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Compositional Impact of Io Volcanic Emissions on Jupiter's Magnetosphere and the Icy Galilean Moons

The magnetospheric ion population of Jupiter is dominated by the 1000 kg/s of iogenic material constantly ejected by IO volcanism as neutral gas (approx. 1 kg/s goes out as high speed dust grains), subsequent atmospheric losses to the IO torus, and radial transport of torus ions throughout the magnetosphere. As that magnetosphere is greatly distended in radial size by the iogenic plasma loading, so are surfaces of the other Galilean moons also significantly, and perhaps even dominantly, affected by iogenic plasma bombardment, e.g. at the level up to 0.2 kg/s heavy ions (mostly O and S) onto Europa as per local plasma ion measurements. In comparison, cometary impacts onto IO deliver about 0.02 kg/s of impact ejecta to Europa via ballistic transfer through the Jupiter system. The magnetosphere of this system operates as a powerful engine to produce and transport ions from the IO source to the surfaces of these other moons, and any future orbiter missions to these moons must account for surface distributions of the iogenic material and its chemical effects before real assessments can be made of sensible chemical materials otherwise arising from primordial formation and subsequent evolution of these moons. This is a fundamental problem of space weathering that must be addressed for all planetary bodies with thin atmospheres and direct surface exposure to their space plasma environments. Long-standing debates from Galileo Orbiter measurements about the origins of hydrate sulfates at Europa present examples of this problem, as to whether the sulfates arise from oceanic minerals or from iogenic sulfur chemistry. Any orbiter or landed mission to Europa for astrobiological investigations would further need to separate the potential chemical biosignatures of life or its precursors from the highly abundant background of iogenic material. Although no single ion carries a tag identifying it as of iogenic or other origin, the elemental abundance distributions of ions to be measured throughout the jovian magnetosphere and in the local moon environments can act as tracers if we know from direct measurements and models the distributions at the mostly likely sources, i.e. at IO. However, our knowledge of these abundances are very limited from earlier in-situ and remote measurements, mainly confined to major (S, O) and some minor (Na, K, Cl) species with abundances at or above a few percent relative to O. Future in-situ plasma measurements by the planned Jupiter Europa Orbiter and Jupiter Ganymede Orbiter missions should extend the abundance coverage to minor and even trace elemental species. For Europa astrobiological investigations it is also important to specify iogenic inputs and surface processing of isotopic species. We discuss the range of abundance distributions arising from models for IO hot volcanic emissions, and from the subsequent dynamics of ion injection, magnetospheric transport, and icy moon surface bombardment.

Cooper, John↗

Short Range-Ordered Minerals: Insight into Aqueous Alteration Processes on Mars

Short range-ordered (SRO) aluminosilicates (e.g., allophane) and nanophase ferric oxides (npOx) are common SRO minerals derived during aqueous alteration of basaltic materials. NpOx refers to poorly crystalline or amorphous alteration products that can be any combination of superparamagnetic hematite and/or goethite, akaganeite, schwertmannite, ferrihydrite, iddingsite, and nanometer-sized ferric oxide particles that pigment palagonitic tephra. Nearly 30 years ago, SRO phases were suggested as alteration phases on Mars based on similar spectral properties for altered basaltic tephra on the slopes of Mauna Kea in Hawaii and Martian bright regions measured by Earth-based telescopes. Detailed characterization of altered basaltic tephra on Mauna Kea have identified a variety of alteration phases including allophane, npOx, hisingerite, jarosite, alunite, hematite, goethite, ferrihydrite, halloysite, kaolinite, smectite, and zeolites. The presence of npOx and other Fe-bearing minerals (jarosite, hematite, goethite) was confirmed by the M ssbauer Spectrometer onboard the Mars Exploration Rovers. Although the presence of allophane has not been definitely identified on Mars robotic missions, chemical analysis by the Spirit and Opportunity rovers and thermal infrared spectral orbital measurements suggest the presence of allophane or allophane-like phases on Mars. SRO phases form under a variety of environmental conditions on Earth ranging from cold and arid to warm and humid, including hydrothermal conditions. The formation of SRO aluminosilicates such as allophane (and crystalline halloysite) from basaltic material is controlled by several key factors including activity of water, extent of leaching, Si activity in solution, and available Al. Generally, a low leaching index (e.g., wet-dry cycles) and slightly acidic to alkaline conditions are necessary. NpOx generally form under aqueous oxidative weathering conditions, although thermal oxidative alteration may occasional be involved. The style of aqueous alteration (hydrolytic vs. acid sulfate) impacts which phases will form (e.g., oxides, oxysulfates, and oxyhydroxides). Knowledge on the formation processes of SRO phases in basaltic materials on Earth has allowed significant enhancement in our understanding of the aqueous processes at work on Mars. The 2011 Mars Science Laboratory (MSL) will provide an instrument suite that should improve our understanding of the mineralogical and chemical compositions of SRO phases. CheMin is an X-ray diffraction instrument that may provide broad X-ray diffraction peaks for SRO phases; e.g., broad peaks around 0.33 and 0.23 nm for allophane. Sample Analysis at Mars (SAM) heats samples and detects evolved gases of volatile-bearing phases including SRO phases (i.e., carbonates, sulfates, hydrated minerals). The Alpha Particle X-ray Spectrometer (APXS) and ChemCam element analyzers will provide chemical characterization of samples. The identification of SRO phases in surface materials on MSL will be challenging due to their nanocrystalline properties; their detection and identification will require utilizing the MSL instrument suite in concert. Ultimately, sample return missions will be required to definitively identify and fully characterize SRO minerals with state-of-the-art laboratory instrumentation back on Earth.

Ming, Douglas W.↗

Definitive Mineralogy from the Mars Science Laboratory Chemin Instrument

The Mars Science Laboratory (MSL) rover will land in Gale Crater on Mars in August 2012. The planned landing site is an alluvial fan near the base of the crater's central mound. Orbital remote sensing of this 5 km high mound indicates the presence of hydrated sulfates, interstratified with smectite and hematite-bearing layers. Minerals formed in an aqueous environment are of particular interest given that water is a fundamental ingredient of living systems and that MSL's prime science objective is to investigate martian habitability.

Yen, A. S.↗

Chemical and Mineralogical Characterization of a Hematite-bearing Ridge on Mauna Kea, Hawaii: A Potential Mineralogical Process Analog for the Mount Sharp Hematite Ridge

The Mars Science Laboratory (MSL) rover Curiosity landed in Gale Crater in August 2012 and is currently roving towards the layered central mound known as Mount Sharp [1]. Compact Reconnaissance Imaging Spectrometer for Mars (CRISM) hyperspectral data indicate Mount Sharp contains an ~5 km stratigraphic sequence including Fe-Mg smectites, hematite, and hydrated sulfates in the lower layers separated by an unconformity from the overlying anhydrous strata [1,2,3]. Hematite was initially detected in CRISM data to occur in the lower sulfate layers on the north side of the mound [2]. [3] further mapped a distinct hematite detection occurring as part of a ~200 m wide ridge that extends ~6.5 km NE-SW, approximately parallel with the base of Mount Sharp. It is likely a target for in-situ analyses by Curiosity. We document here the occurrence of a stratum of hematite-bearing breccia that is exposed on the Puu Poliahu cinder cone near the summit of Mauna Kea volcano (Hawaii) (Fig.1). The stratum is more resistant to weathering than surrounding material, giving it the appearance of a ridge. The Mauna Kea hematite ridge is thus arguably a potential terrestrial mineralogical and process analog for the Gale Crater hematite ridge. We are acquiring a variety of chemical and mineralogical data on the Mauna Kea samples, with a focus on the chemical and mineralogical information already available or planned for the Gale hematite ridge.

Graff, T. G.↗

Mineral Trends in Early Hesperian Lacustrine Mudstone at Gale Crater, Mars

The Mars Science Laboratory Curiosity rover landed in Gale crater in August 2012 to study the layered sediments of lower Aeolis Mons (i.e., Mount Sharp), which have signatures of phyllosilicates, hydrated sulfates, and iron oxides in orbital visible/near-infrared observations. The observed mineralogy within the stratigraphy, from phyllosilicates in lower units to sulfates in higher units, suggests an evolution in the environments in which these secondary phases formed. Curiosity is currently investigating the sedimentary structures, geochemistry, and mineralogy of the Murray formation, the lowest exposed unit of Mount Sharp. The Murray formation is dominated by laminated lacustrine mudstone and is approx.200 m thick. Curiosity previously investigated lacustrine mudstone early in the mission at Yellowknife Bay, which represents the lowest studied stratigraphic unit. Here, we present the minerals identified in lacus-trine mudstone from Yellowknife Bay and the Murray formation. We discuss trends in mineralogy within the stratigraphy and the implications for ancient lacustrine environments, diagenesis, and sediment sources.

Rampe, E. B.↗

Formation of Fe(III) (hydr)oxides from Fe(II) sulfides: Implications for akaganeite detection on Mars

Akaganeite (β-FeO(OH,Cl)) is a Fe(III) (hydr)oxide with a tunnel structure typically occupied by chloride. This mineral was first proposed to be present in Meridiani Planum and Gusev crater on Mars and akaganeite was subsequently detected by X-ray diffraction in Yellowknife Bay and Vera Rubin Ridge locations in Gale crater. Akaganeite in Gale crater has been proposed to form from Fe(II) sulfides but formation conditions remain unconstrained. We investigated akageneite formation by oxidative alteration of natural Fe(II) sulfide pyrrhotite exposed to HCl and oxidation-hydrolysis of Fe(II) HCl-leached from pyrrhotite at initial pH0 1.5, 2, 3, and 4. X-ray diffraction and Mössbauer analyses revealed formation of poorly-crystallized akageneite in oxidative alteration experiments. Air-exposure of the HCl-reacted dry pyrrhotite led to an increase in akageneite formation and precipitation of Fe(II) hydrated sulfates, goethite, and hydronium jarosite. Iron(II) oxidation-hydrolysis was sensitive to Si dissolved from phyllosilicates in one pyrrhotite sample. Akaganeite and goethite formed at pH0 1.5 and 2 with akageneite more abundant at dissolved Si/Fe ratio of 0.08 and goethite more abundant at Si/Fe of 0.01. Akaganeite formed together with hematite, ferrihydrite, and goethite at pH0 3, and formation was suppressed at pH0 4. Well-crystallized akageneite precipitated at pH0 1.5 while akaganeite of poorer crystallinity formed at pH0 2 and 3. Akageneite in Gale crater could form from sulfides by both mechanisms: oxidative alteration of sulfide minerals and oxidation-hydrolysis of leached Fe(II). The processes likely occurred during late diagenetic events triggered by interactions of acidic Cl-bearing groundwater with Fe(II) sulfides. Akaganeite in Yellowknife Bay, Gale crater could have formed by Fe(II) oxidation-hydrolysis either as a sole Fe(III) (hydr)oxide at pH<2 or along with ferrihydrite and hematite at 2<pH<4 in Si-enriched conditions. Akaganeite formation at Vera Rubin Ridge, Gale crater could have occurred through oxidative alteration of sulfides in Cl-bearing pH 1.2-1.5 solutions. The presence of well-crystalline akageneite in Vera Rubin Ridge indicates that Fe(II) oxidation-hydrolysis contributed to akageneite formation.

Mars gale crater akaganeite↗

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.↗

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.↗

Thermal emission spectra of Mars (5.4-10.5 microns) - Evidence for sulfates, carbonates, and hydrates

Spectra of the Martian thermal emission in the 5.4-10.5 micron region are reported. Emission features at 7.8 and 9.7 microns are attributed to surface silicates, and an emission feature at 6.1 micron is attributed to a molecular water component of the surface material. An absorption band at 8.7 micron and a possible one at 9.8 microns is attributed to sulfate or bisulfate anions probably located at a distorted crystalline site, and an absorption band at 6.7 microns is attributed to carbonate or bicarbonate anions located in a distorted crystalline site. Spectral simulations indicate that the sulfate- and carbonate-bearing minerals are contained in the same particles of airborne dust as the dominant silicate minerals, that the dust optical depth is about 0.6 at a reference wavelength of 0.3 micron over the area of the observed spots, and that sulfates and carbonates constitute 10-15 percent and 1-3 percent by volume of the airborne dust, respectively.

Pollack, James B.↗

Mineralogy, Abundance, and Hydration State of Sulfates and Chlorides at the Mars Pathfinder Landing Site

Detection of elevated concentrations of S and Cl at the landing sites of Viking 1 and 2 [1], and Mars Pathfinder (MP) [2-5] reveals the presence of sulfates and chlorides in soil and rock samples [1-10]. These data are consistent with the findings of Ca sulfates and NaCl in Martian meteorites [11,12], and with Earth-based spectroscopic observations [13,14] tentatively indicating the presence of sulfates on Mars. Although the correlation of S and Mg in Viking and MP samples could reveal the occurrence of Mg sulfate [1-10], the mineralogy of sulfates and chlorides remains unclear.

Zolotov, M. Y.↗

Testing Destruction of Clay Minerals By Silica-Poor Brines in Gale Crater, Mars Using Laboratory and Field Experiments

The Mars Science Laboratory (MSL) Curiosity rover landed in Gale crater to investigate the cause for mineralogical changes seen from orbit, including the clay-sulfate mineral transition observed on its central mound, Aeolis Mons. The lower strata show spectral signatures of clay minerals, hematite, and hydrated Mg sulfates, and the upper strata are dominated by hydrated Mg sulfate signatures. This significant transition has been observed in other locations on Mars, and therefore processes related to the clay mineral-sulfate transition are likely important broadly across Mars. The bulk mineralogy of ~3.7 Ga sedimentary rocks in Gale crater is a product of variations in sediment sources and depositional processes, with overprinting by episodes of early and late diagenetic alteration. Sedimentary analyses of the smectite clay minerals observed in the Glen Torridon (GT) region of Mount Sharp suggest formation in a lacustrine aqueous environment. Examination of the Vera Rubin ridge (VRR) strata indicate that it was formed at the same time as GT and later altered by extensive diagenesis. Recent work suggests that the observed mineral transition from smectites and talc-serpentinites in GT to iron oxides and oxyhydroxides and VRR may have resulted from extensive diagenetic alteration by density driven, silica-poor brines sourced from the overlying sulfur-bearing unit on Mount Sharp. This process of alteration by silica-poor brines is observed in limited locations on Earth. We are therefore working to demonstrate the impacts of silica poor brines on clay mineral alteration in laboratory column and terrestrial analog burial experiments. Column experiments allow the investigation of dissolution and precipitation under conditions that represent a closer analog to natural environments, while burial experiments allow examination of weathering reactions of a known starting material after a specific period of time in a natural field environment. Both methods are valuable for interpreting the water-rock interactions between clay minerals and brines. In preparation for these longer-term column and burial experiments, we are performing preliminary batch dissolution experiments on materials relevant to Glen Torridon: nontronite and serpentinite. We are using magnesium sulfate brine solutions relevant to those proposed on Mars. The results of this study can provide constraints on the characteristics of the diagenetic fluids that formed the altered minerals in Gale crater. They can also provide insights into the role of brine density-driven diagenesis in past aqueous environments on Mars, which have been proposed to be widespread.

J E Valdueza↗

The magnesium sulfate-water system at pressures to 4 kilobars

Hydrated magnesium sulfate constitutes up to 1/6 of the mass of carbonaceous chondrites, and probably is important in many icy asteroids and satellites. It occurs naturally in meteorites mostly as epsomite. MgSO4, considered anhydrously, comprises nearly 3/4 of the highly soluble fraction of C1 chondrites. Thus, MgSO4 is probably an important solute in cryovolcanic brines erupted on certain icy objects in the outer solar system. While the physiochemical properties of the water-magnesium sulfate system are well known at low pressures, planetological applications of these data are hindered by a dearth of useful published data at elevated pressures. Accordingly, solid-liquid phase equilibria was recently explored in this chemical system at pressures extending to about 4 kilobars. The water magnesium sulfate system in the region of the eutectic exhibits qualitatively constant behavior between pressures of 1 atm and 2 kbar. The eutectic melting curve closely follows that for water ice, with a freezing point depression of about 4 K at 1 atm decreasing to around 3.3 K at 2 kbars. The eutectic shifts from 17 pct. MgSO4 at 1 atm to about 15.3 pct at 2 kbars. Above 2 kbars, the eutectic melting curve again tends to follow ice.

Hogenboom, D. L.↗

Mineralogical Evidence for Environmental Change in the Clay-Sulfate Transition at Gale Crater, Mars

A primary reason for selecting Gale crater as the Mars Science Laboratory (MSL) Curiosity rover landing site was a clear mineralogical transition from Fe/Mg smectite in older strata to hydrated Mg sulfate salts in younger strata observed in orbital visible/shortwave-infrared reflectance data. This transition has been observed in other early-Hesperian terrains on Mars and has been hypothesized to signal a planet-wide change in climate from relatively warm and wet to cold and dry. Curiosity studied the sedimentology and geochemical and mineralogical composition of rocks in this “clay-sulfate transition” region from sols 3052 to 3572 (i.e., March 2021 to August 2022), with arrival at the sulfate unit on sol 3574. Here, we report on the mineralogical measurements made by the CheMin X-ray diffractometer of the six drill targets in the clay-sulfate transition and the first drill target in the sulfate unit. We use compositional data and sedimentological observations to interpret depositional and diagenetic environments and present hypotheses to explain the transition from clay minerals to hydrated Mg sulfates.

E. B. Rampe↗

Mineralogical Trends Over the Clay-Sulfate Transition in Gale Crater from the Mars Science Laboratory CheMin Instrument

The Mars Science Laboratory Curiosity rover landed in Gale crater in 2012 to explore a sedimentary sequence in lower Aeolis Mons (informally known as Mount Sharp)that shows changes in mineralogy from orbital visible/near-infrared reflectance spectroscopy[1]. Sedimentary layers with spectral signatures of hydrated Mg sulfate overly layers with signatures of Fe/Mg smectite, a mineralogical stratigraphy that is seen in other ancient sedimentary rocks across Mars[e.g., 2-4]. Curiosity recently completed its campaign in a valley with a strong orbital signature of smectite, named Glen Torridon. Mineralogical measurements by the CheMin X-ray diffractometer(XRD), complemented by evolved gas analyses by the Sample Analysis at Mars (SAM) instrument suite, allowed the identification of abundant Fe3+-bearing dioctahedral smectite (i.e., nontronite) in Glen Torridon [5-6]. Curiosity left Glen Torridon in February 2021 and began traversing through a “clay-sulfate transition” zone on the way to the pediment and the sulfate unit[e.g., 7]. This clay-sulfate transition is defined in orbital reflectance spectroscopy as having a weak signature of hydrated Mg sulfate. Curiosity has drilled five outcrops over the traverse through the clay-sulfate transition and delivered the rock powders to CheMin for mineralogical analysis. Here, we report on the mineral assemblages of those five targets derived from CheMin XRD patterns and discuss mineralogical trends as the rover approaches the sulfate unit.

Mars↗

Lunar and Planetary Science XXXV: Weird Martian Minerals: Complex Mars Surface Processes

The session "Complex Mars Surface" included the following reports:A Reappraisal of Adsorbed Superoxide Ion as the Cause Behind the Reactivity of the Martian Soils; Sub-Surface Deposits of Hydrous Silicates or Hydrated Magnesium Sulfates as Hydrogen Reservoirs near the Martian Equator: Plausible or Not?; Thermal and Evolved Gas Analysis of Smectites: The Search for Water on Mars; Aqueous Alteration Pathways for K, Th, and U on Mars; Temperature Dependence of the Moessbauer Fraction in Mars-Analog Minerals; Acid-Sulfate Vapor Reactions with Basaltic Tephra: An Analog for Martian Surface Processes; Iron Oxide Weathering in Sulfuric Acid: Implications for Mars; P/Fe as an Aquamarker for Mars; Stable Isotope Composition of Carbonates Formed in Low-Temperature Terrestrial Environments as Martian Analogs; Can the Phosphate Sorption and Occlusion Properties Help to Elucidate the Genesis of Specular Hematite on the Mars Surface?; Sulfate Salts, Regolith Interactions, and Water Storage in Equatorial Martian Regolith; Potential Pathways to Maghemite in Mars Soils: The Key Role of Phosphate; and Mineralogy, Abundance, and Hydration State of Sulfates and Chlorides at the Mars Pathfinder Landing Site.

Source record↗

Derivation of the midinfrared (5.0-25.0 micron) optical constants of hydrous carbonate and sulfate

There is ample theoretical and observational evidence suggesting liquid water was once stable at the surface of Mars. Because water is essential to the evolution of life, it is important to understand the types of environments in which the liquid water was present. For example, if water were present early in Mars' history, then this raises the possibility that biological activity may have evolved only to eventually become extinct as liquid water became scarce. Alternatively, if liquid water were stable only later in Mars' history, then it becomes problematic to envision mechanisms by which biological activity evolved and remained viable without water until more favorable conditions existed. Even without biological activity, atmospheric carbon dioxide dissolved in water can assist the chemical weathering of primary igneous minerals producing common secondary phases such as hydartes, carbonates, and sulfates. While the identification of hydrates, carbonates, and sulfates on Mars cannot provide direct evidence of biological activity, it can provide significant information regarding the presence and duration of an environment that would support the presence of liquid water at the surface. The specific mineralogy of these secondary phases can provide insight into the environments of their formation. For example, the slow precipitation that occurs in large standing bodies of water, e.g. oceans or lakes, commonly results in the formation of calcite, magnesite, dolomite, siderite, and rhodochrosite. Rapid precipitation that occurs in ephemeral bodies of water, e.g. hypersaline lakes or playas, can result in the formation of all of the above phases as well as aragonite, vaterite, hydrated carbonates, alkali carbonates, bicarbonates, and other poorly ordered phases. Absorption features identified in recent near-infrared spectra of Mars have been interpreted as being due to bicarbonate and bisulfate located in the mineral scaplite. Spectral data returned by the Mariner 6 and 7 spacecraft have been inerpreted as remaining consistent with the presence of hydrated carbonates. Additional, airborne thermal infrared spectra of Mars have been interpreted as implying the presence of carbonates, sulfates, and hydrates. Modeling of the thermal infrared data relied upon the optical constants of calcite anhydrite and a mixture of water in basalt because of their availability. The derived abundances of carbonate and sulfate were 1-3 percent and 10-15 percent by volume. However, the observed complexity and positions of the bands suggested other carbonate-, and sulfate-bearing species. We have already derived optical constants for hydrous and anhydrous silicates, and we are now applying these techniques to the derivation of the optical constants of hydrous carbonate and sulfate.

Roush, Ted L.↗

Organic Products of Fatty Acid and Magnesium Sulfate Mixtures after Gamma Radiolysis: Implications for Missions to Europa

If ocean-derived materials are present at Europa’s surface, they would represent accessible records of ocean chemistry and habitability, but such materials would be further processed by the moon’s harsh radiation environment. In this study, saturated fatty acids were precipitated onto a Europa-relevant hydrated magnesium sulfate and exposed to gamma radiation doses up to 2 MGy at -196° C. Alkane chains, with carbon numbers one less than those of the starting fatty acids, were the most abundant radiolysis products in solvent and thermal extracts analyzed by gas chromatography mass spectrometry. Detections of monounsaturated fatty acids and combined radiolysis products were attributed to the experiment’s Europa-like parameters. Additionally, elevated concentrations of shorter-chain saturated fatty acids suggest that gamma radiation induced charge remote fragmentation of the alkyl chains of some starting fatty acids under these experimental conditions. Quantitation of fatty acid concentrations in the irradiated samples enabled the calculation of a radiolysis constant that indicated exposure to a 5 MGy dose of gamma radiation would have resulted in a ~90% loss of the initial fatty acid population. The samples were further studied by Raman spectroscopy and laser desorption and ionization mass spectrometry, which characterized the distribution of fatty acids and their radiolysis products on sulfate surfaces. The substantial loss of starting fatty acids typically seen with increasing radiation dose, along with the remarkable diversity of radiolysis products identified, suggest that the detection of fatty acids in irradiated sulfate deposits on Europa will be challenged by rapid destruction of any initial fatty acid populations and scrambling of their residual signals by a myriad of organic radiolysis products. If missions to Europa encounter sulfate deposits, targeting minimally irradiated units may still enable the detection of surviving fatty acid signatures that could inform about Europa’s subsurface chemistry and habitability.

James M T Lewis↗

Sampling the oxidative weathering products and the potentially acidic permafrost on Mars

Large areas of Mars' surface are covered by oxidative weathering products containing ferric and sulfate ions having analogies to terrestrial gossans derived from sulfide mineralization associated with iron-rich basalts. Chemical weathering of such massive and disseminated pyrrhotite-pentlandite assemblages and host basaltic rocks in the Martian environment could have produced metastable gossaniferous phases (limonite containing poorly crystalline hydrated ferric sulfates and oxyhydroxides, clay silicates and opal). Underlying groundwater, now permafrost on Mars, may still be acidic due to incomplete buffering reactions by wall-rock alteration of unfractured host rock. Such acidic solutions stabilize temperature-sensitive complex ions and sols which flocculate to colloidal precipitates at elevated temperatures. Sampling procedures of Martian regolith will need to be designed bearing in mind that the frozen permafrost may be corrosive and be stabilizing unique complex ions and sols of Fe, Al, Mg, Ni and other minor elements.

Burns, Roger G.↗