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At least 217 records · Page 12

Remediation Technologies Eliminate Contaminants

All research and development has a story behind it, says Jacqueline Quinn, environmental engineer at Kennedy Space Center. For Quinn, one such story begins with the Saturn 1B launch stand at Kennedy and ends with a unique solution to a challenging environmental problem. Used in a number of Apollo missions and during the Skylab program, the Saturn 1B launch stand was dismantled following the transition to the Space Shuttle Program and stored in an open field at Kennedy. Decades later, the Center s Environmental Program Office discovered evidence of chemicals called polychlorinated biphenyls (PCBs) in the field s soil. The findings were puzzling since PCBs a toxin classified as a probable carcinogen by the Environmental Protection Agency (EPA) have been banned in the United States since 1979. Before the ban, PCBs were commonly used in transformer oils that leached into the ground when the oils were changed out and dumped near transformer sites, but there were no electrical transformers near the dismantled stand. It soon became apparent that the source of the PCBs was the launch stand itself. Prior to the ban, PCBs were used extensively in paints to add elasticity and other desirable characteristics. The PCB-laden paint on the Saturn 1B launch stand was flaking off into the field s soil. Nobody knew there were PCBs in the paint, says Quinn, noting that the ingredient was not monitored carefully when it was in use in 1960s. In fact, she says, the U.S. EPA was not even established until 1970, a year after Neil Armstrong first set foot on the Moon. Nobody knew any better at the time, Quinn says, but today, we have the responsibility to return any natural environmental media to as close to pristine a condition as possible. Quinn, fellow engineer Kathleen Loftin, and other Kennedy colleagues already had experience developing unprecedented solutions for environmental contamination; the team invented the emulsified zero-valent iron (EZVI) technology to safely treat groundwater tainted by chlorinated solvents once used to clean rocket engine components. The award-winning innovation (Spinoff 2010) is now NASA s most licensed technology to date. PCBs in paint presented a new challenge. Removing the launch stand for recycling proved a difficult operation; the toxic paint had to be fully stripped from the steel structure, a lengthy and costly process that required the stripped paint to be treated before disposal. Noting the lack of efficient, environmentally friendly options for dealing with PCBs, Quinn and her colleagues developed the Activated Metal Treatment System (AMTS). AMTS is a paste consisting of a solvent solution containing microscale particles of activated zero-valent metal. When applied to a painted surface, the paste extracts and degrades the PCBs into benign byproducts while leaving the paint on the structure. This provides a superior alternative to other methods for PCB remediation, such as stripping the paint or incinerating the structure, which prevents reuse and can release volatized PCBs into the air. Since its development, AMTS has proven to be a valuable solution for removing PCBs from paint, caulking, and various insulation and filler materials in older buildings, naval ships, and former munitions facilities where the presence of PCBs interferes with methods for removing trace explosive materials. Miles of potentially toxic caulking join sections of runways at airports. Any of these materials installed before 1979 potentially contain PCBs, Quinn says. "This is not just a NASA problem," she says. "It s a global problem."

Source record↗

A Novel Method for Remediation of PCBs in Weathered Coatings

Polychlorinated biphenyls (PCBs) are a group of synthetic aromatic compounds with the general formula C 12H1oCl that were historically used in industrial paints, caulking material and adhesives, as their properties enhanced structural integrity, reduced flammability and boosted antifungal properties. Although the United States Environmental Protection Agency (USEPA) has banned the manufacture of PCBs since 1979, they have been found in at least 500 of the 1,598 National Priorities List (Superfund) sites identified by the USEPA. Prior to the USEPA's ban on PCB production, PCBs were commonly used as additives in paints and asphalt-based adhesives that were subsequently applied to a variety of structures. Government facilities constructed as early as 1930 utilized PCB-containing binders or PCB-containing paints, which are now leaching into the environment and posing ecological and worker health concerns. To date, no definitive in situ, non-destructive method is available for the removal of PCBs found in weathered coatings or on painted structures/equipment. The research described in this paper involves the laboratory development and field-scale deployment of a new and innovative solution for the removal and destruction of PCBs found in painted structures or within the binding or caulking material on structures. The technology incorporates a Bimetallic Treatment System (BTS) that extracts and degrades only the PCBs found on the facilities, leaving the structure virtually unaltered.

Brooks, Kathleen B.↗

Three Dimensionally Interlinked, Dense, Solid Form of Single-Walled CNT Ropes

A 3D networked, dense form of single-walled carbon nanotubes (SWNT) has been made through isotropic shrinking of a gel-like SWNT-water paste by very slow evaporation. Approximately 35 g of Raw HiPco nanotubes were cleaned by the method of soft baking (250 C for 15 hours in air saturated with water vapor) in a glass beaker followed by leaching with concentrated hydrochloric acid. Typically, one liter of concentrated hydrochloric acid was added to the soft-baked voluminous mass in the same large beaker, and allowed to digest at room temperature with stirring overnight. The acid-digested SWNT slurry was filtered through a large porcelain Buchner funnel under atmospheric pressure. The slurry was continuously flushed, while still in the funnel, with a very slow but steady stream of deionized water employing a peristaltic pump. This process, referred to as gwashing, h continued until the filtrate water dripping from the Buchner funnel was clear, colorless, and neutral to a pH paper. This took about 15 liters of water to flow through the slurry over a day. At this point, the water pump was stopped and the SWNT-water slurry was allowed to drain the excess water for about 10 hours. The resulting thick paste of SWNT-neutral water was transferred to a beaker. The beaker was covered with aluminum foil with few holes and allowed to dry very slowly in a hood at room temperature. In about eight weeks, the sample gradually dried isotropically to a cylindrical dense mass referred to as a carbon nanotube block (CNB). There was no carbonaceous matter sticking to any of the glass surface where the SWNT-water paste made contact. The approximate dimensions of the cylindrical SWNT block that weighed 28 g were 1.5 in. (.3.8 cm) in diameter and 1.25 in. (.3.2 cm) in height. The bottom portion of the cylinder that was in contact with the beaker surface was slightly wider, indicating some resistance to shrinking. The cylindrical mass also consisted of several pores. The cylindrical mass was very tough and could not be broken with a small hammer using considerable force. The mass of the solid could be polished over a fine grain emery paper or even a smooth, stainless steel surface indicative of alignment at finer levels.

Smalley, Richard E.↗

Petrologic and In Situ Geochemical Constraints on Diogenite Genesis

Diogenites, members of the howardite, eucrite and diogenite (HED) clan, are orthopyroxenite, harzburgite and dunite meteorites [1-3]. Most are breccias, but remnant textures indicate they were originally coarse-grained rocks, with grain sizes of order of cm. Their petrography and compositions support an origin as crustal cumulates from a differentiated asteroid. Astronomical observations, and surface mineralogy and composition of Vesta determined by the Dawn spacecraft suggest that asteroid (4) Vesta is the parent object for HED meteorites [4-6]. The origin of diogenites is an unsettled issue. It is difficult to fit their bulk compositional characteristics into global magma ocean models that successfully describe the compositions of basaltic and cumulate eucrites [7]. Compositional analyses of acid-leached bulk samples have led to the hypothesis that many diogenites were formed late by interaction of their parent melts with a eucritic crust [8]. Those observations may alternatively be explained by subsolidus equilibration of trace elements between orthopyroxene and minor/ accessory phases in the rocks such as plagioclase and phosphate [7]. These competing hypotheses can be tested through in situ measurements of trace and minor elements in orthopyroxene. Our new petrologic observations and in situ minor and trace element data for a suite of diogenites are used to discuss the petrologic evolution of diogenites. Our preliminary data on two diogenites are consistent with the hypothesis that subsolidus element mobilization processes caused unusual trace element signatures seen in some diogenites [7]. We cannot stress strongly enough, however, that the sample set is too small and that additional data are required before definitive conclusions can be made.

Mittlefehldt, David W.↗

The Halite-Bearing Zag and Monahans (1998) Meteorite Breccias: Shock Metamorphism, Thermal Metamorphism and Aqueous Alteration on the H-Chondrite Parent Body

Zag and Monahans (1998) are H-chondrite regolith breccias comprised mainly of lightcolored metamorphosed clasts, dark clasts that exhibit extensive silicate darkening, and a halite-bearing clastic matrix. These meteorites reflect a complex set of modification processes that occurred on the H-chondrite parent body. The light-colored clasts are thermally metamorphosed H5 and H6 rocks that were fragmented and deposited in the regolith. The dark clasts formed from light-colored clasts during shock events that melted and mobilized a significant fraction of their metallic Fe-Ni and troilite grains. The clastic matrices of these meteorites are rich in solar-wind gases. Parent-body water was required to cause leaching of chondri tic minerals and chondrule glass; the fluids became enriched in Na, K, CI, Br, AI, Ca, Mg and Fe. Evaporation of the fluids caused them to become brines as halides and alkalies became supersaturated; grains of halite (and, in the case of Monahans (1998), halite with sylvite inclusions) precipitated at low temperatures (less than or equal to 100 C) in the porous regolith. In both meteorites fluid inclusions were trapped inside the halite crystals. Primary fluid inclusions were trapped in the growing crystals; secondary inclusions formed subsequently from fluid trapped within healed fractures.

Rubin, Alan E.↗

Application of CO2 Snow Jet Cleaning in Conjunction with Laboratory Based Total Reflection X-Ray Fluorescence

The Genesis mission was the first mission returning solar material to Earth since the Apollo program [1,2]. Unfortunately the return of the space craft on September 8, 2004 resulted in a crash landing, which shattered the samples into small fragments and exposed them to desert soil and other debris. Thus only small fragments of the original collectors are available, each having different degrees of surface contamination. Thorough surface cleaning is required to allow for subsequent analysis of solar wind material embedded within. An initial cleaning procedure was developed in coordination with Johnson Space Center which focused on removing larger sized particulates and a thin film organic contamination acquired during collection in space [3]. However, many of the samples have additional residues and more rigorous and/or innovative cleaning steps might be necessary. These cleaning steps must affect only the surface to avoid leaching and re-distribution of solar wind material from the bulk of the collectors. To aid in development and identification of the most appropriate cleaning procedures each sample has to be thoroughly inspected before and after each cleaning step. Laboratory based total reflection X-ray fluorescence (TXRF) spectrometry lends itself to this task as it is a non-destructive and surface sensitive analytical method permitting analysis of elements from aluminum onward present at and near the surface of a flat substrate [4]. The suitability of TXRF has been demonstrated for several Genesis solar wind samples before and after various cleaning methods including acid treatment, gas cluster ion beam, and CO2 snow jet [5 - 7]. The latter one is non-invasive and did show some promise on one sample [5]. To investigate the feasibility of CO2 snow jet cleaning further, several flown Genesis samples were selected to be characterized before and after CO2 snow application with sample 61052 being discussed below.

Schmeling, M.↗

The Ability of AMSTAR Dechlorination Solution to Remove and Degrade PCBs from Contaminated Surfaces

Polychlorinated biphenyls (PCBs) are a group of synthetic aromatic compounds with the general formula C12H(10-x)Cl(-x) that were historically used in industrial paints, caulking material and adhesives, as their properties enhanced structural integrity, reduced flammability and boosted antifungal properties. Although the United States Environmental Protection Agency (USEPA) has banned the manufacture of PCBs since 1979, they have been found in at least 500 of the 1,598 National Priorities List (Superfund) sites identified by the USEPA. Prior to the US EPA's ban on PCB production, PCBs were commonly used as additives in paints and asphalt-based adhesives that were subsequently applied to a variety of structures. Government facilities constructed as early as 1930 utilized PCB-containing binders or PCB-containing paints, which are now leaching into the environment and posing ecological and worker health concerns. In 2006, a commercially available product known as AMSTAR Dechlorination Solution was tested at NASA's Kennedy Space Center for its ability to remove and degrade PCBs from structural materials. This evaluation was requested by the Environmental Security Technology Certification Program (ESTCP) evaluating the ability of NASA's Bimetallic Treatment System (BTS) to remove and degrade PCBs from structural materials. The results of the laboratory testing are to be used to determine if a side-by-side field-scale test comparing BTS to AMSTAR was warranted. A recommended sampling and analysis testing program was submitted to ESTCP that included triplicate screening of AMSTAR's PCB dechlorination capabilities on a variety of surfaces including glass, bare metal, and painted metal coupons. The test procedures, analytical techniques and results obtained are presented in this interim report to ESTCP.

Quinn, Jacqueline E.↗

High-Voltage Clock Driver for Photon-Counting CCD Characterization

A document discusses the CCD97 from e2v technologies as it is being evaluated at Goddard Space Flight Center's Detector Characterization Laboratory (DCL) for possible use in ultra-low background noise space astronomy applications, such as Terrestrial Planet Finder Coronagraph (TPF-C). The CCD97 includes a photoncounting mode where the equivalent output noise is less than one electron. Use of this mode requires a clock signal at a voltage level greater than the level achievable by the existing CCD (charge-coupled-device) electronics. A high-voltage waveform generator has been developed in code 660/601 to support the CCD97 evaluation. The unit generates required clock waveforms at voltage levels from -20 to +50 V. It deals with standard and arbitrary waveforms and supports pixel rates from 50 to 500 kHz. The system is designed to interface with existing Leach CCD electronics.

Baker, Robert↗

IVGEN Post Flight Analysis

The Intravenous Fluid Generation (IVGEN) Experiment was a technology demonstration experiment that purified ISS potable water, mixed it with salt, and transferred it through a sterilizing filter. On-orbit performance was verified as appropriate and two 1.5 l bags of normal saline solution were returned to earth for post-flight testing by a FDA certified laboratory for compliance with United States Pharmacopiea (USP) standards. Salt concentration deviated from required values and an analysis identified probable causes. Current efforts are focused on Total Organic Content (TOC) testing, and shelf life.The Intravenous Fluid Generation (IVGEN) Experiment demonstrated the purification of ISS potable water, the mixing of the purified water with sodium chloride, and sterilization of the solution via membrane filtration. On-orbit performance was monitored where feasible and two 1.5-liter bags of normal saline solution were returned to earth for post-flight testing by a FDA-registered laboratory for compliance with United States Pharmacopeia (USP)standards [1]. Current efforts have been focused on challenge testing with identified [2] impurities (total organic-carbon), and shelf life testing. The challenge testing flowed known concentrations of contaminants through the IVGEN deionizing cartridge and membrane filters to test their effectiveness. One finding was that the filters and DI-resin themselves contribute to the contaminant load during initial startup, suggesting that the first 100 ml of fluid be discarded. Shelf life testing is ongoing and involves periodic testing of stored DI cartridges and membrane filters that are capped and sealed in hermetic packages. The testing is conducted at six month intervals measuring conductivity and endotoxins in the effluent. Currently, the packaging technique has been successfully demonstrated for one year of storage testing. The USP standards specifies that the TOC be conducted at point of generation as opposed to point of consumption. Samples were generated and shipped to an FDA facility however, testing determined that the samples failed the TOC specification with most likely due to leaching from the sample container. Shelf life testing is examining packaging techniques and periodic testing of samples of DI cartridges that are capped and sealed in hermetic packages. Periodic testing of the purified water output will be conducted at six month intervals.

microgravity applications↗

Aqueous Alteration of Enstatite Chondrites

The Kaidun meteorite is different from all other meteorites [1], consisting largely of a mixture of “incompatible” types of meteoritic material – carbonaceous and enstatite chondrites, i.e. corre-sponding to the most oxidized and the most reduced samples of meteorite materials, including CI1, CM1-2, CV3, EH3-5, and EL3. In addition to these, minor amounts of ordinary and R chondrites are present. In addition, approximately half of the Kaidun lithologies are new materials not known as separate meteorites. Among these are aqueously altered enstatite chondrites [1], which are of considerable interest because they testify that not all reduced asteroids escaped late-stage oxidation, and hydrolysis, and also because hydrated poorly crystalline Si-Fe phase, which in turn is re-placed by serpentine (Figs 3-5). In the end the only indication of the original presence of metal is the re-sidual carbides. In other enstatite chondrite lithogies (of uncertain type) original silicates and metal have been thoroughly replaced by an assemblage of authi-genic plagioclase laths, calcite boxwork, and occasion-al residual grains of silica, Cr-rich troilite, ilmenite, and rare sulfides including heideite (Fig. 6). Fe and S have been largely leached from the rock (Fig. 4). Again the accessory phases are the first clue to the original character of the rock, which can be verified by O isotopes. It is fortunate that Kaidun displays every step of the alteration process.

Zolensky, M. E.↗

Preliminary Report on U-Th-Pb Isotope Systematics of the Olivine-Phyric Shergottite Tissint

Geochemical studies of shergottites suggest that their parental magmas reflect mixtures between at least two distinct geochemical source reservoirs, producing correlations between radiogenic isotope compositions, and trace element abundances.. These correlations have been interpreted as indicating the presence of a reduced, incompatible-element- depleted reservoir and an oxidized, incompatible-element-rich reservoir. The former is clearly a depleted mantle source, but there has been a long debate regarding the origin of the enriched reservoir. Two contrasting models have been proposed regarding the location and mixing process of the two geochemical source reservoirs: (1) assimilation of oxidized crust by mantle derived, reduced magmas, or (2) mixing of two distinct mantle reservoirs during melting. The former clearly requires the ancient martian crust to be the enriched source (crustal assimilation), whereas the latter requires a long-lived enriched mantle domain that probably originated from residual melts formed during solidification of a magma ocean (heterogeneous mantle model). This study conducts Pb isotope and U-Th-Pb concentration analyses of the olivine-phyric shergottite Tissint because U-Th-Pb isotope systematics have been intensively used as a powerful radiogenic tracer to characterize old crust/sediment components in mantle- derived, terrestrial oceanic island basalts. The U-Th-Pb analyses are applied to sequential acid leaching fractions obtained from Tissint whole-rock powder in order to search for Pb isotopic source components in Tissint magma. Here we report preliminary results of the U-Th-Pb analyses of acid leachates and a residue, and propose the possibility that Tissint would have experienced minor assimilation of old martian crust.

Moriwaki, R.↗

Ancient Aqueous Environments at Endeavour Crater, Mars

Opportunity has investigated in detail rocks on the rim of the Noachian age Endeavour crater, where orbital spectral reflectance signatures indicate the presence of Fe(+3)-rich smectites. The signatures are associated with fine-grained, layered rocks containing spherules of diagenetic or impact origin. The layered rocks are overlain by breccias, and both units are cut by calcium sulfate veins precipitated from fluids that circulated after the Endeavour impact. Compositional data for fractures in the layered rocks suggest formation of Al-rich smectites by aqueous leaching. Evidence is thus preserved for water-rock interactions before and after the impact, with aqueous environments of slightly acidic to circum-neutral pH that would have been more favorable for prebiotic chemistry and microorganisms than those recorded by younger sulfate-rich rocks at Meridiani Planum.

Research Support, U.S. Gov't, Non-P.H.S.↗

Lead Isotope Compositions of Acid Residues from Olivine-Phyric Shergottite Tissint: Implications for Heterogeneous Shergottite Source Reservoirs

Geochemical studies of shergottites suggest that their parental magmas reflect mixtures between at least two distinct geochemical source reservoirs, producing correlations between radiogenic isotope compositions and trace element abundances. These correlations have been interpreted as indicating the presence of a reduced, incompatible element- depleted reservoir and an oxidized, incompatible- element-enriched reservoir. The former is clearly a depleted mantle source, but there is ongoing debate regarding the origin of the enriched reservoir. Two contrasting models have been proposed regarding the location and mixing process of the two geochemical source reservoirs: (1) assimilation of oxidized crust by mantle derived, reduced magmas, or (2) mixing of two distinct mantle reservoirs during melting. The former requires the ancient Martian crust to be the enriched source (crustal assimilation), whereas the latter requires isolation of a long-lived enriched mantle domain that probably originated from residual melts formed during solidification of a magma ocean (heterogeneous mantle model). This study conducts Pb isotope and trace element concentration analyses of sequential acid-leaching fractions (leachates and the final residues) from the geochemically depleted olivine-phyric shergottite Tissint. The results suggest that the Tissint magma is not isotopically uniform and sampled at least two geochemical source reservoirs, implying that either crustal assimilation or magma mixing would have played a role in the Tissint petrogenesis.

Moriwaki, R.↗

Mineralogy of the Pahrump Hills Region, Gale Crater, Mars

The Pahrump Hills region of Gale crater is a approximately 12 millimeter thick section of sedimentary rocks in the Murray formation, interpreted as the basal geological unit of Mount Sharp. The Mars Science Laboratory, Curiosity, arrived at the Pahrump Hills in September, 2014, and performed a detailed six-month investigation of the sedimentary structures, geochemistry, and mineralogy of the area. During the campaign, Curiosity drilled and delivered three rock samples to its internal instruments, including the CheMin XRD/XRF. The three targets, Confidence Hills, Mojave 2, and Telegraph Peak, contain variable amounts of plagioclase, pyroxene, iron oxides, jarosite, phyllosilicates, and X-ray amorphous material. Hematite was predicted at the base of Mount Sharp from orbital visible/near-IR spectroscopy, and CheMin confirmed this detection. The presence of jarosite throughout Pahrump Hills suggests the sediments experienced acid-sulfate alteration, either in-situ or within the source region of the sediments. This acidic leaching environment is in stark contrast to the environment preserved within the Sheepbed mudstone on the plains of Gale crater. The minerals within Sheepbed, including Fe-saponite, indicate these sediments were deposited in a shallow lake with circumneutral pH that may have been habitable.

Rampe, E. B.↗

Lead Isotopes in Olivine-Phyric Shergottite Tissint: Implications for the Geochemical Evolution of the Shergottite Source Mantle

Geochemically-depleted shergottites are basaltic rocks derived from a martian mantle source reservoir. Geochemical evolution of the martian mantle has been investigated mainly based on the Rb-Sr, Sm-Nd, and Lu-Hf isotope systematics of the shergottites [1]. Although potentially informative, U-Th- Pb isotope systematics have been limited because of difficulties in interpreting the analyses of depleted meteorite samples that are more susceptible to the effects of near-surface processes and terrestrial contamination. This study conducts a 5-step sequential acid leaching experiment of the first witnessed fall of the geochemically-depleted olivinephyric shergottite Tissint to minimize the effect of low temperature distrubence. Trace element analyses of the Tissint acid residue (mostly pyroxene) indicate that Pb isotope compositions of the residue do not contain either a martian surface or terrestrial component, but represent the Tissint magma source [2]. The residue has relatively unradiogenic initial Pb isotopic compositions (e.g., 206Pb/204Pb = 10.8136) that fall within the Pb isotope space of other geochemically-depleted shergottites. An initial μ-value (238U/204Pb = 1.5) of Tissint at the time of crystallization (472 Ma [3]) is similar to a time-integrated mu- value (1.72 at 472 Ma) of the Tissint source mantle calculated based on the two-stage mantle evolution model [1]. On the other hand, the other geochemically-depleted shergottites (e.g., QUE 94201 [4]) have initial μ-values of their parental magmas distinctly lower than those of their modeled source mantle. These results suggest that only Tissint potentially reflects the geochemical signature of the shergottite mantle source that originated from cumulates of the martian magma ocean

Moriwaki, R.↗

Nutrient Recovery of Plant Leachates Under Thermal, Biological, and Photocatalytic Pretreatments

Nutrient recovery has always been a problem for long distance and long-term space missions. To allow humans to man these missions, a steady source of oxygen, water, and food are necessary for survival beyond Earth's atmosphere. Plants are currently an area of interest since they are capable of providing all three resources for life sustainability. We are currently interested in nutrient recovery for future plant growth and simple aqueous leachate extractions can recover some of the nutrients. However, leaching plants also removes water-soluble organic plant wastes, which inhibits plant growth if not separated properly. To combat the issues with waste and maximize nutrient recovery, we are attempting to pre-treat the plant matter using biological, thermal, and photocatalytic methods before subjecting the solution with variable-strength acid digestion. For the biological method, the inoculums: mixed heterotrophic/nitrifying bioreactor effluent and Trichoderma vessei are used in an attempt to liberate more nutrients from the plant matter. For the thermal method, plants are subjected to varying temperatures at different retention times to determine nutrient recovery. Lastly, the photocatalytic method utilizes TiO (sub 2)'s oxidizing abilities under specific pHs and retention times to reduce organic wastes and improve nutrient gains. A final acid digestion serves to liberate nutrients even further in order to maximize recovery. So far, we have tested ideal acid digestion variables for practicality and performance in our experiments. We found that a low retention time of 10 minutes and a high acid concentration of 0.1 and 1 mole HCl were the most effective at nutrient recovery. For space travel purposes, 0.1 mole currently looks like a viable acid digestion to use since it is relatively effective and sustainable from a mass and energy balance if acid recovery can be performed on waste brines. Biological pretreatments do not look to be too effective and the thermal and photocatalytic methods may be preferred since they show a potential to recover more than 70 percent of the nutrients.

Photocatalytic↗

Mineralogy of Layered Outcrops at Mawrth Vallis and Implications for Early Aqueous Geochemistry on Mars

Recently developed CRISM parameters and newly available DTMs are enabling refined characterization of the mineralogy at Mawrth Vallis. A stratigraphy including 5 units is mapped using HRSC DTMs across 100s of kms and using HiRISE DTMs across 100s of meters. Transitions in mineralogic units were characterized using spectral properties and surface morphology. The observations point to an ancient wet and warm geologic record that formed the thick nontronite unit, a period of wet/dry cycling to create acid alteration, followed by leaching or pedogenesis to result in Al-phyllosilicates, and finally a drier, colder climate that left the altered ash in the form of nanophase aluminosilicates, rather than crystalline clays.

Bishop, J. L.↗

Acid Sulfate Alteration in Gusev Crater, Mars

The Mars Exploration Rover (MER) Spirit landed on the Gusev Crater plains west of the Columbia Hills in January, 2004, during the Martian summer (sol 0; sol = 1 Martian day = 24 hr 40 min). Spirit explored the Columbia Hills of Gusev Crater in the vicinity of Home Plate at the onset on its second winter (sol approximately 900) until the onset of its fourth winter (sol approximately 2170). At that time, Spirit became mired in a deposit of fined-grained and sulfate-rich soil with dust-covered solar panels and unfavorable pointing of the solar arrays toward the sun. Spirit has not communicated with the Earth since sol 2210 (January, 2011). Like its twin rover Opportunity, which landed on the opposite side of Mars at Meridiani Planum, Spirit has an Alpha Particle X-Ray Spectrometer (APXS) instrument for chemical analyses and a Moessbauer spectrometer (MB) for measurement of iron redox state, mineralogical speciation, and quantitative distribution among oxidation (Fe(3+)/sigma Fe) and coordination (octahedral versus tetrahedral) states and mineralogical speciation (e.g., olivine, pyroxene, ilmenite, carbonate, and sulfate). The concentration of SO3 in Gusev rocks and soils varies from approximately 1 to approximately 34 wt%. Because the APXS instrument does not detect low atomic number elements (e.g., H and C), major-element oxide concentrations are normalized to sum to 100 wt%, i.e., contributions of H2O, CO2, NO2, etc. to the bulk composition care not considered. The majority of Gusev samples have approximately 6 plus or minus 5 wt% SO3, but there is a group of samples with high SO3 concentrations (approximately 30 wt%) and high total iron concentrations (approximately 20 wt%). There is also a group with low total Fe and SO3 concentrations that is also characterized by high SiO2 concentrations (greater than 70 wt%). The trend labeled "Basaltic Soil" is interpreted as mixtures in variable proportions between unaltered igneous material and oxidized and SO3-rich basaltic dust. The Moessbauer parameters are not definitive for mineralogical speciation (other than octahedrally-coordinated Fe(3+) but are consistent with a schwertmannite-like phase (i.e., a nanophase ferric oxide). The high oxidation state and values of Moessbauer parameters (center shift and quadrupole splitting) for the high-SO3 samples imply ferric sulfate (i.e., oxidized sulfur), although the hydration state cannot be constrained. In no case is there an excess of SO3 over available cations (i.e., no evidence for elemental sulfur), and Fe sulfide (pyrite) has been detected in only one Gusev sample. The presence of both high-SiO2 (and low total iron and SO3) and high SO3 (and high total iron as ferric sulfate) can be accommodated by a two-step geochemical model developed with the Geochemist's Workbench. (1) Step 1 is anoxic acid sulfate leaching of Martian basalt at high water-to rock ratios (greater than 70). The result is a high-SiO2 residue0, and anoxic conditions are required to solubilize Fe as Fe(2+). (2) Step 2 is the oxic precipitation of sulfate salts from the leachate. Oxic conditions are required to produce the high concentrations of ferric sulfate with minor Mg-sulfates and no detectable Fe(2+)-sulfates.

Morris, R. V.↗