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At least 379 records · Page 21

Shergottite Lead Isotope Signature in Chassigny and the Nakhlites

The nakhlites/chassignites and the shergottites represent two differing suites of basaltic martian meteorites. The shergottites have ages less than or equal to 0.6 Ga and a large range of initial Sr-/Sr-86 and epsilon (Nd-143) ratios. Conversely, the nakhlites and chassignites cluster at 1.3-1.4 Ga and have a limited range of initial Sr-87/Sr-86 and epsilon (Nd-143). More importantly, the shergottites have epsilon (W-182) less than 1, whereas the nakhlites and chassignites have epsilon (W-182) approximately 3. This latter observation precludes the extraction of both meteorite groups from a single source region. However, recent Pb isotopic analyses indicate that there may have been interaction between shergottite and nakhlite/chassignite Pb reservoirs.Pb Analyses of Chassigny: Two different studies haveinvestigated 207Pb/204Pb vs. 206Pb/204Pb in Chassigny: (i)TIMS bulk-rock analyses of successive leaches and theirresidue [3]; and (ii) SIMS analysis of individual minerals[4]. The bulk-rock analyses fall along a regression of SIMSplagioclase analyses that define an errorchron that is olderthan the Solar System (4.61±0.1 Ga); i.e., these define amixing line between Chassigny’s principal Pb isotopic components(Fig. 1). Augites and olivines in Chassingy (notshown) also fall along or near the plagioclase regression [4].This agreement indicates that the whole-rock leachateslikely measure indigenous, martian Pb, not terrestrial contamination[5]. SIMS analyses of K-spars and sulfides definea separate, sub-parallel trend having higher 207Pb/206Pbvalues ([4]; Fig. 1). The good agreement between the bulkrockanalyses and the SIMS analyses of plagioclases alsoindicates that the Pb in the K-spars and sulfides cannot be amajor component of Chassigny.The depleted reservoir sampled by Chassigny plagioclaseis not the same as the solar system initial (PAT) andrequires a multi-stage origin. Here we show a two-stagemodel (Fig. 1) with a 238U/204Pb (μ) of 0.5 for 4.5-2.4 Gaand a μ of 7 for 2.4-1.4 Ga. This is not a unique model butdoes produce a Pb composition that falls on the plagioclaseregression at 1.4 Ga, the approximate igneous age of Chassigny [1]. It should be noted that low-μ single-stage modelsare not capable of producing sufficiently radiogenic 206Pb/204Pb at 1.4 Ga.Relation to Shergottites: The Chassigny K-spars and sulfides fall along a second mixing line defined by leachesand residues of depleted and intermediate shergottites [6]. This mixing line falls above the plagioclase regression.Therefore, we also interpret the radiogenic component of this mixing line to represent indigenous martian Pb. It ispossible that the depleted and intermediate shergottites and the Chassigny plagioclases sample radiogenic Pb from thethe same source, i.e., the mixing lines may intersect at high 206Pb/204Pb.Both K-spar and sulfide are late-stage phases. At the time of their crystallization, the Chassigny system appearsto have remained open to a depleted shergottite Pb reservoir. The depleted component of the shergottite mixing linecan be generated by a single-stage evolution from PAT (4.5 to 1.4 Ga) in a reservoir having a μ ~2. A similar modelfor the most depleted shergottites is also possible: μ = 1.5 for 4.5 to 0.3 Ga.Nakhlites: Nakhlite analyses plot between the shergottite and Chassigny plagioclase regressions [3]. So again,members of the nakhlite/chassignite suite show affinities to shergottite Pb.

Jones, J. H.↗

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

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

Gale Crater↗

Hypogenic Karst of the Great Basin

Discoveries in the 1980s greatly expanded speleologists’ understanding of therole that hypogenic groundwater flow can play developingcaves at depth. Ascending groundwater charged with carbon dioxide and,especially,hydrogen sulfide,can readily dissolve carbonate bedrock just below and above the water table. Sulfuric acid speleogenesis, in which anoxic, rising, sulfidic groundwater mixes with oxygenated cave atmosphere to form aggressive sulfuric acid (H2SO4), formed spectacular caves in CarlsbadCaverns National Park. Cueva de Villa Luz in Mexico provides an aggressively active example of sulfuric acid speleogenesisprocesses, and the Frasassi Caves in Italy preserve the results of sulfuric acid speleogenesis in its upper levels while sulfidic groundwater currently enlarges cave passages in the lower levels. Manycaves in east-central Nevada and western Utah are products of hypogenic speleogenesis and formed before the current topography fully developed. Wet climate during the late Neogeneand Pleistocene brought extensive meteoric infiltration into the caves and calcite speleothems (e.g., stalactites, stalagmites, shields) coat the walls and floors of the caves, concealing evidence of the earlier hypogenic stage. However, by studying the speleogenetic features in well-established sulfuric acid speleogenesis caves, evidence ofhypogenic, probably sulfidic, speleogenesis inmany Great Basin caves can be teased out.Compelling evidence of hypogenicspeleogenesis in these cavesinclude folia, mammillaries, bubble trails, cupolas, and metatyuyamunite. Sulfuric acid speleogenesis signsinclude hollowcoralloidstalagmites,trays, gypsum crust, pseudoscallops, rills, and acid pool notches. Lehman Caves is particularly informative as a low-permeability capstone protected about half of the cave from significant meteoric infiltration, preserving early speleogeneticfeatures.

Louise D Hose↗

Oxygen and sulfur interactions with a clean iron surface and the effect of rubbing contact on these interactions

The interaction of sulfur and oxygen with an iron surface was studied with Auger spectroscopy analysis both statically and during sliding-friction experiments in a vacuum environment. Oxygen, hydrogen sulfide, methyl mercaptan, and sulfur dioxide were adsorbed to an iron surface. Results indicate that sulfide films formed on clean iron surfaces are completely displaced by oxygen. Hydrocarbons containing sulfur, such as methyl mercaptan, adsorb dissociatively. Less sulfur is adsorbed during sliding with hydrogen sulfide and methyl mercaptan than in the absence of sliding. With both oxygen and sulfur dioxide, sliding did not affect the amount of material adsorbed to iron.

Buckley, D. H.↗

Formation of iron sulphide in solar nebula

Noting that the iron sulfide in the Orgueil carbonaceous meteorite is an Fe-deficient monosulfide (pyrrhotite), it is suggested that such mineral chemistry is inconsistent with equilibrium condensation of the solar nebula and that the course of condensation may have been modified by kinetic effects. The effect of Ni on the reaction between Fe and S to produce FeS is examined, and possible reasons are considered for the fact that the cited meteorite differs in both crystal structure and Ni content from the predictions of equilibrium condensation. It is proposed that sulfide formation in the solar nebula may have been inhibited by sluggish diffusion, so that sulfur began to react with previously condensed troilite to form pyrrhotite. On this basis, observations of the Orgueil sulfides are shown to suggest that the course of solar-system condensation was modified by kinetic effects below about 700 K and that equilibrium may not have been achieved.

Kerridge, J. F.↗

Sulfur compounds in coal

The literature on the chemical structure of the organic sulfur compounds (or functional groups) in coal is reviewed. Four methods were applied in the literature to study the sulfur compounds in coal: direct spectrometric and chemical analysis, depolymerization in drastic conditions, depolymerization in mild conditions, and studies on simulated coal. The data suggest that most of the organic sulfur in coal is in the form of thiophenic structures and aromatic and aliphatic sulfides. The relative abundance of the sulfur groups in bituminous coal is estimated as 50:30:20%, respectively. The ratio changes during processing and during the chemical analysis. The main effects are the transformation during processing of sulfides to the more stable thiophenic compounds and the elimination of hydrogen sulfide.

Attar, A.↗

Photo sensor array technology development

The development of an improved capability photo sensor array imager for use in a Viking '75 type facsimile camera is presented. This imager consists of silicon photodiodes and lead sulfide detectors to cover a spectral range from 0.4 to 2.7 microns. An optical design specifying filter configurations and convergence angles is described. Three electronics design approaches: AC-chopped light, DC-dual detector, and DC-single detector, are investigated. Experimental and calculated results are compared whenever possible using breadboard testing and tolerance analysis techniques. Results show that any design used must be forgiving of the relative instability of lead sulfide detectors. A final design using lead sulfide detectors and associated electronics is implemented by fabrication of a hybrid prototype device. Test results of this device show a good agreement with calculated values.

Rossman, M. W.↗

Metallic phases in the Luna 24 soil samples

The metal and sulfide phases in the Luna 24 soil samples were studied with the optical microscope and the electron microprobe. The compositions of the metal particles fall into three groups based on their Ni and Co contents: (1) Samples of meteoritic composition which have undergone metamorphism on the lunar surface. (2) Samples of submeteoritic, low Ni and low Co contents, including most of the metal particles observed. These particles are contained in glass and agglutinate particles and were probably formed by the mixing of meteoritic metal with lunar metal produced by the reduction of silicates during shock-impact. (3) Samples of high-CO content probably formed by mixing of meteoritic material with high-Co metal from the mare basalt or by fractional crystallization from a metal silicate melt. The sulfide minerals were also studied. These are almost pure FeS, and crystallized from a late stage liquid in the mare basalt. Three high-Ni sulfides were also found in the glass phase of agglutinates.

Friel, J. J.↗

Sulfur Isotropic Studies of Archean Slate and Graywacke from Northern Minnesota: Evidence for the Existence of Sulfate Reducing Bacteria

Sulfur isotopic studies of pyrite from metasediments in the 2.6 b.y. old Deer Lake greenstone sequence, Minnesota, were conducted in order to evaluate the possible importance of sulfate reducing bacteria in sulfide formation. Pyrite occurs as ovules up to 2 cm in diameter within graphitic slates, and as fine disseminations in metagraywacke units. SEM studies indicate the pyrite is framboidal in morphology. Delta notation values of pyrite from the Deer Lake sediments range from -2.3 to 11.1 0/00, with a peak at approximately +2 o/oo. Isotopic data is consistent with either high temperature inorganic reduction of circulating seawater sulfate, or low temperature bacterial reduction. However, the lack of sulfide bands or massive occurrences in the sediments, the restriction of pyrite mineralization to the sediments, and the absence of evidence for hot spring activity suggest that a diagenetic origin of pyrite is more feasible. Sulfide in such an environment would be produced principally by the action of sulfate reducing bacteria.

Ripley, E. M.↗

Investigations of submicron sized metal particles in glass coatings of lunar breccia 15286

Almost all the submicron metal particles in the glass coating of breccia 15286 are rounded and contain two phases, metal and sulfide (FeS). The Ni content of the metal phase as determined by scanning transmission electron microscope X-ray analysis ranged from 9.4 to 15.5 wt %. The sulfide was nearly stoichiometric troilite containing up to 1.3 wt % Ni. The close chemical and microstructural similarities between the coarse (greater than 1-micron) and the submicron sized metal indicate a common origin probably as meteoritic debris. Metal-silicate melt experiments under controlled oxygen partial pressured indicate that the metal particles may have formed from a fine dispersion of immiscible metal-sulfide droplets into an impact-generated silicate melt.

Mehta, S.↗

Venus: Halide cloud condensation and volatile element inventories

Several Venus cloud condensates, including A12C16 as well as halides, oxides and sulfides of arsenic and antimony, are assessed for their thermodynamic and geochemical plausibility. Aluminum chloride can confidently be ruled out, and condensation of arsenic sulfides on the surface will cause arsenic compounds to be too rare to produce the observed clouds. Antimony may conceivably be sufficiently volatile, but the expected molecular form is gaseous SbS, not the chloride. Arsenic and antimony compounds in the atmosphere will be regulated at very low levels by sulfide precipitation, irrespective of the planetary inventory of As and Sb. Thus the arguments for a volatile-deficient origin for Venus based on the depletion of water and mercury (relative to Earth) cannot be tested by a search for atmospheric arsenic or antimony.

Lewis, J. S.↗

Vaporization thermodynamics of K2S and K2SO3

The vaporization reactions, vapor pressures, and thermodynamics of potassium sulfide and potassium sulfite were studied for purposes of providing fundamental data for the seed cycle in magnetohydrodynamic electric power generation. Rate of effusion studies, supported by tube furnace experiments, X-ray powder diffraction, mass spectrometry and appropriate chemical analyses and tests, revealed that potassium sulfite disproportionates at high temperatures to form potassium sulfide and potassium sulfate. Potassium sulfide was observed to vaporize incongruently, the initial vapors beng predominantly potassium atoms, with minor species being S2 and various K-S molecules. The ratio of K/S2 in the vapor is very large initially and decreases steadily with prolonged heating. Several materials were evaluated for purposes of containing K2S/K2SO3 at temperatures or = 800 C: Pt, Mo, W, quartz, machinable glass, BN, high density graphite, pyrolytic coated graphite, and alumina. Of these, only alumina was observed to be chemically inert to both K2S but reacted with K2SO3. The other materials were not suitable for either substance. Thermodynamic calculations based on measured vapor pressures and approximate free energy functions are described. Results from isothermal total mass loss experiments and from thermogravimetric experiments are also included.

Bennet, J. E.↗

A three-dimensional study of metal grains in equilibrated, ordinary chondrites

Metal particles in Guarena (H6), Colby (L6) and St. Severin (LL6) were studied by optical microscopy and by electron microprobe analysis. Observations from successive polished sections through the metal particles show that kamacite and taenite grains, which often appear to be isolated particles, are connected directly or by intervening sulfides. Also tetrataenite rims are widest when adjacent to sulfide or kamacite. These observations indicate that transfer of Ni during cooling when kamacite-taenite phase growth takes place does not occur through the silicate phases but proceeds through metal and sulfide phases or along grain boundaries. By utilizing the central Ni content of taenite grains from successive sections, metallographic cooling rates were determined more precisely than by using one arbitrary section. Cooling rates determined in this manner for Guarena, Colby, and St. Severin are 4.3 K, 4.0 K, and 1.0 K per million years, respectively.

Willis, J.↗

Development of advanced thermoelectric materials

The development of an advanced thermoelectric material for radioisotope thermoelectric generator (RTG) applications is reported. A number of materials were explored. The bulk of the effort, however, was devoted to improving silicon germanium alloys by the addition of gallium phosphide, the synthesis and evaluation of lanthanum chrome sulfide and the formulation of various mixtures of lanthanum sulfide and chrome sulfide. It is found that each of these materials exhibits promise as a thermoelectric material.

Source record↗

Sulfur diagenesis in marine sediments

Bacterial sulfate reduction occurs in all marine sediments that contain organic matter. Aqueous sulfide (HS-, H2S), one of the initial products of bacterial sulfide reduction, is extremely reactive with iron bearing minerals: sulfur is fixed into sediments as iron sulfide (first FeS and then Fe2S2). A working definition is given of sulfur diagenesis in marine sediments. Controls and consequences of sulfate reduction rates in marine sediments are examined.

Goldhaber, M.↗

Structure and physiology of Beggiatoa and Thiothrix

Reggiatoa and Thiothrix are genera of filamentous, colorless, sulfide oxidizing bacteria. These organisms are microaerophilic, oxidizing sulfide to sulfur in the presence of oxygen. The sulfur accumulates in intracellular sulfur globules - the outstanding morphological feature of these bacteria. Some strains are able to further oxidize the sulfur to sulfate aerobically or reduce the sulfur to sulfide anaerobically. This metabolic versatility makes these bacteria important links in aquatic sulfur cycles.

Schmidt, T. M.↗