.↗

NASA NTRS2012

The Alteration History of Clovis Class Rocks in Gusev Crater as Determined by Ti-Normalzed Mass Balance Analysis

The West Spur Clovis class rocks in Gusev Crater are some of the most altered rocks in Gusev Crater and likely contain a mixed sulfate and phyllosilicate mineralogy [1,2]. The high S and Cl content of the Clovis rocks suggests that acidic vapors or fluids of H2SO4 and HCl reacted with the Clovis parent rock to form Ca, Mg,- sulfates, iron-oxyhydroxides and secondary aluminosilicates (approx.60 wt.%) of a poorly crystalline nature (e.g., allophane) [1]. Up to 14-17 wt.% phyllosilicates (e.g., kaolinite, chlorite, serpentine) are hypothesized to exist in the Clovis materials suggesting that Clovis parent materials while possibly exposed to acidic pHs were likely neutralized by basalt dissolution which resulted in mildly acidic pHs (4-6) [1, 2]. This work proposes that subsequent to the alteration of the Clovis rocks, alteration fluids became concentrated in ions resulting in the addition of silicate and salts. The objective of this work is to utilize Ti-normalized mass balance analysis to evaluate (1) mineral gains and losses and (2) elemental gains and losses in the Clovis rocks. Results of this work will be used evaluate the nature of geochemical conditions that affect phyllosilicate and sulfate formation at Gusev crater.

Sutter, Brat↗

NASA NTRS2013

The Multi-Stage History of Mt. Sharp

The Curiosity rover is exploring Gale crater and Mt. Sharp, Gale's 5‐km high central mound. We are investigating the history of alteration and erosion of Mt. Sharp using orbital imagery, spectroscopy and rover observations. Our results suggest a significant time gap between emplacement of the upper and lower sections of the mound. Crater counts show that the lower mound was formed soon after Gale itself, and that it contains distinct units ranging in altitude from approximately ‐4,500 to ‐1,800 m. Spectral data suggest that many units contain phyllosilicates. We found that these clay‐bearing rocks occur in distinct layers concentrated below ‐2,900 m. Parts of the lower mound exhibit a transition from clays to sulfates with increasing altitude. The lower mound shows evidence of flowing water, including canyons and inverted channels. Wind erosion produced km‐scale yardangs and scalloped cliffs. Our mapping shows that many yardangs in the lower mound are clay‐bearing, with a predominant orientation of around N‐S. Curiosity's ground‐level images show myriad fine‐scale, mainly horizontal layers in the lower mound. The rover has found stream beds and conglomerates, indicating that water once flowed on the crater floor. Drilling near the deepest point in Gale produced abundant clay, providing additional evidence of aqueous alteration. Upper mound units range in altitude from ‐2,100 m to +500 m, and mantle the lower mound above an angular unconformity. Most upper mound units are composed of layers. The formation age of the upper mound is unknown, since few craters are preserved. Clay‐bearing layers are detectable in several locations, mainly at altitudes near ‐2,000 m. There is no evidence of water flow, but wind erosion has scalloped the surfaces and edges of layers, and fine‐scale yardangs are common. Correlations between yardangs and clay spectra are apparent only in the lowermost units of the upper mound. Yardang orientations vary, and include N‐S, NW‐SE, and NE‐SW. Upper mound units resemble the planet‐wide Medusae Fossae formation, dated as Hesperian and argued to be composed of ignimbrites. Medusae Fossae layers are easily eroded by wind, and our mapping demonstrates their resemblance to upper mound fine‐scale yardangs. The history of Mt. Sharp started with deposition and lithification of sediments shortly after crater formation. Some lower mound layers were partially altered to clays and sulfates, and water formed streams and canyons. Wind erosion of the lower mound produced large‐scale yardangs, particularly in clay‐rich layers, oriented generally N‐S. Upper mound units were emplaced following a considerable period of wind erosion. The absence of water flow on the upper mound suggests that these units were emplaced after atmospheric loss rendered water unstable at the surface. The shift in dominant wind direction, as indicated by yardang orientations, also argues for a time gap between erosion of the lower and upper mound. These observations are consistent with upper mound units being related to the Hesperian Medusae Fossae formation. During 2014 Curiosity is expected to reach the foot of Mt. Sharp and ascend through the clay‐rich layers, into the sulfate‐rich layers, and possibly past the interface with the upper mound. This will be a unique opportunity to field check geologic models on the surface of Mars.

Allen, C.↗

NASA NTRS2013

Ion Exchange Technology Development in Support of the Urine Processor Assembly

The urine processor assembly (UPA) on the International Space Station (ISS) recovers water from urine via a vacuum distillation process. The distillation occurs in a rotating distillation assembly (DA) where the urine is heated and subjected to sub-ambient pressure. As water is removed, the original organics, salts, and minerals in the urine become more concentrated and result in urine brine. Eventually, water removal will concentrate the urine brine to super saturation of individual constituents, and precipitation occurs. Under typical UPA DA operating conditions, calcium sulfate or gypsum is the first chemical to precipitate in substantial quantity. During preflight testing with ground urine, the UPA achieved 85% water recovery without precipitation. However, on ISS, it is possible that crewmember urine can be significantly more concentrated relative to urine from ground donors. As a result, gypsum precipitated in the DA when operating at water recovery rates at or near 85%, causing the failure and subsequent re14 NASA Tech Briefs, September 2013 placement of the DA. Later investigations have demonstrated that an excess of calcium and sulfate will cause precipitation at water recovery rates greater than 70%. The source of the excess calcium is likely physiological in nature, via crewmembers' bone loss, while the excess sulfate is primarily due to the sulfuric acid component of the urine pretreatment. To prevent gypsum precipitation in the UPA, the Precipitation Prevention Project (PPP) team has focused on removing the calcium ion from pretreated urine, using ion exchange resins as calcium removal agents. The selectivity and effectiveness of ion exchange resins are determined by such factors as the mobility of the liquid phase through the polymer matrix, the density of functional groups, type of functional groups bound to the matrix, and the chemical characteristics of the liquid phase (pH, oxidation potential, and ionic strength). Previous experience with ion exchange resins has demonstrated that the most effective implementation for an ion exchange resin is a cartridge, or column, in which the resin is contained. Based on the results of equilibrium and sub-scale dynamic column testing, a possible solution for mitigating the calcium precipitation issue on the ISS has been identified. From an original pool of 13 ion exchange resins, two candidates have been identified that demonstrate substantial calcium removal on the sub-scale. The dramatic reduction in resin performance from published calcium uptake demonstrates the need for thorough evaluation of resins at the low pH and strong oxidizing environment present in the UPA. Chemical variations in the influent (calcium concentrations and pretreatment dosing) appear to have a noticeable impact on the calcium capacity of the resin. Low calcium concentrations and high pretreatment dosing will likely result in a decrease in calcium capacity. Conversely, low pre trea t - ment dosing will likely result in an increase in calcium capacity. In contrast, investigations at a variety of flow rates, length-to-diameter ratios, resin volumes, and flow regimes (continuous versus pulsed) show that changes in physical parameters do not have substantial impacts on resin performance in the very low specific velocity ranges of interest. This result is particularly useful because most commercial applications at higher specific velocities do show a relatively strong relationship between flow and capacity. The lack of a strong relationship will allow more flexibility in the implementation of an ion exchange bed for flight. Verification of subscale tests with flight-scale resin beds is recommended prior to implementation in the on-orbit UPA.

Mitchell, Julie↗

NASA NTRS2013

The XRD Amorphous Component in John Klein Drill Fines at Yellowknife Bay, Gale Crater, Mars

Drill fines of mudstone (targets John Klein and Cumberland) from the Sheepbed unit at Yel-lowknife Bay were analyzed by MSL payload elements including the Chemistry and Mineralogy (CheMin), APXS (Alpha Particle X-Ray Spectrometer), and Sample Analysis at Mars (SAM) instruments. CheMin XRD results show a variety of crystalline phases including feldspar, pyroxene, olivine, oxides, oxyhydroxides, sulfates, sulfides, a tri-octahedral smectite, and XRD amorphous material. The drill fines are distinctly different from corresponding analyses of the global soil (target Rocknest) in that the mudstone samples contained detectable phyllosilicate. Here we focus on John Klein and combine CheMin and APXS data to calculate the chemical composition and concentration of the amorphous component. The chemical composition of the amorphous plus smectite component for John Klein was calculated by subtracting the abundance-weighted chemical composition of the individual XRD crystalline components from the bulk composition of John Kline as measured by APXS. The chemical composition of individual crystalline components was determined either by stoichiometry (e.g., hematite and magnetite) or from their unit cell parameters (e.g., feldspar, olivine, and pyroxene). The chemical composition of the amorphous + smectite component (approx 71 wt.% of bulk sample) and bulk chemical composition are similar. In order to calculate the chemical composition of the amorphous component, a chemical composition for the tri-octahedral smectite must be assumed. We selected two tri-octahedral smectites with very different MgO/(FeO + Fe2O3) ratios (34 and 1.3 for SapCa1 and Griffithite, respectively). Relative to bulk sample, the concentration of amorphous and smectite components are 40 and 29 wt.% for SapCa1 and 33 and 36 wt.% for Griffithite. The amount of smectite was calculated by requiring the MgO concentration to be approx 0 wt.% in the amorphous component. Griffithite is the preferred smectite because the position of its 021 diffraction peak is similar to that reported for John Klein. In both cases, the amorphous component has low SiO2 and MgO and high FeO + Fe2O3, P2O5, and SO3 concentrations relative to bulk sample. The chemical composition of the bulk drill fines and XRD crystalline, smectite, and amorphous components implies alteration of an initially basaltic material under near neutral conditions (not acid sulfate), with the sulfate incorporated later as veins of CaSO4 injected into the mudstone.

Morris, Richard V.↗

NASA NTRS2014

Exploring Mars for Evidence of Habitable Environments and Life

The climate of Mars has been more similar to that of Earth than has the climate of any other planet in our Solar System. But Mars still provides a valuable alternative example of how planetary processes and environments can affect the potential presence of life elsewhere. For example, although Mars also differentiated very early into a core, mantle and crust, it then evolved mostly if not completely without plate tectonics and has lost most of its early atmosphere. The Martian crust has been more stable than that of Earth, thus it has probably preserved a more complete record of its earliest history. Orbital observations determined that near-surface water was once pervasive. Orbiters have identified the following diverse aqueous sedimentary deposits: layered phyllosilicates, phyllosilicates in intracrater fans, plains sediments potentially harboring evaporitic minerals, deep phyllosilicates, carbonate-bearing deposits, intracrater clay-sulfate deposits, Meridiani-type layered deposits, valles-type layered deposits, hydrated silica-bearing deposits, and gypsum plains. These features, together with evidence of more vigorous past geologic activity, indicate that early climates were wetter and perhaps also somewhat warmer. The denser atmosphere that was required for liquid water to be stable on the surface also provided more substantial protection from radiation. Whereas ancient climates might have favored habitable environments at least in some localities, clearly much of the Martian surface for most of its history has been markedly less favorable for life. The combination of dry conditions, oxidizing surface environments and typically low rates of sedimentation are not conducive to the preservation of evidence of ancient environments and any biota. Thus a strategy is required whereby candidate sites are first identified and then characterized for their potential to preserve evidence of past habitable environments. Rovers are then sent to explore the most promising candidates. The Mars Exploration Rover (MER) Opportunity revealed that water once flowed to the surface across the vast Meridiani plains, creating saline lakes whose waters were roiled by ancient winds that also sculptured their salt deposits into sand dunes. Opportunity then drove more than 30 km to explore even older deposits on a crater rim. MER Spirit found evidence that thermal waters (heated by volcanism or by impacts?) altered rocks to create sulfate salts, and siliceous sinters. These discoveries indicate that an early hydrological cycle apparently sustained precipitation, streams and lakes. Liquid water participated in rock weathering reactions, such as iron and sulfur oxidation, that created distinctive weathering regimes. Volcanism, impacts, groundwater and ice interacted at least locally. Redox chemical energy from volcanism, hydrothermal activity and weathering of crustal materials would have been available for any life. Thus conditions might have supported life in the past, at least locally. The main objective of the Mars Science Laboratory (MSL) Curiosity rover is to determine the extent to which Gale crater hosted environments capable of supporting microbial life. The rover has already found stream gravels as well as sediments that might have been deposited in an ancient lake. The rover is now traversing to Mt. Sharp, a 5 km-high mound that is located on the crater floor and that exhibits layered sedimentary rocks having diverse minerals (sulfates and clays) that apparently formed in the presence of liquid water. This rock sequence was deposited over an extended time period in diverse potentially habitable watery environments. Curiosity is poised to characterize a a well-preserved rock record of hundreds of millions of years of diverse environments and profound climate change.

layered phyllosilicates↗

NASA NTRS2015

Gusev-Meridiani-Type Soil Component Dissolved in Some Shock Glasses in Shergottites

Modal analysis, based on APXS, MiniTES and Mossbauer results obtained at Gusev and Meridiani sites on Mars, indicates that Martian soils consist predominantly of igneous minerals such as olivine, pyroxene and feldspar (approximately70 - 80%), with the balance consisting of alteration minerals such as sulfates, silica and chlorides]. These studies also showed that soil alteration did not occur in-situ and igneous and alteration components are derived from different sources. Below, we analyse the chemical abundance data obtained from shock glasses in shergottites using mass balance mixing models. In these models, the two main end members used are (a) host rock chemical composition and (b) the GM soils average composition as the second component. Here, we consider the S-bearing phases as indicators of added alteration phases in the shock glasses and GM soils. Although the S-bearing phase in shock glasses occurs as micron sized sulfide blebs, we showed in earlier abstracts that sulfur was originally present as sulfate in impact glass-precursor materials and was subsequently reduced to sulfide during shock melting. This conclusion is based on results obtained from S-K XANES studies, Fe/S atomic ratios in sulfide blebs and 34S/32S isotopic measurements in these sulfide blebs. Additionally, sulfur in several EET79001 Lith. A glasses is found to correlate positively with Al2O3 and CaO (and negatively with FeO and MgO), suggesting the presence of Al- and Ca- sul-fate-bearing phases. The distribution of the 87Sr/86Sr iso-topic ratios determined in Lith. A glasses (,27 &,188 and,54) indicate that Martian soil gypsum and host rock material were mixed with each other in the glass precursors. In some vugs in Lith A glass,27 detected gypsum laths. Furthermore, the Martian regolith-de-rived component (where sulfur typically occurs as sul-fate) is identified in these glasses by determining neutron produced isotopic excesses/deficits in 80Kr and 149Sm isotopes. Moreover, the suggestion that the large amount of sulfur found in,507 was sourced from pyrrhotite in the host rock, would require that excessive quantities of host rock would need to be stripped of sulfur to make this sulfide-rich glass. These results provide ample evidence that S occurred as sulfate and was added to glass precursor materials prior to impact shock.

Ross, D. K.↗

NASA NTRS2015

Diagenetic Mineralogy at Gale Crater, Mars

Three years into exploration of sediments in Gale crater on Mars, the Mars Science Laboratory rover Curiosity has provided data on several modes and episodes of diagenetic mineral formation. Curiosity determines mineralogy principally by X-ray diffraction (XRD), but with supporting data from thermal-release profiles of volatiles, bulk chemistry, passive spectroscopy, and laser-induced breakdown spectra of targeted spots. Mudstones at Yellowknife Bay, within the landing ellipse, contain approximately 20% phyllosilicate that we interpret as authigenic smectite formed by basalt weathering in relatively dilute water, with associated formation of authigenic magnetite as in experiments by Tosca and Hurowitz [Goldschmidt 2014]. Varied interlayer spacing of the smectite, collapsed at approximately 10 A or expanded at approximately 13.2 A, is evidence of localized diagenesis that may include partial intercalation of metal-hydroxyl groups in the approximately 13.2 A material. Subsequent sampling of stratigraphically higher Windjana sandstone revealed sediment with multiple sources, possible concentration of detrital magnetite, and minimal abundance of diagenetic minerals. Most recent sampling has been of lower strata at Mount Sharp, where diagenesis is widespread and varied. Here XRD shows that hematite first becomes abundant and products of diagenesis include jarosite and cristobalite. In addition, bulk chemistry identifies Mg-sulfate concretions that may be amorphous or crystalline. Throughout Curiosity's traverse, later diagenetic fractures (and rarer nodules) of mm to dm scale are common and surprisingly constant and simple in Ca-sulfate composition. Other sulfates (Mg,Fe) appear to be absent in this later diagenetic cycle, and circumneutral solutions are indicated. Equally surprising is the rarity of gypsum and common occurrence of bassanite and anhydrite. Bassanite, rare on Earth, plays a major role at this location on Mars. Dehydration of gypsum to bassanite in the dry atmosphere of Mars has been proposed but considered unlikely based on lab studies of dehydration kinetics in powdered samples. Dehydration is even less likely for bulk vein samples, as lab data show dehydration rates one to two orders of magnitude slower in bulk samples than in powders. On Mars, exposure ages of 100 Ma or more may be a significant factor in dehydration of hydrous phases.

Vaniman, David↗

NASA NTRS2016

Performing Mineral Hydration Experiments in the CheMin Diffractometer on Mars

Laboratory work is the cornerstone of experimental planetary geochemistry, mineralogy, and petrology, but much is to be gained by "experiments" while on a planet surface. Earth-bound experiments are often limited in ability to control multiple conditions relevant to planetary bodies (e.g. cycles in temperature and vapor pressure of water), but observations on-planet provide a unique opportunity where conditions are native to the planet and those affected by sampling and analysis can be constrained. The CheMin XRD instrument on Mars Science Laboratory has been able to test mineral hydration in samples held for up to 300 Mars days (sols). Clay minerals sampled at Yellowknife Bay early in the mission had both collapsed (10 Å) and expanded (13.2 Å) basal spacing. Collapsed interlayers were expected, but larger spacing was not; it was uncertain whether larger basal spacing would collapse on prolonged exposure to warmer conditions inside CheMin. Observation over several hundred sols showed no collapse, with the conclusion that expanded interlayer spacing was due to partial intercalation by metal-hydroxyl groups that resist dehydration. More recently, a sample of the Murray Formation, Oudam, provided the first XRD detection of gypsum and a chance to observe gypsum stability. Laboratory work suggests gypsum should be stable at Mars surface conditions, and indeed gypsum has been observed from orbit at higher latitudes and in thick veins at Yellowknife Bay by Mastcam reflectance spectra. Laboratory experiments have shown that on dehydration the gypsum would not become X-ray amorphous but would rather transform to a water-deficient bassanite structure. Over a period of 37 sols, it was observed that the Oudam sample in CheMin transformed from an assemblage of gypsum+anhydrite, to gypsum+bassanite+anhydrite, and finally to bassanite+anhydrite. Mg-sulfates were also anticipated but have not been observed in CheMin despite chemical evidence for their presence. Unlike gypsum, hydrated Mg-sulfates can transition to an X-ray amorphous form. Crystalline Mg-sulfates are expected higher in the section on Mount Sharp, where it should be possible to determine whether they persist or are destabilized after sampling, providing further insight into hydrous mineral stability at Mars near-equatorial conditions.

Vaniman, D. T.↗

NASA NTRS2014

Sulfur-Bearing Phases Detected by Evolved Gas Analysis of the Rocknest Aeolian Deposit, Gale Crater, Mars

The Sample Analysis at Mars (SAM) instrument suite detected SO2, H2S, OCS, and CS2 from approx.450 to 800 C during evolved gas analysis (EGA) of materials from the Rocknest aeolian deposit in Gale Crater, Mars. This was the first detection of evolved sulfur species from a Martian surface sample during in situ EGA. SO2(approx. 3-22 micro-mol) is consistent with the thermal decomposition of Fe sulfates or Ca sulfites, or evolution/desorption from sulfur-bearing amorphous phases. Reactions between reduced sulfur phases such as sulfides and evolved O2 or H2O in the SAM oven are another candidate SO2 source. H2S (approx.41-109 nmol) is consistent with interactions of H2O, H2 and/or HCl with reduced sulfur phases and/or SO2 in the SAM oven. OCS (approx.1-5 nmol) and CS2(approx.0.2-1 nmol) are likely derived from reactions between carbon-bearing compounds and reduced sulfur. Sulfates and sulfites indicate some aqueous interactions, although not necessarily at the Rocknest site; Fe sulfates imply interaction with acid solutions whereas Ca sulfites can form from acidic to near-neutral solutions. Sulfides in the Rocknest materials suggest input from materials originally deposited in a reducing environment or from detrital sulfides from an igneous source. The presence of sulfides also suggests that the materials have not been extensively altered by oxidative aqueous weathering. The possibility of both reduced and oxidized sulfur compounds in the deposit indicates a nonequilibrium assemblage. Understanding the sulfur mineralogy in Rocknest materials, which exhibit chemical similarities to basaltic fines analyzed elsewhere on Mars, can provide insight in to the origin and alteration history of Martian surface materials.

evolved gas analysis↗

NASA NTRS2014

Sulfur-bearing Phases Detected by Evolved Gas Analysis of the Rocknest Aeolian Deposit, Gale Crater, Mars

The Sample Analysis at Mars (SAM) instrument suite detected SO2, H2S, OCS, and CS2 from ~450 to 800degC during evolved gas analysis (EGA) of materials from the Rocknest aeolian deposit in Gale Crater, Mars. This was the first detection of evolved sulfur species from a Martian surface sample during in situ EGA. SO2 (~3-22 μmol) is consistent with the thermal decomposition of Fe sulfates or Ca sulfites, or evolution/desorption from sulfur-bearing amorphous phases. Reactions between reduced sulfur phases such as sulfides and evolved O2 or H2O in the SAM oven are another candidate SO2 source. H2S (~41-109 nmol) is consistent with interactions of H2O, H2 and/or HCl with reduced sulfur phases and/or SO2 in the SAM oven. OCS (~1-5nmol) and CS2 (~0.2-1 nmol) are likely derived from reactions between carbon-bearing compounds and reduced sulfur. Sulfates and sulfites indicate some aqueous interactions, although not necessarily at the Rocknest site; Fe sulfates imply interaction with acid solutions whereas Ca sulfites can form from acidic to near-neutral solutions. Sulfides in the Rocknest materials suggest input from materials originally deposited in a reducing environment or from detrital sulfides from an igneous source. The presence of sulfides also suggests that the materials have not been extensively altered by oxidative aqueous weathering. The possibility of both reduced and oxidized sulfur compounds in the deposit indicates a nonequilibrium assemblage. Understanding the sulfur mineralogy in Rocknest materials, which exhibit chemical similarities to basaltic fines analyzed elsewhere on Mars, can provide insight in to the origin and alteration history of Martian surface materials.

Gale Crater↗

NASA NTRS2017

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.↗

NASA NTRS2019

Evolved Gas Analyses of Sedimentary Rocks and Eolian Sediment in Gale Crater, Mars: Results of the Curiosity Rover's Sample Analysis at Mars Instrument.

The Sample Analysis at Mars instrument evolved gas analyzer (SAM-EGA) has detected evolved water, SO2, NO, CO2, CO, O2, and HCl from two eolian sediments and nine sedimentary rocks from Gale Crater, Mars. The SAM-EGA heats samples to 870°C and measures evolved gas releases as function of temperature. These evolved gas detections indicate nitrates, organics, oxychlorine phase, and sulfates are widespread with phyllosilicates and carbonates occurring in select Gale Crater materials. CO2 and CO evolved at similar temperatures suggesting that as much as 2373 ± 820 μgC/g may occur as organic carbon in the Gale Crater rock record while relatively higher temperature CO2 detections are consistent with carbonate (<0.70 ± 0.1 wt % CO3). Evolved NO amounts up to 0.06 ± 0.03 wt % NO3 have been detected while O2 detections suggests chlorates and/or perchlorates (0.05 to 1.05 wt % ClO4) are present. Evolution of SO2 indicated the presence of crystalline and/or poorly crystalline Fe and Mg sulfate and possibly sulfide. Evolved H2O (0.9 - 2.5 wt% H2O) was consistent with the presence of adsorbed water, hydrated salts, interlayer/structural water from phyllosilicates, and possible inclusion water in mineral/amorphous phases. Evolved H2S detections 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, Brad↗

NASA NTRS2017

Drivers of Precipitation Change: An Energetic Understanding

The response of the hydrological cycle to climate forcings can be understood within the atmospheric energy budget framework. In this study precipitation and energy budget responses to five forcing agents are analyzed using 10 climate models from the Precipitation Driver Response Model Intercomparison Project (PDRMIP). Precipitation changes are split into a forcing-dependent fast response and a temperature-driven hydrological sensitivity. Globally, when normalized by top-of-atmosphere (TOA) forcing, fast precipitation changes are most sensitive to strongly absorbing drivers (CO2, black carbon). However, over land fast precipitation changes are most sensitive to weakly absorbing drivers (sulfate, solar) and are linked to rapid circulation changes. Despite this, land-mean fast responses to CO2 and black carbon exhibit more intermodel spread. Globally, the hydrological sensitivity is consistent across forcings, mainly associated with increased longwave cooling, which is highly correlated with intermodel spread. The land-mean hydrological sensitivity is weaker, consistent with limited moisture availability. The PDRMIP results are used to construct a simple model for land-mean and sea-mean precipitation change based on sea surface temperature change and TOA forcing. The model matches well with CMIP5 ensemble mean historical and future projections, and is used to understand the contributions of different drivers. During the twentieth century, temperature-driven intensification of land-mean precipitation has been masked by fast precipitation responses to anthropogenic sulfate and volcanic forcing, consistent with the small observed trend. However, as projected sulfate forcing decreases, and warming continues, land-mean precipitation is expected to increase more rapidly, and may become clearly observable by the mid-twenty-first century.

Richardson, T. B.↗

NASA NTRS2021

Martian subsurface cryosalt expansion and collapse as trigger for landslides

On Mars, seasonal martian flow features known as recurring slope lineae (RSL) are prevalent on sun-facing slopes and are associated with salts. On Earth, subsurface interactions of gypsum with chlorides and oxychlorine salts wreak havoc: instigating sinkholes, cave collapse, debris flows, and upheave. Here, we illustrate (i) the disruptive potential of sulfate-chloride reactions in laboratory soil crust experiments, (ii) the formation of thin films of mixed ice-liquid water “slush” at −40° to −20°C on salty Mars analog grains, (iii) how mixtures of sulfates and chlorine salts affect their solubilities in low-temperature environments, and (iv) how these salt brines could be contributing to RSL formation on Mars. Our results demonstrate that interactions of sulfates and chlorine salts in fine-grained soils on Mars could absorb water, expand, deliquesce, cause subsidence, form crusts, disrupt surfaces, and ultimately produce landslides after dust loading on these unstable surfaces.

J. L. Bishop↗

NASA NTRS2019

Subsurface Cl-bearing salts as potential contributors to recurring slope lineae (RSL) on Mars

We report laboratory experimental results that support a brine-related hypothesis for the recurring slope lineae (RSL) on Mars in which the subsurface Cl-salts, i.e., hydrous chlorides and oxychlorine salts (HyCOS) are the potential source materials. Our experiments revealed that within the observed RSL temperature window TRSL (250–300 K), the deliquescence of HyCOS could occur in relative humidity ranges (RH≥22%–46%) much lower than those for hydrous (Mg, Fe)-sulfates (RH≥75%–96%). In addition, we demonstrated that the RH values kept by common HyCOS and hydrous sulfates in enclosures have a general trend as RH(sulfates) > RH(perchlorates) > RH(chlorides) (with same type of cation) in wide T range. It means that the required RH range for a Cl-bearing salt to deliquescence can be satisfied by a co-existing salt of different type, e.g., in the subsurface layers of mixed salts on Mars. Furthermore, we found a strong temperature dependence of the deliquescence rates for all tested HyCOS, e.g., a duration of 1–5 sols for all HyCOS at the high end (300 K) of TRSL, and of 20–70 sols for all tested HyCOS (except NaClO4·H2O) at the low end (250 K) of TRSL, which is consistent with the observed seasonal behavior of RSL on Mars. From a mass-balance point of view, the currently observed evidences on Mars do not support a fully-brine-wetted track model, thus we suggest a brine-triggered granular-flow model for the most RSL. Considering the recurrence of RSL in consecutive martian years, our experimental results support the rehydration of remnant HyCOS layers during a martian cold season through H2O vapor-to-salt direct interaction. We found that the evidences of HyCOS rehydration under Mars relevant P-T-RH conditions are detectable in a few minutes by in situ Raman spectroscopy. This rehydration would facilitate the recharge of H2O back into subsurface HyCOS, which could serve as the source material to trigger RSL in a subsequent warm season. The major limiting factor for this rehydration is the H2O supply, i.e., the H2O vapor density carried by current Mars atmospheric circulation and the diffusion rate of H2O vapor into the salt-rich subsurface in a cold season. In a worst-case scenario, these H2O supplies can support a maximum increase of hydration degrees of two for totally dehydrated HyCOS, whereas the full rehydration of subsurface HyCOS layers can be easily reached during a>30° obliquity period that has H2O vapor density 10× to 20× times the value of current obliquity. Overall, our results imply the existence of a large amount of Cl-bearing salts in the subsurface at RSL sites.

Alian Wang↗

NASA NTRS2021

Sensitivity of modeled Indian monsoon to Chinese and Indian aerosol emissions

The South Asian summer monsoon supplies over 80 % of India's precipitation. Industrialization over the past few decades has resulted in severe aerosol pollution in India. Understanding monsoonal sensitivity to aerosol emissions in general circulation models (GCMs) could improve predictability of observed future precipitation changes. The aims here are (1) to assess the role of aerosols in India's monsoon precipitation and (2) to determine the roles of local and regional emissions. For (1), we study the Precipitation Driver Response Model Intercomparison Project experiments. We find that the precipitation response to changes in black carbon is highly uncertain with a large intermodel spread due in part to model differences in simulating changes in cloud vertical profiles. Effects from sulfate are clearer; increased sulfate reduces Indian precipitation, a consistency through all of the models studied here. For (2), we study bespoke simulations, with reduced Chinese and/or Indian emissions in three GCMs. A significant increase in precipitation (up to ∼20 %) is found only when both countries' sulfur emissions are regulated, which has been driven in large part by dynamic shifts in the location of convective regions in India. These changes have the potential to restore a portion of the precipitation losses induced by sulfate forcing over the last few decades.

Indian monsoons↗

NASA NTRSDate not supplied

Assessing Organic Preservation and the Implications for Potential Biosignatures in the Bastide Member of the Séítah Formation, Jezero Crater

Introduction: Olivine has the highest CO2 trapping potential of ultramafic minerals, due to its rapid rate of dissolution and high percentage of divalent cations/unpolymerized silicate tetrahedra [1]. It generates divalent carbonates from CO2 and sequesters CO2 into the mineral matrix of the target lithology. The co-occurrence of olivine and carbonate within abraded targets from the Bastide Member of the Séítah Formation (Fm) of the Jezero crater floor [2] suggests the carbonation of olivine occurred within the mineral matrix hosted in a subsurface system. Hydrothermal origins for the subsurface system are hypothesized from orbital data [3]. This is supported by the detection of hydration features within the rock as well as the carbonate features are solely detected within the abrasion patch but not the rock’s surface. Organic preservation potential of abrasion patches: We incorporated the SHERLOC/WATSON results acquired from the Dourbes, Garde, and Quartier abrasion patches in the Séítah Fm to investigate the organomineral associations, and determine the biosignature preservation potential of these rocks. Dourbes is dominated by olivine and has minor amounts of carbonate, hydrated Ca-sulfate, and amorphous or microcrystalline silicate. Fluorescence features (330-340 nm) are detected in discrete locales and could be consistent with double ring aromatic organic molecules; yet, these features do not appear to be associated with an identified mineral phase. Dark subhedral to euhedral olivine grains within the Garde abrasion patch often co-occur with carbonate-consistent spectral signatures in all analyzed scans. The availability of Fe2+ is a known influence on olivine dissolution rates [1] and SuperCam estimates of the olivine composition (Forsterite-60 average for Sols 202-234) may thereby provide a constraint on the carbonation extent. Carbonated olivine phenocrysts within the matrix may be due to aqueous alteration, as the carbonation of nodules is consistent with observations in other hydrothermal systems and within Martian meteorites (ALH84001) [4]. In comparison, the Quartier abrasion patch represents an extensively altered endmember within the Bastide Member of the Séítah Fm. It contains a fluorescence doublet at 305/325 nm that coexists with multiple species of Na-sulfate and Mg-sulfate, Mg-carbonates, olivine [5]. Aqueous alteration and implications for habitability: The identification of primary and secondary mineral phases observed in the Bastide Member suggests the release of cations from primary ultramafic minerals through aqueous alteration. Within Garde, the carbonate detected appears to be Mg-rich and likely formed from the in situ alteration of Mg-rich olivine within the region as carbonate has only been detected within the rock via in situ analysis. Carbonates derived from abiotic and biotic reactions preserve biosignatures (i.e. indices of habitability) on Earth. The detected carbonate phase found in association with fluorescent features within the rock matrix may also indicate potential organic compounds preserved in a putative hydrothermal system. Fluorescent features (~330 nm) are unique to Garde and Dourbes, though they are co-located to carbonate signatures solely within Garde, and between the light toned minerals. Identification of these fluorescent features may be consistent with 1-2 ring aromatic compounds. The limit of detection for Raman is multiple orders of magnitude greater than the limit of detection required for fluorescence [6]. Implications for provenance: Hydrothermal systems represent disequilibrium chemical conditions that are hypothesized to have supported the emergence of life and also preserve ancient carbon within precipitated carbonates [7]. Hydrothermal system associated carbonates are capable of preserving biosignatures up to an estimated ~3.77 – 4.28 Gya [8]. Thus, carbonated olivine found within the Séítah Fm may represent a high-potential biosignature preserving environment on Mars. The formation of carbonates by an aqueous alteration process, such as carbonation of olivine is also consistent with hypotheses for carbonate within the greater regional-olivine bearing unit [2,3], which contains Garde, Dourbes, and Quartier. Acknowledgments: This work was carried out at the Jet Propulsion Laboratory, The California Institute of Technology under a contract from NASA. References: [1] Wood et al., (2019) ES&T, 6, 10. [2] Stack, K. et al., (2020) Space Sci Rev, 216, 127. [3] Tarnas, J. et al., (2021) JGR: Planets, 126, 11. [4] Steele et al., (2007) Meteorit. Planet. Sci., 42, 9. [5] Murphy, A.E. et al., (2022) LPSC [6] Bhartia et al., (2021) Space Sci Rev, 217, 58. [7] Luther (2021) GRL, 48, e2021GL094869. [8] Dodd et al., (2017) Nature, 543, 60-64

E L Cardarelli↗