Search NASA⌕ Search

SEARCH · Search NASA

Results for “Sulfate”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 19 records
All sourcesNASA NTRSDOE OSTI
NASA NTRS2023

Stratigraphic Change from Ca-Sulfate to Mg-Sulfate in the Sedimentary Bedrock of Gale Crater, Mars: Recent Results from Curiosity’s APXS

Curiosity’s APXS instrument has been quantifying sulfates over >30 km of traverse in Gale crater. The rover recently arrived at sedimentary strata where orbital data predicted hydrated Mg-sulfates that may record a change to a drier paleoenvironment. The sequence of strata is in the Marker Band Valley (MBV), the ~10-m-thick, metal-rich Marker Band (MB), and strata above the MB. Here, we report recent sulfate observations by the APXS and provide constraints on the occurrence of Mg-sulfate and the implications for paleoenvironment interpretations. In sedimentary strata below the MBV, Mg-sulfate enrichment (~5-10 wt%) is generally limited to larger diagenetic nodules (~1-3 cm). Ca is positively correlated with S at proportions consistent with Ca-sulfate addition to the bedrock matrix. S variation is thus controlled primarily by Ca-sulfate, which increases ~30% in transitional units below the MBV. The MBV contains the first evidence of Mg-sulfate enrichment in the bedrock matrix, confirmed by the detection of crystalline Mg-sulfate by CheMin. The MBV bedrock has the same overall bulk composition as the underlying Mt. Sharp gp. strata, but with an additional ~5-15 wt% Mg-sulfate. The MB has contrasting sulfate content: (1) targets with very high concentrations of MnO (1.5 wt%), FeO (47 wt%), and Zn (2.2 wt%) are depleted in S and (2) targets with lower metal content have evidence of Mg-sulfate addition. Strata above the MB have a bulk composition that is distinct from other rocks in Gale. For example, the bedrock has molar Fe/Mn (50-60) and Cr/Ti (0.4-0.7) similar to basaltic soil, but ~3X higher Zn and high Ge (50 ppm). Median SO3 above the MB (15 wt%) is higher than the MBV (14 wt%) as well as strata below the MBV (~8 wt%). S does not correlate with Ca or Mg above the MBV. MgO (~9 wt%) is higher than below the MBV (~5 wt%) and the SO3/MgO (1.7) is in the same range as the Mg-sulfate-bearing MBV, suggesting Mg-sulfate enrichment. APXS data indicate that the MBV and above the MB preserve a relatively sharp vertical transition (~5-10 m) from Ca-sulfate to Mg-sulfate in the rock matrix. The sharp contacts with the sulfate-depleted MB and the notable change in bulk composition above the MB may indicate a complex depositional and/or diagenetic history under conditions where enrichments in the highly soluble Mg-sulfates were ultimately preserved.

Jeffrey Allan Berger↗
NASA NTRS2006

Laboratory Simulated Acid-Sulfate Weathering of Basaltic Materials: Implications for Formation of Sulfates at Meridiani Planum and Gusev Crater, Mars

Acid-sulfate weathering of basaltic materials is a candidate formation process for the sulfate-rich outcrops and rocks at the MER rover Opportunity and Spirit landing sites. To determine the style of acid-sulfate weathering on Mars, we weathered basaltic materials (olivine-rich glassy basaltic sand and plagioclase feldspar-rich basaltic tephra) in the laboratory under different oxidative, acid-sulfate conditions and characterized the alteration products. We investigated alteration by (1) sulfuric-acid vapor (acid fog), (2) three-step hydrothermal leaching treatment approximating an open system and (3) single-step hydrothermal batch treatment approximating a "closed system." In acid fog experiments, Al, Fe, and Ca sulfates and amorphous silica formed from plagioclase-rich tephra, and Mg and Ca sulfates and amorphous silica formed from the olivine-rich sands. In three-step leaching experiments, only amorphous Si formed from the plagioclase-rich basaltic tephra, and jarosite, Mg and Ca sulfates and amorphous silica formed from olivine-rich basaltic sand. Amorphous silica formed under single-step experiments for both starting materials. Based upon our experiments, jarosite formation in Meridiani outcrop is potential evidence for an open system acid-sulfate weathering regime. Waters rich in sulfuric acid percolated through basaltic sediment, dissolving basaltic phases (e.g., olivine) and forming jarosite, other sulfates, and iron oxides. Aqueous alteration of outcrops and rocks on the West Spur of the Columbia Hills may have occurred when vapors rich in SO2 from volcanic sources reacted with basaltic materials. Soluble ions from the host rock (e.g., olivine) reacted with S to form Ca-, Mg-, and other sulfates along with iron oxides and oxyhydroxides.

Golden, D. C.↗
NASA NTRS2002

Rationally designed fluorescently labeled sulfate-binding protein mutants: evaluation in the development of a sensing system for sulfate

Periplasmic binding proteins from E. coli undergo large conformational changes upon binding their respective ligands. By attaching a fluorescent probe at rationally selected unique sites on the protein, these conformational changes in the protein can be monitored by measuring the changes in fluorescence intensity of the probe which allow the development of reagentless sensing systems for their corresponding ligands. In this work, we evaluated several sites on bacterial periplasmic sulfate-binding protein (SBP) for attachment of a fluorescent probe and rationally designed a reagentless sensing system for sulfate. Eight different mutants of SBP were prepared by employing the polymerase chain reaction (PCR) to introduce a unique cysteine residue at a specific location on the protein. The sites Gly55, Ser90, Ser129, Ala140, Leu145, Ser171, Val181, and Gly186 were chosen for mutagenesis by studying the three-dimensional X-ray crystal structure of SBP. An environment-sensitive fluorescent probe (MDCC) was then attached site-specifically to the protein through the sulfhydryl group of the unique cysteine residue introduced. Each fluorescent probe-conjugated SBP mutant was characterized in terms of its fluorescence properties and Ser171 was determined to be the best site for the attachment of the fluorescent probe that would allow for the development of a reagentless sensing system for sulfate. Three different environment-sensitive fluorescent probes (1,5-IAEDANS, MDCC, and acylodan) were studied with the SBP171 mutant protein. A calibration curve for sulfate was constructed using the labeled protein and relating the change in the fluorescence intensity with the amount of sulfate present in the sample. The detection limit for sulfate was found to be in the submicromolar range using this system. The selectivity of the sensing system was demonstrated by evaluating its response to other anions. A fast and selective sensing system with detection limits for sulfate in the submicromolar range was developed. Copyright 2002 Wiley Periodicals, Inc. Biotechnol Bioeng 78: 517-526, 2002.

Evaluation Studies↗
NASA NTRS2004

Thermal Emission Spectroscopy of Sulfates: Possible Hydrous Iron-Sulfate in the Soil at the MER-A Gusev Crater Landing Site

Sulfates are likely to be present on Mars as indicated by the sulfur abundances measured at the Viking and Pathfinder landing sites (approx. 5-10% by weight SO3) [1-3] and because of Mars strongly oxidizing environment. Telescopic observations of Mars tentatively identified weak sulfate bands in near infrared [4] and thermal infrared [5] data. The currently orbiting midinfrared instruments (TES, THEMIS) and the Mini-TES on the Mars Exploration Rover landers may enable a positive identification [6] and determination of the chemistry of the sulfates. Critically important to the identification of these minerals is the presence of their spectra in a spectral library. There exist approximately 370 sulfate-mineral species [7]. Sulfate minerals occur in volcanic, hydrothermal, evaporitic, and chemical-weathering environments.

Lane, Melissa D.↗
NASA NTRS1992

Stratospheric sulfate aerosol in and near the Northern Hemisphere polar vortex - The morphology of the sulfate layer, multimodal size distributions, and the effect of denitrification

Measurements were made of stratospheric sulfate aerosols using a passive cavity aerosol spectrometer and a condensation nucleus counter on a NASA ER-2 aircraft in the Airborne Arctic Stratospheric Experiment of 1989. The problems of representative and accurate sampling and particle evaporation were explicitly addressed in the design of the inlets and reduction of the data. The measurements suggest that the sulfate aerosol is bimodal in the polar vortex above the mass mixing ratio maximum in the sulfate layer. It appears that a nuclei mode of small, newly formed particles exists in this region. A stronger case is made for a nuclei mode in the upper few kilometers of the troposphere and in the lower few kilometers of the stratosphere. This mode is probably a global phenomenon occurring in all seasons. Comparison of denitrified and nondenitrified air suggests that denitrification removes some of the larger sulfate particles.

Wilson, J. G.↗
NASA NTRS2017

Acid-Sulfate Alteration at Gusev Crater and Across Mars: High-SiO2 Residues and Ferric Sulfate Precipitates

The Mars Exploration Rover Spirit ended its mission in Gusev crater on sol 2210 after it had become stuck in a deposit of fined-grained and sulfate rich soil with dust covered solar panels unfavorably pointed toward the sun. Final analysis of remaining data from Spirit's Moessbauer spectrometer (Fe redox and mineralogy) for sols 1529 through 2071 is now complete. We focus here on chemical (APXS) and MB data for targets having high-SiO2 or high-SO3 and process link the targets through mixing and geochemical modelling to an acid-sulfate system centered at Home Plate, which is considered to be a hydrovolcanic complex.

Morris, R. V.↗
NASA NTRS2013

Olivine Weathering aud Sulfate Formation Under Cryogenic Conditions

High resolution photography and spectroscopy of the martian surface (MOC, HiRISE) from orbit has revolutionized our view of Mars with one of the most important discoveries being wide‐spread layered sedimentary deposits associated with sulfate minerals across the low to mid latitude regions of Mars. The mechanism for sulfate formation on Mars has been frequently attributed to playa‐like evaporative environments under prolonged warm conditions. An alternate view of the ancient martian climate contends that prolonged warm temperatures were never present and that the atmosphere and climate has been similar to modern conditions throughout most of its history. This view has had a difficult time explaining the sedimentary history of Mars and in particular the presence of sulfate minerals which seemingly need more water. We suggest here that mixtures of atmospheric aerosols, ice, and dust have the potential for creating small films of cryo‐concentrated acidic solutions that may represent an important unexamined environment for understanding weathering processes on Mars. This study seeks to test whether sulfate formation may be possible at temperatures well below 0degC in water limited environments removing the need for prolonged warm periods to form sulfates on early Mars. To test this idea we performed laboratory experiments to simulate weathering of mafic minerals under Mars‐like conditions. The weathering rates measured in this study suggest that fine grained olivine on Mars would weather into sulfate minerals in short time periods if they are exposed to H2SO4 aerosols at temperatures at or above ‐40degC. In this system, the strength of the acidic solution is maximized through eutectic freezing in an environment where the silicate minerals are extremely fine grained and have high surface areas. This provides an ideal environment despite the very low temperatures. On Mars the presence of large deposits of mixed ice and dust is undisputed. The presence of substantial sulfur‐rich volcanism, and sulfur‐rich surface deposits also makes it very likely that sulfate aerosols have also been an important component of the martian atmosphere. Thus mixtures of ice, dust, and sulfate aerosols are likely to have been common on the martian surface. Given the fact that it is not difficult to achieve surface temperatures above ‐40degC on Mars throughout its history, it seems likely that sulfate formation on Mars is controlled by the availability of sulfate aerosols and not by the martian climate. The current polar regions of Mars and Earth provide interesting analogs. Large regions of sulfaterich material have been detected on and around the modern north polar region of Mars. The prevalence of ice‐dust mixtures in this region and the existence of sulfates within the ice cap itself are strong evidence for the origin of the sulfates from inside the ice deposits. In addition sulfates have been found in ice deposits in Greenland and Mount Fuji on Earth that have been attributed to forming within the ice deposit. These sulfates can form either through interaction with dust particles in the atmosphere or through weathering inside the ice itself.

Niles, Paul B.↗
NASA NTRSDate not supplied

Identifying Sources of Sulfate Preserved in High Elevation Lava Tubes From Mauna Loa, Hawaii

Volcanic sulfates record a history of their formation pathways in their triple oxygen isotope compositions, making them a powerful target for understanding atmospheric chemistry. To understand how these isotopic signals may be preserved in sulfate minerals, we investigate multiple O and S isotopes of thenardite, mirabilite, and gypsum from in a Mars analog environment: a pair of lava tubes near the summit of Mauna Loa, Hawaii. Based on 16 O-, 17 O- 18 O compositions, the primary oxygen sources for sulfates in the lava tube are atmospheric oxygen (O 2 ), peroxide (H 2 O 2 ), and ozone (O 3 ). We suggest the isotopic signature of O 2 originates from combustion of reduced sulfur gases and/or elemental sulfur at the eruptive source or within the lava tube soon after skylight collapse. Sulfate with isotopic signatures of peroxide and ozone are typically expected from aqueous reactions in cloud droplets. Chemical modeling indicates the observed proportion of ozone sourced sulfate requires pH greater than ~5.4, higher than measured cloud water pH, instead suggesting the observed O 3 signature could not have formed in cloud water droplets. We interpret that sulfate possessing an ozone signature in the lava tube sulfates formed on wetted surfaces of the lava tubes with alkalinity from alteration of basaltic glass. Furthermore, the oxygen and sulfur isotopes of the sulfate are uncorrelated. Multiple sulfur isotopes ( 32 S- 33 S- 34 S- 36 S) from the Mauna Loa sulfates are consistent with ocean island basalt from Pitcairn, suggesting the sulfate-sulfur has not been modified compared to its volcanic source. The findings of this study indicate that oxidation by ozone plays a key role in the formation of sulfate within lava tubes. We also find that combustion is a significant pathway toward sulfuric acid formation in volcanic environments. Similar signatures should be expected on other planets if volcanism is a significant sulfate source, as has been suggested for Mars. If true, sulfates in returned samples from Mars may hold key information on pO 2 , pCO 2 and planetary scale oxygen fluxes at the time of sulfate formation.

Justin Hayles↗
NASA NTRS1998

Crystallization of Chicken Egg White Lysozyme from Sulfate Salts

It has been "known" that chicken egg white lysozyme does not crystallize from sulfate, particularly ammonium sulfate, salts, but instead gives amorphous precipitates. This has been the basis of several studies using lysozyme comparing macromolecule crystal nucleation and amorphous precipitation. Recently Ries-Kautt et al (Acta Cryst D50, (1994) 366) have shown that purified isoionic CEWL could be crystallized from low concentrations of sulfate at basic pH, and we subsequently showed that in fact CEWL could be purified in both the tetragonal and orthorhombic forms using ammonium sulfate over the pH range 4.0 to 7.8 (Acta Cryst D53, (1997) 795). We have now extended these observations to include a range of common sulfate salts, specifically sodium, potassium, rubidium, magnesium, and manganese sulfates. In all cases but the manganese sulfates both the familiar tetragonal and orthorhombic forms were obtained, with unit cell dimensions close to those known for the "classic" sodium chloride crystallized forms. Manganese sulfate has only yielded orthorhombic crystals to date. All crystallizations were carried out using low (typically less than or equal to 6 M) salt and high (greater than approximately 90 mg/ml) protein concentrations. As with ammonium sulfate, the tetragonal - orthorhombic phase shift appears to be a function of both the temperature and the protein concentration, with higher temperatures and concentrations favoring the orthorhombic and lower the tetragonal form. The phase change range is somewhat reduced for the sulfate salts, depending upon conditions being typically between approximately 15 - 20 C. Both the magnesium and manganese sulfates gave crystals at salt concentrations over 0.6 M as well, with magnesium sulfate giving a very slowly nucleating and growing hexagonal form. A triclinic crystal form, characterized by aggressively small crystals (typically 0.1 mm in size) has been occasionally obtained from ammonium sulfate. Finally, preliminary spot solubility determinations have suggested that in some cases the solubility increases with increasing salt concentrations.

Forsythe, Elizabeth↗
NASA NTRS2012

Sources of Sulfate Found in Mounds and Lakes at the Lewis Cliffs Ice Tongue, Transantarctic

Massive but highly localized Na-sulfate mounds (mirabilite, Na2SO4.10H2O) have been found at the terminal moraine of the Lewis Cliffs Ice Tongue (LCIT), Antarctica. (Sigma)34S and (Sigma)18O values of LCIT mirabilite range from +48.8 to +49.3% (CDT), and -16.6 to -17.1% (V-SMOW), respectively, while (Delta)17O average -0.37% (V-SMOW). LCIT mirabilite mounds are isotopically different from other mirabilite mounds found in coastal regions of Antarctica, which have isotope values close to seawater compositions. (Sigma)18O and (Delta)17O values suggest the incorporation of isotopically light glacial water. Data point to initial sulfate formation in an anoxic water body, either as a stratified anoxic deep lake on the surface, a sub-glacial water reservoir, or a sub-glacial lake. Several surface lakes of varying size are also present within this region of the LCIT, and in some cases are adjacent to the mirabilite mounds. O and D isotope compositions of surface lakes confirm they are derived from a mixture of glacial ice and snow that underwent moderate evaporation. (Sigma)18O and (Sigma)D (V-SMOW) values of snow, ice, and lake water range from -64.2 to -29.7%, and -456.0 to -231.7%, respectively. However, the isotope chemistry of these surface lakes is extremely different from the mounds. Dissolved SO4-2 (Sigma)34S and (Sigma)18O values range from +12.0 to +20.0% and -12.8 to -22.2% (the most negative (Sigma)18O of terrestrial sulfate ever reported), respectively, with sulfate (Delta)17O ranging from +0.93 to 2.24%. Ion chromatography data show that lake water is fresh to brackish in origin, with TDS less than 1500 ppm, and sulfate concentration less than 431 ppm. Isotope and chemical data suggest that these lakes are unlikely the source of the mirabilite mounds. We suggest that lake water sulfate is potentially composed of a mixture of atmospheric sulfate and minor components of sulfate of weathering origin, much like the sulfate in the polar plateau soils of the McMurdo Dry Valleys. A simple model explains mirabilite mound formation at the LCIT. Sulfur redox processes could occur sub-glacially as a result of liquid-water-based glacial conditions (Alpine style glacier), most likely formed by pressure melting of overlying ice (Aharon, GCA, 52, 2321-2331). We suggest that the aqueous base of the LCIT contains dissolved SO42- and is anoxic where sulfate reduction to H2S, HS-, or native sulfur takes place. Sulfide is removed by either precipitation as sulfide minerals or by escape of H2S (neither of which have been observed). Mirabilite precipitation is likely the result of evaporation or freezing of sulfate-rich brines as they reach the surface where they manifest themselves as mounds. Pressure from the overlying ice contributing to a pressure-melting scenario that creates the sub-glacial aqueous environment also contributes to the mechanism of upward transport of the sulfate-rich fluids. Further evidence to support this upward transport model comes from the nature of ice motion at the LCIT. Cassidy et al (Meteoritics, 27, 490-525, 1992) pointed out that it is the vertical ice motion in this area that creates the meteorite-stranding surface that could also account for upward transport of sulfate-rich fluids. Alternatively, mirabilite was deposited in a similar condition as present-day coastal Antarctica when the LCIT was wetter and warmer

Socki, Richard↗
NASA NTRS2002

The Effects of Low Sulfate Concentrations on Modern Microbial Mat Communities: A Long Term Manipulation

Microbial mats were widespread during the first ca. 2 Ga. of our biosphere's history. To better understand microbial ecosystems and their biomarkers under the low sulfate levels present in early oceans, we attempted a long-term (ca. 1 year) manipulation of sulfate in modem mats. Mats collected from salt ponds at Guerrero Negro, Baja Calif. Sur were incubated in a Greenhouse "Collaboratory" at Ames. Mats were maintained in artificial seawater brine containing either: 1) sulfate levels normal for these mats (70 mM), or 2) brine in which sulfate was replaced by chloride. Sulfate concentrations in the "low sulfate" brine gradually approached their lowest (to date) value of 0. 1 mM as sulfate was consumed and/or diffused out of the mat over a period of ca. 4 months. During that period of time, a number of differences between the treatments emerged. Relative to the "low sulfate" mats, "normal sulfate" mats had: 1) lower consumption of oxygen in the lower levels of the mat, 2) higher efficiencies of oxygenic photosynthesis, and 3) higher rates of nitrogen fixation. Rates of methane production by the mats increased greatly as sulfate concentrations fell below ca. 0.2 mM. In contrast, "low" and "normal" sulfate mats had similar net rates of exchange of O2 and dissolved inorganic C between the mats and overlying water. Reduced sulfate levels have diverse impacts upon these ecosystems.

Bebout, Brad↗
NASA NTRS2006

Sulfates on Mars: Indicators of Aqueous Processes

Recent analyses by MER instruments at Meridiani Planum and Gusev crater and the OMEGA instrument on Mars Express have provided detailed information about the presence of sulfates on Mars [1,2,3]. We are evaluating these recent data in an integrated multi-disciplinary study of visible-near-infrared, mid-IR and Mossbauer spectra of several sulfate minerals and sulfate-rich analog sites. Our analyses suggest that hydrated iron sulfates may account for features observed in Mossbauer and mid-IR spectra of Martian soils [4]. The sulfate minerals kieserite, gypsum and other hydrated sulfates have been identified in OMEGA spectra in the layered terrains in Valles Marineris and Terra Meridiani [2]. These recent discoveries emphasize the importance of studying sulfate minerals as tracers of aqueous processes. The sulfate-rich rock outcrops observed in Meridiani Planum may have formed in an acidic environment similar to acid rock drainage environments on Earth [5]. Because microorganisms typically are involved in the oxidation of sulfides to sulfates in terrestrial sites, sulfate-rich rock outcrops on Mars may be a good location to search for evidence of past life on that planet. Whether or not life evolved on Mars, following the trail of sulfate minerals will lead to a better understanding of aqueous processes and chemical weathering.

Bishop, Janice L.↗
NASA NTRS2012

Chemical and Mineralogical Characterization of Acid-Sulfate Alteration of Basaltic Material on Mauna Kea Volcano, Hawaii: Jarosite and Hydrated Halloysite

Sulfates have been identified on the martian surface during robotic surface exploration and by orbital remote sensing. Measurements at Meridiani Planum (MP) by the Alpha-Particle X-ray Spectrometer (APXS) and Mossbauer (MB) instruments on the Mars Exploration Rover Opportunity document the presence of a ubiquitous sulfate-rich outcrop (20-40% SO3) that has jarosite as an anhydrous Fe3+-sulfate [1- 3]. The presence of jarosite implies a highly acidic (pH <3) formation environment [4]. Jarosite and other sulfate minerals, including kieserite, gypsum, and alunite have also been identified in several locations in orbital remote sensing data from the MEx OMEGA and MRO CRISM instruments [e.g. 5-8]. Acid sulfate weathering of basaltic materials is an obvious pathway for formation of sulfate-bearing phases on Mars [e.g. 4, 9, 10]. In order to constrain acid-sulfate pathways on Mars, we are studying the mineralogical and chemical manifestations of acid-sulfate alteration of basaltic compositions in terrestrial environments. We have previously shown that acidsulfate alteration of tephra under hydrothermal conditions on the Puu Poliahu cone (summit region of Mauna Kea volcano, Hawaii) resulted in jarosite and alunite as sulfate-bearing alteration products [11-14]. Other, more soluble, sulfates may have formed, but were leached away by rain and melting snow. Acidsulfate processes on Puu Poliahu also formed hematite spherules similar (except in size) to the hematite spherules observed at MP as an alteration product [14]. Phyllosilicates, usually smectite }minor kaolinite are also present as alteration products [13]. We discuss here an occurrence of acid-sulfate alteration on Mauna Kea Volcano (Hawaii). We report VNIR spectra (0.35-2.5 microns ASD spectrometer), Mossbauer spectra (MER-like ESPI backscatter spectrometer), powder XRD (PANalytical), and major element chemical compositions (XRF with LOI and Fe redox) for comparison to similar data acquired or to be acquired by MRO-CRISM and MEx OMEGA, MERMB, MSL-CheMin, and MER and MSL APXS, respectively.

Graff, Trevor G.↗
NASA NTRS2018

Multi-model Comparison of the Volcanic Sulfate Deposition from the 1815 Eruption of Mt. Tambora

The eruption of Mt. Tambora in 1815 was the largest volcanic eruption of the past 500 years. The eruption had significant climatic impacts, leading to the 1816 "year without a summer", and remains a valuable event from which to understand the climatic effects of large stratospheric volcanic sulfur dioxide injections. The eruption also resulted in one of the strongest and most easily identifiable volcanic sulfate signals in polar ice cores, which are widely used to reconstruct the timing and atmospheric sulfate loading of past eruptions. As part of the Model Intercomparison Project on the climatic response to Volcanic forcing (VolMIP), five state-of-the-art global aerosol models simulated this eruption. We analyze both simulated background (no Tambora) and volcanic (with Tambora) sulfate deposition to polar regions and compare to ice core records. The models simulate overall similar patterns of background sulfate deposition, although there are differences in regional details and magnitude. However, the volcanic sulfate deposition varies considerably between the models with differences in timing, spatial pattern and magnitude. Mean simulated deposited sulfate on Antarctica ranges from 19 to 264 kgkm-2 and on Greenland from 31 to 194 kgkm-2, as compared to the mean ice-core derived estimates of roughly 50 kgkm-2 for both Greenland and Antarctica. The ratio of the hemispheric atmospheric sulfate aerosol burden after the eruption to the average ice sheet deposited sulfate varies between models by up to a factor of 15. Sources of this inter-model variability include differences in both the formation and the transport of sulfate aerosol. Our results suggest that deriving relationships between sulfate deposited on ice sheets and atmospheric sulfate burdens from model simulations may be associated with greater uncertainties than previously thought.

Marshall, Lauren↗
NASA NTRS2016

Similarities Across Mars: Acidic Fluids at Both Meridiani Planum and Gale Crater in the Formation of Magnesium-Nickel Sulfates

In-situ identification of sulfates at the martian surface by the Mars Exploration Rovers and the Mars Science Laboratory have included calcium sulfates with various states of hydration (gypsum, bassanite, anhydrite), iron sulfates of likely fumarolic origin, massive deposits of iron hydroxysulfates indicative of an acidic history, and minor occurrences of magnesium sulfates. Recent measurements by the Opportunity and Curiosity Alpha Particle X-ray Spectrometers (APXS) have indicated the presence of Ni-substituted Mg-sulfates at the Meridiani Planum and Gale Crater landing sites. The Opportunity rover has traversed nearly 43 km and is currently exploring the impact breccias of the rim of Endeavour crater, near a location where signatures of aqueous alteration have been established from orbit. APXS analyses of subsurface materials excavated by a rover wheel show clear evidence for a Mg(Ni)-sulfate with Mg:Ni (is) approximately 100:1 (molar). On the other side of the planet, Curiosity is continuing its climb up Mount Sharp after driving (is) approximately 13 km since landing. Over the last 4 km of the traverse, there have been multiple chemical analyses of erosionally-resistant nodules and dendritic features in a finely laminated mudstone unit which also indicate Mg(Ni)-sulfate (Mg:Ni (is) approximately 30:1, molar). The geologic settings for the Endeavour rim and the Mount Sharp mudstones are clearly different, but similar formation conditions for these sulfates may be possible. Ni(2+) readily substitutes for Mg(2+) in a variety of geochemical processes due to their comparable ionic radii. The availability of soluble Ni at the time of Mg-sulfate precipitation suggests acidic solutions. The fluids responsible for alteration in the Endeavour rim and for the formation of nodules in Gale mudstones may have had similar chemical characteristics at the time the Mg-sulfates were formed.

Yen, Albert S.↗
NASA NTRSDate not supplied

Triple Oxygen Isotope Kinetics of Sulfate From Pyrite Oxidation

Sulfates from low temperature terrestrial and marine environments are out of equilibrium with their oxygen sources. Instead, oxygen isotope compositions of sulfate imply they are dominated by kinetic signatures of oxidative and reductive processes (Killingsworth et al., 2022) that are under-constrained compared to equilibrium effects (Hayles and Killingsworth, 2022). Consequently, the specific role of pyrite oxidation in setting the oxygen isotope composition of sulfate is also under-constrained. This scenario inhibits a more nuanced understanding of small variations in the oxygen isotopes of sulfate and their implications for tracing oxygen sources and sulfur cycle transformations, particularly in low-temperature relatively sulfate-limited freshwater systems such as rivers, lakes, aquifers, and mining-affected environments. To alleviate these knowledge gaps, we conduct pyrite oxidation experiments at time scales spanning minutes to years, analyze the triple oxygen isotope compositions (∆ 17 O and δ 18 O) of sulfate products, and interpret results using molecular modeling. Our preliminary results show isotopic relationships of 1) pyrite-derived sulfate ∆ 17 O reaching above the meteoric water line as its δ 18 O becomes lighter than water, and 2) sulfate ∆ 17 O and δ 18 O extending between water and O 2 . From these results we interpret a kinetic isotope effect between sulfate and water and mixing between sulfate end members containing most of their oxygen atoms from water and from O 2 .

Oxygen isotopes↗