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NASA NTRS1986

Adsorption of O2, SO2, and SO3, on nickel oxide - Mechanism for sulfate formation

Calculations based on the atom superposition and electron delocalization molecular orbital technique suggest that O2 will adsorb preferentially end-on at an angle 45 deg from normal on a nickel cation site on the (100) surface of NiO. SO2 adsorption is also stronger on the nickel site; SO2 bonds through the sulfur atom in a plane perpendicular to the surface. Adsorption energies for SO3 on the nickel and oxygen sites are comparable in the preferred orientation in which the SO3 plane is parallel to the surface. The calculations suggest that the strength of adsorption varies as O2 greater than SO2 greater than SO3. On activation, SO3 adsorbed to an O(2-) site forms a trigonal pyramidal SO4 species which yields, with a low barrier, a tetrahedral sulfate anion. Subsequently the anion reorients on the surface. Alternative mechanisms which require the formation of Ni(3+) or O(-) are discussed. NiSO4 thus formed may play a passivating role for the corrosion of Ni at low temperatures in the SO2 + O2 + SO3 atmospheres and an active role at high temperatures, as discussed in the experimental literature.

Mehandru, S. P.↗

NASA NTRS1985

Adsorption of O2, SO2, and SO3 on nickel oxide. Mechanism for sulfate formation

Calculations based on the atom superposition and electron delocalization molecular orbital (ASED-MO) technique suggest that O2 will adsorb perferentially end-on at an angle 45 deg from normal on a nickel cation site on the (100) surface of NiO. SO2 adsorption is also stronger on the nickel site; SO2 bonds through the sulfur atom is a plane perpendicular to the surface. Adsorption energies for SO3 on the nickel and oxygen sites are comparable in the perferred orientation in which the SO3 plane is parallel to the surface. On activation, SO3 adsorbed to an O2(-) site forms a trigonal pyramidal SO4 species which yields, with a low barrier, a tetrahedral sulfate anion. Subsequently the anion reorients on the surface. Possibilities for alternative mechanisms which require the formation of Ni3(+) or O2(-) are discussed. NiSO4 thus formed leads to the corrosion of Ni at high temperatures in the SO2+O2/SO3 The SO2+O2/SO3 atmosphere, as discussed in the experimental literature.

Mehandru, S. P.↗

NASA NTRS1985

Ceramic oxide reactions with V2O5 and SO3

Ceramic oxides are not inert in combustion environments, but can react with, inter alia, SO3, and Na2SO4 to yield low melting mixed sulfate eutectics, and with vanadium compounds to produce vanadates. Assuming ceramic degradation to become severe only when molten phases are generated in the surface salt (as found for metallic hot corrosion), the reactivity of ceramic oxides can be quantified by determining the SO3 partial pressure necessary for molten mixed sulfate formation with Na2SO3. Vanadium pentoxide is an acidic oxide that reacts with Na2O, SO3, and the different ceramic oxides in a series of Lux-Flood type of acid-base displacement reactions. To elucidate the various possible vanadium compound-ceramic oxide interactions, a study was made of the reactions of a matrix involving, on the one axis, ceramix oxides of increasing acidity, and on the other axis, vanadium compounds of increasing acidity. Resistance to vanadium compound reaction increased as the oxide acidity increased. Oxides more acidic than ZrO2 displaced V2O5. Examination of Y2O3- and CeO2-stabilized ZrO2 sintered ceramics which were degraded in 700 C NaVO3 has shown good agreement with the reactions predicted above, except that the CeO2-ZrO2 ceramic appears to be inexplicably degraded by NaVO3.

Jones, R. L.↗

NASA NTRS1981

An experimental study of SO3 dissociation as a mechanism for converting and transporting solar energy

The high temperature catalytic dissocation of SO3 is an important chemical process being considered in the development and application of solar-thermal energy conversion, transport, and storage systems. A facility for evaluating chemical converter-heat exchangers at temperatures to 1000 C with high flow rates of gaseous SO3 feedstock has been assembled and operated on the NMSU campus. Several quartz and metal reactors containing different catalyst configurations have been tested. Descriptions of the test facility and of the reactors are given along with a presentation and discussion of experimental results.

Mccrary, J. H.↗

NASA NTRS1983

Reactions of NaCl with Gaseous SO3, SO2, and O2

Hot corrosion of gas turbine engine components involves deposits of Na2SO4 which are produced by reactions between NaCl and oxides of sulfur. For the present investigation, NaCl single crystals were exposed at 100 to 850 C to gaseous mixtures of SO3, SO2, and O2. The products formed during this exposure depend, primarily, on the temperatures. The four product films were: NaCl-SO3; Na2S2O7; Na2SO4; and NaCl-Na2SO4. The kinetics of the reactions were measured.

Fielder, W. L.↗

NASA NTRS1984

Reactions of NaCl with gaseous SO3, SO2, and O2

Fielder, W. L.↗

NASA NTRS2010

Determination of the Rate Coefficients of the SO2 plus O plus M yields SO3 plus M Reaction

Rate coefficients of the title reaction R(sub 31) (SO2 +O+M yields SO3 +M) and R(sub 56) (SO2 + HO2 yields SO3 +OH), important in the conversion of S(IV) to S(VI),were obtained at T =970-1150 K and rho (sub ave) = 16.2 micro mol/cubic cm behind reflected shock waves by a perturbation method. Shock-heated H2/ O2/Ar mixtures were perturbed by adding small amounts of SO2 (1%, 2%, and 3%) and the OH temporal profiles were then measured using laser absorption spectroscopy. Reaction rate coefficients were elucidated by matching the characteristic reaction times acquired from the individual experimental absorption profiles via simultaneous optimization of k(sub 31) and k(sub 56) values in the reaction modeling (for satisfactory matches to the observed characteristic times, it was necessary to take into account R(sub 56)). In the experimental conditions of this study, R(sub 31) is in the low-pressure limit. The rate coefficient expressions fitted using the combined data of this study and the previous experimental results are k(sub 31,0)/[Ar] = 2.9 10(exp 35) T(exp ?6.0) exp(?4780 K/T ) + 6.1 10(exp 24) T(exp ?3.0) exp(?1980 K/T ) cm(sup 6) mol(exp ?2)/ s at T = 300-2500 K; k(sub 56) = 1.36 10(exp 11) exp(?3420 K/T ) cm(exp 3)/mol/s at T = 970-1150 K. Computer simulations of typical aircraft engine environments, using the reaction mechanism with the above k(sub 31,0) and k(sub 56) expressions, gave the maximum S(IV) to S(VI) conversion yield of ca. 3.5% and 2.5% for the constant density and constant pressure flow condition, respectively. Moreover, maximum conversions occur at rather higher temperatures (?1200 K) than that where the maximum k(sub 31,0) value is located (approximately 800 K). This is because the conversion yield is dependent upon not only the k(sup 31,0) and k(sup 56) values (production flux) but also the availability of H, O, and HO2 in the system (consumption flux).

Hwang, S. M.↗

NASA NTRS1977

Physical-chemical examination of the N2O3-SO3-H2O system

It was found that when (NO)HSO4 is added to absolute H2SO4, specific conductivity rises sharply, possibly due to an increase in mutual interionic effects and viscosity as the (NO)HSO4 concentration rises. The addition of SO3 to the solution yielded a precipitate; a combination of analysis, IR spectroscopy and X-ray diffraction techniques indicated that this precipitate was (NO)HS2O7.

Linstroem, C.↗

NASA NTRS1977

Inorganic chemistry: Direct syntheses from pure liquid SO3 and from trivalent and pentavalent nitrogen derivatives

From pure liquid SO3 direct synthesis reactions were carried out with N2O5, NO2Cl, NOCl which yielded N2O54SO3, 3SO3, 2SO3-NO2Cl2SO3-NOCl2SO3 and NOCl2SO3, the latter being obtained for the first time in the pure state. In all cases the crystallized product was obtained by separating the constituents of the mixture and then going through a single viscous liquid phase.

Vandorpe, B.↗

NASA NTRS1984

Effects of SO2 and SO3 on the Na2SO4 induced corrosion of nickel

The effects of SO2 and SO3 in the environment on the hot-corrosion behavior of Ni in the temperature range 750-950 C has been studied. Below the melting point of Na2SO4 (884 C), rapid corrosion takes place by formation of a Na2SO4-NiSO4 melt which can penetrate the porous oxide scale and give rise to sulfide information by coming in contact with the metal. The distribution of the sulfides depends on the SO2 level in the ambient gas. Continued corrosion occurs by a sulfidation-oxidation mechanism. At temperatures above the melting point of Na2SO4, accelerated degradation occurs via dissolution of the surface scale, followed by reprecipitation of the oxide in a nonprotective form.

Misra, A. K.↗

NASA NTRS1977

Knowledge of the systems H2O-SO3-N2O3. Report 1: The system H2SO4-H2O-N2O3

The amount of N2O3 being absorbed in 50-100% H2SO4 at 19, 60, and 95 C is directly proportional to the acid concentration and inversely proportional to the temperature. NO+ formation according to the above-formulated equation occurs only at H2SO4 concentrations greater than 52%. Absorption in highly concentrated sulfuric acid results in the formation of crystalline NOHSO4.

Stopperka, K.↗

NASA NTRS2004

Evidence for Differential Comminution/Aeolian Sorting and Chemical Weathering of Martian Soils Preserved in Mars Meteorite EET79001

Impact-melt glasses containing Martian atmospheric gases in Mars meteorite EET79001 are formed from Martian soil fines that had undergone meteoroid-comminution and aeolian sorting accompanied by chemical weathering near Mars surface. Using SiO2 and SO3 as proxy for silicates and salts respectively in Mars soils, we find that SiO2 and SO3 correlate negatively with FeO and MgO and positively with Al2O3 and CaO in these glasses, indicating that the mafic and felsic components are depleted and enriched relative to the bulk host (Lith A/B) respectively as in the case of Moon soils. Though the overall pattern of mineral fractionation is similar between the soil fines on Mars and Moon, the magnitudes of the enrichments/depletions differ between these sample-suites because of pervasive aeolian activity on Mars. In addition to this mechanical processing, the Martian soil fines, prior to impact-melting, have undergone acid-sulfate dissolution under oxidizing/reducing conditions. The S03 content in EET79001,507 (Lith B) glass is approx.18% compared to < 2% in EET79001, 506 (Lith A). SiO2 and SO3 negatively correlate with each other in ,507 glasses similar to Pathfinder soils. The positive correlation found between FeO and SO3 in ,507 glasses as well as Pathfinder rocks and soils is consistent with the deposition of ferric-hydroxysulfate on regolith grains in an oxidizing environment. As in the case of Pathfinder soils, the Al 2O3 vs SiO2 positive correlation and FeO VS S102 negative correlation observed in ,507 glasses indicate that SiO2 from the regolith is mobilized as soluble silicic acid at low pH. The large off-set in the end-member FeO abundance ( SO3=0) between Pathfinder soil-free rock and sulfur-free rock in ,507 glass precursors suggests that the soils comprising the ,507 glasses contain much larger proportion of fine-grained Martian soil fraction that registers strong mafic depletion relative to Lith B. This inference is strongly supported by the Al2O3 - SO3 negative correlation observed in both ,507 glasses and pathfinder soils. Furthermore, the flat MgO-SO3 correlation observed in the case of ,507 glasses shows that the solubilized MgSO4 is mobilized by the aqueous solutions leaving behind the rock-residue with approx.2-3% MgO. This value is similar to the approx.2% MgO found for the soil-free rock at the Pathfinder site. The EET79001 ,506 glasses, in contrast, show that Al2O3 and CaO positively correlate with SO3 indicating that Al is precipitated as amorphous hydroxysulfate at relatively high pH. The FeO - SO3 negative correlation observed in ,506 glasses yields an end-member FeO abundance of approx.21% for the sulfur-free rock, which is consistent with the 22% FeO deduced for the Viking soil-free rock. Further, the FeO and MgO negative correlation with S03 observed in ,506 glasses indicates that the divalent Fe and Mg released from ferromagnesian minerals by acid sulfate dissolution are mobilized away from the reaction sites as soluble sulfates under reducing environment. A similar negative correlation between FeO and SO3 and a positive correlation between Al2O3 and SO3 found in Viking soils suggest that they also had undergone acid-sulfate dissolution under relatively reducing conditions.

Rao, M. N.↗

NASA NTRS2016

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.↗

NASA NTRS1999

Trace Chemistry

The goals of the trace chemistry group were to identify the processes relevant to aerosol and aerosol precursor formation occurring within aircraft gas turbine engines; that is, within the combustor, turbine, and nozzle. The topics of discussion focused on whether the chemistry of aerosol formation is homogeneous or heterogeneous; what species are important for aerosol and aerosol precursor formation; what modeling/theoretical activities to pursue; what experiments to carry out that both support modeling activities and elucidate fundamental processes; and the role of particulates in aerosol and aerosol precursor formation. The consensus of the group was that attention should be focused on SO2, SO3, and aerosols. Of immediate concern is the measurement of the concentration of the species SO3, SO2, H2SO4 OH, HO2, H2O2, O, NO, NO2, HONO, HNO3, CO, and CO2 and particulates in various engines, both those currently in use and those in development. The recommendation was that concentration measurements should be made at both the combustor exit and the engine exit. At each location the above species were classified into one of four categories of decreasing importance, Priority I through IV, as follows: Combustor exit: Priority I species - SO3:SO2 ratio, SO3, SO2, and particulates; Priority II species: OH and O; Priority III species - NO and NO2; and Priority IV species - CO and CO2. For the Engine exit: Priority I species - SO3:SO2 ratio, SO3, SO2,H2SO4, and particulates; Priority II species: OH,HO2, H2O2, and O; Priority III species - NO, NO2, HONO, and HNO3; and Priority IV species - CO and CO2. Table I summarizes the anticipated concentration range of each of these species. For particulate matter, the quantities of interest are the number density, size distribution, and composition. In order to provide data for validating multidimensional reacting flow models, it would be desirable to make 2-D, time-resolved measurements of the concentrations of the above species and, in addition, of the pressure, temperature, and velocity. A near term goal of the experimental program should be to confirm the nonlinear effects of sulfur speciation, and if present, to provide an explanation for them. It is also desirable to examine if the particulate matter retains any sulfur. The recommendation is to examine the effects on SOx production of variations in fuel-bound sulfur and aromatic content (which may affect the amount of particulates formed). These experiments should help us to understand if there is a coupling between particulate formation and SO, concentration. Similarly, any coupling with NOx can be examined either by introducing NOx into the combustion air or by using fuel-bound nitrogen. Also of immediate urgency is the need to establish and validate a detailed mechanism for sulfur oxidation/aerosol formation, whose chemistry is concluded to be homogeneous, because there is not enough surface area for heterogeneous effects. It is envisaged that this work will involve both experimental and theoretical programs. The experimental work will require, in addition to the measurements described above, fundamental studies in devices such as flow reactors and shock tubes. Complementing this effort should be modeling and theoretical activities. One impediment to the successful modeling of sulfur oxidation is the lack of reliable data for thermodynamic and transport properties for several species, such as aqueous nitric acid, sulfur oxides, and sulfuric acid. Quantum mechanical calculations are recommended as a convenient means of deriving values for these properties. Such calculations would also help establish rate constants for several important reactions for which experimental measurements are inherently fraught with uncertainty. Efforts to implement sufficiently detailed chemistry into computational fluid dynamic codes should be continued. Zero- and one-dimensional flow models are also useful vehicles for elucidating the minimal set of species and reactions that must be included in two- and three-dimensional modeling studies.

Radhakrishnan, Krishnan↗

NASA NTRS2007

Iron Mineralogy and Aqueous Alteration on Mars from the MER Moessbauer Spectrometers

The twin Mars Exploration Rovers Spirit (Gusev crater) and Opportunity (Meridiani Planum) used MIMOS II Moessbauer spectrometers to analyze martian surface materials in the first application of extraterrestrial Moessbauer spectroscopy. The instruments acquired spectra that identified the speciation of Fe according to oxidation state, coordination state, and mineralogical composition and provided quantitative information about the distribution of Fe among oxidation states, coordination states, and Fe-bearing phases. A total of 12 unique Fe-bearing phases were identified: Fe(2+) in olivine, pyroxene, and ilmenite; Fe(2+) and Fe(3+) in magnetite and chromite; Fe(3+) in nanophase ferric oxide (npOx), hematite, goethite, jarosite, an unassigned Fe3+ sulfate, and an unassigned Fe(3+) phase associated with jarosite; and Fe(0) in kamacite. Weakly altered basalts at Gusev crater (SO3 = 2.5 +/- 1.4 wt.% and Fe(3+)/Fe(sub T) = 0.24 +/- 0.11) are widespread on the Gusev plains and occur in less abundance on West Spur and Husband Hill in the Columbia Hills. Altered low-S rocks (SO3 = 5.2 +/- 2.0 wt.% and Fe(3+)/Fe(sub T) = 0.63 +/- 0.18) are the most common type of rock in the Columbia Hills. Ilm-bearing, weakly altered basalts were detected only in the Columbia Hills, as was the only occurrence of chromite in an altered low-S rock named Assemblee. Altered high-S rocks (SO3 > 14.2 wt.% and Fe(3+)/Fe(sub T) = 0.83 +/- 0.05) are the outcrop rocks of the ubiquitous Burns formation at Meridiani Planum. Two Fe(0)-bearing rocks at Meridiani Planum (Barberton and Heat Shield Rock) are meteorites. Laguna Class soil is weakly altered (SO3 = 6 +/- 2 wt.% and Fe(3+)/Fe(sub T) = 0.29 +/- 0.08) and widely distributed at both Gusev crater and Meridiani Planum, implying efficient global mixing processes or a global distribution of precursor rocks with comparable Fe mineralogical compositions. Paso Robles Class soil is heavily altered (SO3 approx. 31 wt.% and Fe(3+)/Fe(sub T) = 0.83 +/- 0.05), is relatively uncommon, and occurs as subsurface deposits in the Columbia Hills. Berry Class soil is also heavily altered (SO3 = 5 +/- 1 wt.% and Fe(3+)/Fe(sub T) = 0.60 +/- 0.13) and occurs at Meridiani Planum as lag deposits, at the crests of aeolian bedforms, and as isolated pockets on outcrop surfaces. Magnetite is identified as the strongly magnetic component in martian soil. Jarosite (in the Burns outcrop at Meridiani Planum) and goethite (in Clovis Class rocks at Gusev crater) are mineralogical markers for aqueous processes because they contain the hydroxide anion (OH(-)) as an essential part of their structure. Each yields approx.10 wt.% H2O upon dehydroxylation. The presence of Fe sulfates on opposite sides of Mars is evidence that aqueous processes under acid sulfate conditions are or were common. Except for Independence Class rocks in the Columbia Hills, the overall Fe mineralogical compositions and similar basaltic bulk chemical compositions (calculated with respect to S = Cl = 0) of the population of altered rocks analyzed by MER imply isochemical alteration of basaltic precursors at low water-to-rock ratios.

Morris, Richard V.↗

NASA NTRS1986

Spectral reflectance of solid sulfur trioxide (0.25-5.2 micron) - Implications for Jupiter's satellite Io

Laboratory data on the UV and near-IR spectra of SO3 are compared with spectra obtained for the Jovian moon Io by the Voyager and IUE satellites. The experimental data were taken at wavelengths from 0.25 micron to nearly 6 microns, although only order-of-magnitude estimates could be made of the associated particle sizes. Tests were also performed to identify the spectral characteristics with succeedingly lower concentrations of SO3 relative to SO2, which is apparently abundant on the Io surface. No evidence was found for the presence of solid SO3 in the spectra of Io down to projected concentrations lower than 1 percent. The findings are considered surprising since it is known that particle bombardment will cause SO3 to form in SO2 concentrations. It is expected that SO3 will be detected by the IR mapping instrument to be carried by the Galileo spacecraft.

Nelson, R. M.↗

NASA NTRS2009

Sulfur Speciation in the Martian Regolith Component in Shergottite Glasses

We have shown that Gas-Rich Impact-Melt (GRIM) glasses in Shergotty, Zagami, and EET79001 (Lith A and Lith B) contain Martian regolith components that were molten during impact and quenched into glasses in voids of host rock materials based on neutron-capture isotopes, i.e., Sm-150 excesses and Sm-149 deficits in Sm, and Kr-80 excesses produced from Br [1, 2]. These GRIM glasses are rich in S-bearing secondary minerals [3.4]. Evidence for the occurrence of CaSO4 and S-rich aluminosilicates in these glasses is provided by CaO-SO3 and Al2O3-SO3 correlations, which are consistent with the finding of gypsum laths protruding from the molten glass in EET79001 (Lith A) [5]. However, in the case of GRIM glasses from EET79001 (Lith B), Shergotty and Zagami, we find a different set of secondary minerals that show a FeO-SO3 correlation (but no MgOSO3 correlation), instead of CaO-SO3 and Al2O3-SO3 correlations observed in Lith A. These results might indicate different fluidrock interactions near the shergottite source region on Mars. The speciation of sulfur in these salt assemblages was earlier studied by us using XANES techniques [6], where we found that Lith B predominantly contains Fe-sulfide globules (with some sulfate). On the other hand, Lith A showed predominantly Casulfite/ sulfate with some FeS. Furthermore, we found Fe to be present as Fe2+ indicating little oxidation, if any, in these glasses. To examine the sulfide-sulfate association in these glasses, we studied their Fe/Ni ratios with a view to find diagnostic clues for the source fluid. The Fe-sulfide mineral (Fe(0.93)Ni(0.3)S) in EET79001, Lith A is pyrrhotite [7, 8]. It yields an Fe/Ni ratio of 31. In Shergotty, pyrrhotite occurs with a molar ratio of Fe:S of 0.94 and a Ni abundance of 0.12% yielding a Fe/Ni ratio of approx.500 [8]. In this study, we determined a NiO content of approx.0.1% and FeO/NiO ratio of approx.420 in S-rich globules in #507 (EET79001, Lith B) sample using FE-SEM. In the same sample (bulk), using EMPA, we determined a FeO/NiO ratio of approx.700 (raster mode). Using similar techniques, we determined a NiO content of approx.0.015% and a FeO/NiO ratio of approx.800 in #506 (EET79001, Lith A). Moreover, a NiO content of approx.150 ppm and 6.1% FeO were found in Lith A GRIM glasses using neutron activation analysis [9] yielding a FeO/NiO ratio of approx.420. The FeO/NiO ratios in secondary mineral phases in S-rich pockets of EET79001 (Lith A/B) and Shergotty are high (approx.400) compared to the FeO/NiO ratio of 31 in Lith A pyrrhotite. These results suggest similar kind of fluids interacted with different rock materials to yield the observed variations in GRIM glasses in EET79001 Lith A and B.

Rao, M. N.↗

NASA NTRS2016

Acid Sulfate Alteration on Mars

A variety of mineralogical and geochemical indicators for aqueous alteration on Mars have been identified by a combination of surface and orbital robotic missions, telescopic observations, characterization of Martian meteorites, and laboratory and terrestrial analog studies. Acid sulfate alteration has been identified at all three landing sites visited by NASA rover missions (Spirit, Opportunity, and Curiosity). Spirit landed in Gusev crater in 2004 and discovered Fe-sulfates and materials that have been extensively leached by acid sulfate solutions. Opportunity landing on the plains of Meridiani Planum also in 2004 where the rover encountered large abundances of jarosite and hematite in sedimentary rocks. Curiosity landed in Gale crater in 2012 and has characterized fluvial, deltaic, and lacustrine sediments. Jarosite and hematite were discovered in some of the lacustrine sediments. The high elemental abundance of sulfur in surface materials is obvious evidence that sulfate has played a major role in aqueous processes at all landing sites on Mars. The sulfate-rich outcrop at Meridiani Planum has an SO3 content of up to 25 wt.%. The interiors of rocks and outcrops on the Columbia Hills within Gusev crater have up to 8 wt.% SO3. Soils at both sites generally have between 5 to 14 wt.% SO3, and several soils in Gusev crater contain around 30 wt.% SO3. After normalization of major element compositions to a SO3-free basis, the bulk compositions of these materials are basaltic, with a few exceptions in Gusev crater and in lacustrine mudstones in Gale crater. These observations suggest that materials encountered by the rovers were derived from basaltic precursors by acid sulfate alteration under nearly isochemical conditions (i.e., minimal leaching). There are several cases, however, where acid sulfate alteration minerals (jarosite and hematite) formed in open hydrologic systems, e.g., in Gale crater lacustrine mudstones. Several hypotheses have been suggested for the aqueous formation of sulfate-bearing phases under acidic conditions on the surface of Mars including (1) sulfuric acid weathering of basaltic materials; (2) oxidative weathering of ultramafic igneous rocks containing sulfides; (3) acid fog weathering of basaltic materials, and (4) near-neutral pH subsurface solutions rich in Fe2(+) that were rapidly oxidized to Fe3(+), which produced excess acidity as iron was oxidized on exposure to O2 or photo-oxidized by ultraviolet radiation at the martian surface. Next, we briefly describe evidence for these hypothesis.

Ming, D. W.↗