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At least 505 records · Page 28

Enstatite chondrites and achondrites as asteroidal resources

The highly reduced nature of the enstatite meteorites (chondrites and achondrites) differs from that of all other types of stony meteorites. The silicates in the enstatite meteorites contain almost no FeO. In addition, many normally lithophile elements such as Na, Ca, Mg, Cr, and Ti display chalcophilic behavior. A study of the chemistry and mineralogy of the enstatite meteorites was undertaken to determine their resource potential. On average, about 99 percent of the volume of an enstatite achondrite, or aubrite, consists of only four silicate minerals: enstatite, Na-rich plagioclase, diopside, and forsterite, with enstatite being by far the most abundant mineral. The remaining one percent of the volume consists of troilite, kamacite, and trace amounts of oldhamite, daubreelite, ferromagnesian albandite, and schreibersite. Thus, the aubrites can be considered as a possible source for large quantities of Mg, Si, and O, but are of little interest as a source of anything else. The enstatite chondrites appear to be more promising candidates for resource utilization. The chondrites are generally divided into two groups: EH (high iron, fine-grained, with abundant chondrules); and EL (low iron, coarse-grained, with little or no evidence of chondrules). Metallic Ni-Fe makes up roughly 20-25 weight percent of each type of enstatite chondrite. These meteorites are also a good source of nitrogen. This is due in part to the presence of osbornite and sinoite. The latter mineral is restricted to EL chondrites, which typically have a higher bulk nitrogen content than the EH chondrites. Three valuable metals, Cr, Mn, and Ti, are concentrated in a few distinct sulfide phases in the enstatite chondrites. These sulfide phases are troilite and niningerite in EH chondrites and troilite, daubreelite, and ferroan alabandite in EL chondrites.

Hutson, M. L.↗

Mars surface weathering products and spectral analogs: Palagonites and synthetic iron minerals

There are several hypotheses regarding the formation of Martian surface fines. These surface fines are thought to be products of weathering processes occurring on Mars. Four major weathering environments of igneous rocks on Mars have been proposed; (1) impact induced hydrothermal alterations; (2) subpermafrost igneous intrusion; (3) solid-gas surface reactions; and (4) subaerial igneous intrusion over permafrost. Although one or more of these processes may be important on the Martian surface, one factor in common for all these processes is the reaction of solid or molten basalt with water (solid, liquid, or gas). These proposed processes, with the exception of solid-gas surface reactions, are transient processes. The most likely product of transient hydrothermal processes are layer silicates, zeolites, hydrous iron oxides and palagonites. The long-term instability of hydrous clay minerals under present Martian conditions has been predicted; however, the persistence of such minerals due to slow kinetics of dehydration, or entrapment in permafrost, where the activity of water is high, can not be excluded. Anhydrous oxides of iron (e.g., hematite and maghemite) are thought to be stable under present Martian surface conditions. Oxidative weathering of sulfide minerals associated with Martian basalts has been proposed. Weathering of sulfide minerals leads to a potentially acidic permafrost and the formation of Fe(3) oxides and sulfates. Weathering of basalts under acidic conditions may lead to the formation of kaolinite through metastable halloysite and metahalloysite. Kaolinite, if present, is thought to be a thermodynamically stable phase at the Martian surface. Fine materials on Mars are important in that they influence the surface spectral properties; these fines are globally distributed on Mars by the dust storms and this fraction will have the highest surface area which should act as a sink for most of the absorbed volatiles near the surface of Mars. Therefore, the objectives of this study were to: (1) examine the fine fraction mineralogy of several palagonitic materials from Hawaii; and (2) compare spectral properties of palagonites and submicron sized synthetic iron oxides with the spectral properties of the Martian surface.

Golden, D. C.↗

Additional complexity in the lunar crust - Petrology of sodic anorthosites and sulfur-rich, ferroan noritic anorthosites

Lunar breccia 67016 contains two suites of unusual highlands rocks: sulfur-rich, noritic anorthosites, and sodic anorthosites. Mineral compositions of the sulfur-rich noritic anorthosites closely match those of ferroan anorthosites. Unusually large amounts of sulfides, and sulfidation reactions involving olivine in these clasts probably reflect endogenous volatile transfer. The sodic anorthosites are mafic-poor, with mineral compositions intermediate between those of pristine ferroan and alkali anorthosites. Rare examples of pristine rocks with similar mineral compositions are known, and may represent a distinct class of lunar crustal rocks.

Norman, Marc D.↗

Iodine-xenon, chemical, and petrographic studies of Semarkona chondrules - Evidence for the timing of aqueous alteration

The relationship of the I-Xe system of the Semarkona meteorite to other measured properties is investigated via INAA, petrographic, and noble-gas analyses on 17 chondrules from the meteorite. A range of not less than 10 Ma in apparent I-Xe ages is observed. The three latest apparent ages fall in a cluster, suggesting the possibility of a common event. It is argued that the initial I-129/I-127 ratio (R0) is related to chondrule type and/or mineralogy, with nonporphyritic and pyroxene-rich chondrules showing evidence for lower R0s than porphyritic and olivine-rich chondrules. Chondrules with sulfides on or near the surface have lower R0s than other chondrules. The He-129/Xe-132 ratio in the trapped Xe component anticorrelates with R0, consistent with the evolution of a chronometer in a closed system or in multiple systems. It is concluded that the variations in R0 represent variations in ages, and that later events, possibly aqueous alteration, preferentially affected chondrules with nonporphyritic textures and/or sulfide-rich exteriors about 10 Ma after the formation of the chondrules.

Swindle, T. D.↗

Early Archean spherule beds of possible impact origin from Barberton, South Africa: A detailed mineralogical and geochemical study

The Barberton Greenstone belt is a 3.5- to 3.2-Ga-old formation situated in the Swaziland Supergroup near Barberton, northeast Transvaal, South Africa. The belt includes a lower, predominantly volcanic sequence, and an upper sedimentary sequence (e.g., the Fig Tree Group). Within this upper sedimentary sequence, Lowe and Byerly identified a series of different beds of spherules with diameters of around 0.5-2 mm. Lowe and Byerly and Lowe et al. have interpreted these spherules to be condensates of rock vapor produced by large meteorite impacts in the early Archean. We have collected a series of samples from drill cores from the Mt. Morgan and Princeton sections near Barberton, as well as samples taken from underground exposures in the Sheba and Agnes mines. These samples seem much better preserved than the surface samples described by Lowe and Byerly and Lowe et al. Over a scale of just under 30 cm, several well-defined spherule beds are visible, interspaced with shales and/or layers of banded iron formation. Some spherules have clearly been deposited on top of a sedimentary unit because the shale layer shows indentions from the overlying spherules. Although fresher than the surface samples (e.g., spherule bed S-2), there is abundant evidence for extensive alteration, presumably by hydrothermal processes. In some sections of the cores sulfide mineralization is common. For our mineralogical and petrographical studies we have prepared detailed thin sections of all core and underground samples (as well as some surface samples from the S-2 layer for comparison). For geochemical work, layers with thicknesses in the order of 1-5 mm were separated from selected core and underground samples. The chemical analyses are being performed using neutron activation analysis in order to obtain data for about 35 trace elements in each sample. Major elements are being determined by XRF and plasma spectrometry. To clarify the history of the sulfide mineralization, sulfur isotopic compositions are being determined.

Koeberl, Christian↗

Emissions of sulfur gases from marine and freshwater wetlands of the Florida Everglades - Rates and extrapolation using remote sensing

Rates of emissions of the biogenic sulfur (S) gases carbonyl sulfide (COS), methyl mercaptan (MSH), dimethyl sulfide (DMS), and carbon disulfide (CS2) were measured in a variety of marine and freshwater wetland habitats in the Florida Everglades during a short duration period in October using dynamic chambers, cryotrapping techniques, and gas chromatography. The most rapid emissions of over 500 nmol/sq m/h occurred in red mangrove-dominated sites that were adjacent to open seawater and contained numerous crab burrows. Poorly drained red mangrove sites exhibited lower fluxes of about 60 nmol/sq m/h, which were similar to fluxes from the black mangrove areas which dominated the marine-influenced wetland sites in the Everglades. DMS was the dominant organo-S gas emitted especially in the freshwater areas. Spectral data from a scene from the Landsat TM were used to map habitats in the Everglades. Six vegetation categories were delineated using geographical information system software and S gas emissions were extrapolated for the entire Everglades National Park. The black mangrove-dominated areas accounted for the largest portion of S gas emissions to the area. The large area extent of the saw grass communities accounted for about 24 percent of the total S emissions.

Hines, Mark E.↗

Venus mountain-top mineralogy: Misconceptions about pyrite as the high radar-reflecting phase

Altitude-dependent, high radar-reflectivity surfaces on Venus are observed on most mountainous volcanic terranes above a planetary radius of about 6054 km. However, high radar-reflectivity areas also occur at lower altitudes in some impact craters and plain terranes. Pyrite (FeS2) is commonly believed to be responsible for the high radar reflectivities at high elevations on Venus, on account of large dielectric constants measured for sulfide-bearing rocks that were erroneously attributed to pyrite instead of pyrrhotite. Pentlandite-pyrrhotite assemblages may be responsible for high reflectivities associated with impact craters on the Venusian surface, by analogy with Fe-Ni sulfide deposits occurring in terrestrial astroblemes. Mixed-valence Fe(2+)-Fe(3+) silicates, including oxyhornblende, oxybiotite, and ilvaite, may contribute to high radar reflecting surfaces on mountain-tops of Venus.

Burns, Roger G.↗

Rhenium-osmium isotope systematics of Group 2A and Group 4A iron meteorites

We are investigating the Re-Os isotope systematics of two groups of magmatic iron meteorites (2A, 4A) in an attempt to establish precise 'total rock' isochrons by the Re-Os system. The Re-187/Os-187 isotope system is recognized as a method by which the ages of iron meteorites can be directly determined and that can provide information on the timing of FeNi segregation and core formation in planetesimals. The Re-Os isotope system permits the direct absolute dating of the metal phase in iron meteorites. Indirect dating of iron meteorites has been achieved in the past through the Rb-Sr, K-Ar, and most recently, Sm-Nd for silicate inclusions, where present. Relative dating has been obtained directly by extensive studies of the short-lived system Pd-107/Ag-107 for the metal and sulfide phases and indirectly using I-129/Xe-129 in silicate and sulfide inclusions.

Creaser, R. A.↗

Emissions of biogenic sulfur gases from Alaskan tundra

Fluxes of the biogenic sulfur gases carbonyl sulfide (COS), dimethyl sulfide (DMS), methyl mercaptan (MeSH), and carbon disulfide (CS2) were determined for several freshwater and coastal marine tundra habitats using a dynamic enclosure method and gas chromatography. In the freshwater tundra sites, highest emissions, with a mean of 6.0 nmol/m(sup -2)H(sup -1) (1.5-10) occurred in the water-saturated wet meadow areas inhabited by grasses, sedges, and Sphagnum mosses. In the drier upland tundra sites, highest fluxes occurred in areas inhabited by mixed vegetation and labrador tea at 3.0 nmol/m(sup -2)h(sup -1) (0-8.3) and lowest fluxes were from lichen-dominated areas at 0.9 nmol/m(sup -2)h(sup -1). Sulfur emissions from a lake surface were also low at 0.8 nmol/m(sup -2)h(sup -1). Of the compounds measured, DMS was the dominant gas emitted from all of these sites. Sulfure emissions from the marine sites were up to 20-fold greater than fluxes in the freshwater habitats and were also dominated by DMS. Emissions of DMS were highest from intertidal soils inhabited by Carex subspathacea (150-250 nmol/m(sup -2)h(sup -1)). This Carex sp. was grazed thoroughly by geese and DMS fluxes doubled when goose feces were left within the flux chamber. Emissions were much lower from other types of vegetation which were more spatially dominant. Sulfure emissions from tundra were among the lowest reported in the literature. When emission data were extrapolated to include all tundra globally, the global flux of biogenic sulfur from this biome is 2-3 x 10(exp 8) g/yr. This represents less than 0.001 percent of the estimated annual global flux (approximately 50 Tg) of biogenic sulfur and less than 0.01 percent of the estimated terrestrial flux. The low emissions are attributed to the low availability of sulfate, certain hydrological characteristics of tundra, and the tendency for tundra to accumulate organic matter.

Hines, Mark E.↗

Emissions of sulfur gases from marine and freshwater wetlands of the Florida Everglades: Rates and extrapolation using remote sensing

Rates of emissions of the biogenic sulfur (S) gases carbonyl sulfide (COS), methyl mercaptan (MSH), dimethyl sulfide (DMS), and carbon disulfide (CS2) were measured in a variety of marine and freshwater wetland habitats in the Florida Everglades during a short duration period in October using dynamic chambers, cryotrapping techniques, and gas chromatography. The most rapid emissions of greater than 500 nmol/m(sup -2)h(sup -1) occurred in red mangrove-dominated sites that were adjacent to open seawater and contained numerous crab burrows. Poorly drained red mangrove sites exhibited lower fluxes of approximately 60 nmol/m(sup -2)h(sup -1) which were similar to fluxes from the black mangrove areas which dominated the marine-influenced wetland sites in the Everglades. DMS was the dominant organo-S gas emitted especially in the freshwater areas. Spectral data from a scene from the Landsat thematic mapper were used to map habitats in the Everglades. Six vegetation categories were delineated using geographical information system software and S gas emission were extrapolated for the entire Everglades National Park. The black mangrove-dominated areas accounted for the largest portion of S gas emissions to the area. The large area extent of the saw grass communities (42 percent) accounted for approximately 24 percent of the total S emissions.

Hines, Mark E.↗

The effects of acid deposition on sulfate reduction and methane production in peatlands

Peatlands, as fens and bods, make up a large percentage of northern latitude terrestrial environments. They are organic rich and support an active community of anaerobic bacteria, such as methanogenic and sulfate-reducing bacteria. The end products of these microbial activities, methane and hydrogen sulfide, are important components in the global biogeochemical cycles of carbon and sulfur. Since these two bacterial groups compete for nutritional substrates, increases in sulfate deposition due to acid rain potentially can disrupt the balance between these processes leading to a decrease in methane production and emission. This is significant because methane is a potent greenhouse gas that effects the global heat balance. A section of Mire 239 in the Experimental Lakes Area, in Northwestern Ontario, was artificially acidified and rates of sulfate reduction and methane production were measured with depth. Preliminary results suggested that methane production was not affected immediately after acidification. However, concentrations of dissolved methane decreased and dissolved sulfide increased greatly after acidification and both took several days to recover. The exact mechanism for the decrease in methane was not determined. Analyses are under way which will be used to determine rates of sulfate reduction. These results will be available by Spring and will be discussed.

Murray, Georgia L.↗

Factors controlling sulfur gas exchange in Sphagnum-dominated wetlands

Atmosphere-peatland exchange of reduced sulfur gases was determined seasonally in fen in NH, and in an artificially-acidified fen at the Experimental Lakes Area (ELA) in Canada. Dimethyl sulfide (DMS) dominated gas fluxes at rates as high as 400 nmol/m(sup -2)hr(sup -1). DMS fluxes measured using enclosures were much higher than those calculated using a stagnant-film model, suggesting that Sphagnum regulated efflux. Temperature controlled diel and seasonal variability in DMS emissions. Use of differing enclosure techniques indicated that vegetated peatlands consume atmospheric carbonyl sulfide. Sulfate amendments caused DMS and methane thiol concentrations in near-surface pore waters to increase rapidly, but fluxes of these gases to the atmosphere were not affected. However, emission data from sites experiencing large differences in rates of sulfate deposition from the atmosphere suggested that chronic elevated sulfate inputs enhance DMS emissions from northern wetlands.

Demello, William Zamboni↗

Euhedral metallic-Fe-Ni grains in extraterrestrial samples

Metallic Fe-Ni is rare in terrestrial rocks, being largely restricted to serpentinized peridotites and volcanic rocks that assimilated carbonaceous material. In contrast, metallic Fe-Ni is nearly ubiquitous among extraterrestrial samples (i.e., meteorites, lunar rocks, and interplanetary dust particles). Anhedral grains are common. For example, in eucrites and lunar basalts, most of the metallic Fe-Ni occurs interstitially between silicate grains and thus tends to have irregular morphologies. In many porphyritic chondrules, metallic Fe-Ni and troilite form rounded blebs in the mesostasis because their precursors were immiscible droplets. In metamorphosed ordinary chondrites, metallic Fe-Ni and troilite form coarse anhedral grains. Some of the metallic Fe-Ni and troilite grains has also been mobilized and injected into fractures in adjacent silicate grains where local shock-reheating temperatures reached the Fe-FeS eutectic (988 C). In interplanetary dust particles metallic Fe-Ni most commonly occurs along with sulfide as spheroids and fragments. Euhedral metallic Fe-Ni grains are extremely rare. Several conditions must be met before such grains can form: (1) grain growth must occur at free surfaces, restricting euhedral metallic Fe-Ni grains to systems that are igneous or undergoing vapor-deposition; (2) the metal (+/-) sulfide assemblage must have an appropriate bulk composition so that taenite is the liquidus phase in igneous systems or the stable condensate phase in vapor-deposition systems; and (3) metallic Fe-Ni grains must remain underformed during subsequent compaction, thermal metamorphism, and shock. Because of these restrictions, the occurrence of euhedral metallic Fe-Ni grains in an object can potentially provide important petrogenetic information. Despite its rarity, euhedral metallic Fe-Ni occurs in a wide variety of extraterrestrial materials. Some of these materials formed in the solar nebula; others formed on parent body surfaces by meteoroid impacts.

Rubin, Alan E.↗

Lewis Cliff 87057: A new metal-rich E3 chondrite with similarities to Mt. Egerton, Shallowater and Happy Canyon

The Antarctic meteorites LEW87057, LEW87220, LEW87223, LEW87234, LEW87237, and LEW87285 were described as paired E3 chondrites by Brian Mason (Antarctic Meteorite Newsletters, 12(1) and 15(1,2)). LEW87223 is texturally unusual, containing abundant chondrules and jagged troilite grains which are enclosed in metal. Our INAA data show that the siderophile element abundance in two splits of LEW87223 are higher than the EH range, while chalcophile elements (Cr excepted) are highly depleted. Mineral compositions are unlike those normally found in EH or EL chondrites or aubites, and in some respects resemble those of several anomalous enstatite meteorites such as Shallowater, Mt. Egerton, and Happy Canyon. The bulk and mineral compositions are consistent with the addition of EL chondrite metal to an EL3 chondrite with the removal of sulfides other than troilite which is now Cr-rich. We suggest that this meteorite is an EL3 chondrite into which metal was introduced and sulfides redistributed during an event involving impact melting and brecciation.

Zhang, Y.↗

Biogeochemical cycles of carbon, sulfur, and free oxygen in a microbial mat

Complete budgets for carbon and oxygen have been constructed for cyanobacterial mats dominated by Microcoleus chthonoplastes from the evaporating ponds of a salt works. We infer from the data the various sinks for O2 as well as the sources of carbon for primary production. Although seasonal variability exists, a major percentage of the O2 produced during the day did not diffuse out of the mat but was used within the mat to oxidize both organic carbon and the sulfide produced by sulfate reduction. At night, most of the O2 that diffused into the mat was used to oxidize sulfide, with O2 respiration of minor importance. During the day, the internal mat processes of sulfate reduction and O2 respiration generated as much or more inorganic carbon (DIC) for primary production as diffusion into the mat. Oxygenic photosynthesis was the most important process of carbon fixation. At night, the DIC lost from the mat was mostly from sulfate reduction. Elemental fluxes across the mat/brine interface indicated that carbon with an oxidation state of greater than zero was taken up by the mat during the day and liberated from the mat at night. Overall, carbon with an average oxidation state of near zero accumulated in the mat. Both carbon fixation and carbon oxidation rates varied with temperature by a similar amount.

Canfield, Donald E.↗

One-step synthesis of dithiocarbamates from metal powders

Neutral metal dithiocarbamate complexes (M(NR2CS2)X) are well-known precursors to metal sulfides, a class of materials with numerous technological applications. We are involved in a research effort to prepare new precursors to metal sulfides using simple, reproducible synthetic procedures. We describe the results of our synthetic and characterization studies for M = Fe, Co, Ni, Cu. and In. For example, treatment of metallic indium with tetramethylthiuram disulfide (tmtd) in 4-methylpyridine (4-Mepy) at 25 deg C produces a new homoleptic indium (III) dithiocarbamate, In(N(CH3)2CS2)3(I), in yields of over 60 percent. The indium (III) dithiocarbamate was characterized by X-ray crystallography; (I) exists in the solid state as discrete distorted-octahedral molecules. Compound (I) crystallizes in the P1bar (No. 2) space group with lattice parameters: a = 9.282(1) A, b = 10.081(1) A, c = 12.502 A, alpha = 73.91(1) deg, beta = 70.21(1) deg, gamma = 85.8(1)deg, and Z = 2. X-ray diffraction and mass spectral data were used to characterize the products of the analogous reactions with Fe, Co, Ni, and Cu. We discuss both use of dithiocarbamates as precursors and our approach to their preparation.

Hepp, Aloysius F.↗

Alkali element depletion by core formation and vaporization on the early Earth

The depletion of Na, K, Rb, and Cs in the Earth's upper mantle and crust relative to their abundances in chondrites is a long standing problem in geochemistry. Here we consider two commonly invoked mechanisms, namely core formation, and vaporization, for producing the observed depletions. Our models predict that a significant percentage of the Earth's bulk alkali element inventory is in the core (30 percent for Na, 52 percent for K, 74 percent for Rb, and 92 percent for Cs). These predictions agree with independent estimates from nebular volatility trends and (for K) from terrestrial heat flow data. Our models also predict that vaporization and thermal escape during planetary accretion are unlikely to produce the observed alkali element depletion pattern. However, loss during the putative giant impact which formed the Moon cannot be ruled out. Experimental, observational, and theoretical tests of our predictions are also described. Alkali element partitioning into the Earth's core was modeled by assuming that alkali element partitioning during core formation on the aubrite parent body (APB) is analogous to that on the early Earth. The analogy is reasonable for three reasons. First, the enstatite meteorites are the only known meteorites with the same oxygen isotope systematics as the Earth-Moon system. Second, the large core size of the Earth and the V depletion in the mantle requires accretion from planetesimals as reduced as the enstatite chondrites. Third, experimental studies of K partitioning between silicate and metal plus sulfide show that more K goes into the metal plus sulfide at higher pressures than at one atmosphere pressure. Thus partitioning in the relatively low pressure natural laboratory of the APB is a good guide to alkali elemental partitioning during the growth of the Earth.

Lodders, K.↗

Chemically anomalous, pre-accretionally irradiated grains in interplanetary dust -- interstellar grains?

Ultrafine-grained matrix is a unique and fundamental building block of chondritic porous (CP) interplanetary dust particles. Most IDPs so far determined to be of cometary origin belong to the CP class. The matrix in CP IDPs is not homogeneous but rather a loose mixture of discrete single crystals (e.g., olivine, pyroxene, Fe sulfides) and polyphase grains. The petrographic diversity observed among the polyphase grains suggest that they were formed under variable physiochemical conditions. One particular class of polyphase grains are a dominant component in cometary IDPs. Although their occurrence is well documented, the terminology used to describe them is confused. They have been called many names. Here they are simply called GEMS (Glass with Embedded Metal and Sulfides). The bulk compositions of GEMS are within a factor of 3 chondritic (solar) for all major elements except C. Quantitative thin-film X-ray (EDS) analyses have shown that GEMS are systematically depleted in Mg and Si, enriched in S, Fe, and Ni, and stoichiometrically enriched in O. Electron energy-loss spectroscopy (EELS) suggests that the excess O is present as hydroxyl (-OH) groups. These same chemical 'anomalies' were observed in solar-wind-irradiated amorphous rims on the surfaces of IDPs, suggesting that the compositions of GEMS reflect prior exposure to ionizing radiation. In order to test this hypothesis, a sample of Allende (CV3) matrix was exposed to proton flux. Radiation-damaged amorphous rims on olivine and pyroxene crystals in the Allende sample were found to be depleted in Mg and Ca, enriched in S, Fe, and Ni, and stoichiometrically enriched in O. Thus, the compositions of GEMS are indeed consistent with exposure to ionizing radiation. This study suggests that chemical as well as isotopic anomalies may be used to identify presolar interstellar grains in primitive meteoritic materials.

Bradley, J. P.↗