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Galactic interstellar abundance surveys with IUE. III - Silicon, manganese, iron, sulfur, and zinc

This paper continues a survey of intestellar densities, abundances, and cloud structure in the Galaxy using the IUE satellite. A statistical data set of 223 O3-B2.5 stars is constructed, including 53 stars in the Galactic halo. It is found that S II lines in B stars, of luminosity classes IV and V, have possible contamination from stellar S II, particular for stars with v sin i less than 200 km/s. The mean logarithmic depletions are -1.00, -1.19. -0.63, and -0.23 (Si, Mn,Fe,S, Zn). Depletions of Si, Mn, and Fe correlate with the mean hydrogen density n-bar along the line of sight, with a turnover for n-bar greater than 1/cm. Sulfur depletions correlate with n-bar along the line of sight. The slight Zn depletion correlation also appears to be statistically insignificant. No correlation of depletion is found with the physical density derived from H2 rotational states in 21 lines of sight. Depletion variations in the disk are consistent with a Galactic abundance gradient or with enhanced mean depletions in the anticenter region.

Van Steenberg, Michael E.↗

Iron and manganese in anaerobic respiration: environmental significance, physiology, and regulation

Dissimilatory iron and/or manganese reduction is known to occur in several organisms, including anaerobic sulfur-reducing organisms such as Geobacter metallireducens or Desulfuromonas acetoxidans, and facultative aerobes such as Shewanella putrefaciens. These bacteria couple both carbon oxidation and growth to the reduction of these metals, and inhibitor and competition experiments suggest that Mn(IV) and Fe(III) are efficient electron acceptors similar to nitrate in redox abilities and capable of out-competing electron acceptors of lower potential, such as sulfate (sulfate reduction) or CO2 (methanogenesis). Field studies of iron and/or manganese reduction suggest that organisms with such metabolic abilities play important roles in coupling the oxidation of organic carbon to metal reduction under anaerobic conditions. Because both iron and manganese oxides are solids or colloids, they tend to settle downward in aquatic environments, providing a physical mechanism for the movement of oxidizing potential into anoxic zones. The resulting biogeochemical metal cycles have a strong impact on many other elements including carbon, sulfur, phosphorous, and trace metals.

Review, Academic↗

Geochemistry of Pallasite Olivines and the Origin of Main-Group Pallasites

Main-group pallasites (PMG) are mixtures of iron-nickel metal and magnesian olivine thought to have been formed at the core-mantle boundary of an asteroid [1]. Some have anomalous metal compositions (PMG-am) and a few have atypically ferroan olivines (PMG-as) [2]. PMG metal is consistent with an origin as a late fractionate of the IIIAB iron core [2]. Most PMG olivines have very similar Fe/Mg ratios, likely due to subsolidus redox reaction with the metal [3]. In contrast, minor and trace elements show substantial variation, which may be explained by either: (i) PMG were formed at a range of depths in the parent asteroid; the element variations reflect variations in igneous evolution with depth, (ii) the pallasite parent asteroid was chemically heterogeneous; the heterogeneity partially survived igneous processing, or (iii) PMG represent the core-mantle boundaries of several distinct parent asteroids [4, 5]. We have continued doing major, minor and trace elements by EMPA and INAA on a wider suite of PMG olivines, and have begun doing precise oxygen isotope analyses to test these hypotheses. Manganese is homologous with Fe(2+), and can be used to distinguish between magmatic and redox processes as causes for Fe/Mg variations. PMG olivines have a range in molar 1000*Mn/Mg of 2.3-4.6 indicating substantial igneous fractionation in olivines with very similar Fe/Mg (0.138-0.148). The Mg-Mn-Fe distributions can be explained by a fractional crystallization-reduction model; higher Mn/Mg ratios reflect more evolved olivines while Fe/Mg is buffered by redox reactions with the metal. There is a positive association between Mn/Mg and Sc content that is consistent with igneous fractionation. However, most PMG olivines fall within a narrow Mn/Mg range (3.0-3.6), but these show a substantial range in Sc (1.00-2.29 micro-g/g). Assuming fractional crystallization, this Sc range could have resulted from approx.65% crystallization of an ultramafic magma. This is inconsistent with formation at the core-mantle boundary of a single asteroid [4]. One alternative is that the PMG are fragments of several asteroids, and these could have had different initial Sc contents, Mn/Mg and differences in igneous history. Our preliminary O isotope data and those of [6, 7] do not support this, although the coverage of PMG olivines is incomplete. The PMG-as Springwater is not easily fit in any scenario. Its olivine has among the highest Mn/Mg suggesting it is one of the most evolved, but the lowest Sc content suggesting it is the least evolved. The O isotopic composition of Springwater olivine is the same as that of other PMG. Thus there is no indication that it represents a distinct parent asteroid. Our preliminary O isotopic data favor a single PMG parent asteroid. In this case, the olivines are more likely melt-residues, and that the parent asteroid was initially heterogeneous in chemical, but not isotopic, composition.

Mittlefehldt, D. W.↗

Metal dynamics in Lake Vanda (Wright Valley, Antarctica)

Data are reported for Mn, Fe, Co, Ni, Cu and Cd in the Onyx River, and for Mn, Co, Ni, Cu and Cd in Lake Vanda, a closed-basin Antarctic lake. Oxic water concentrations for Co, Ni, Cu and Cd were quite low and approximate pelagic ocean values. Scavenging of these metals by sinking particles is strongly indicated. Deep-lake profiles reveal a sharp peak in the concentrations of Mn, Fe and Co at the oxic-anoxic boundary at 60 m. Maxima for Ni, Cu and Cd occur higher in the water column, in the vicinity of a Mn submaximum, suggesting early release of these metals from sinking manganese oxide-coated particles. A rough steady-state model leads to the conclusion that there is a large downward flux of Mn into the deep lake and that this flux is sufficient to explain the annual loss of Co, Ni, Cu and Cd. A pronounced geochemical separation between Fe and Mn apparently occurs in this system--Fe being best lost in near-shore environments and Mn being lost in deeper waters. Comparison of metal residence times in Lake Vanda with those in the oceans shows that in both systems Mn, Fe and Co are much more reactive than Ni, Cu and Cd. Energetically favorable inclusion of the more highly charged metals, Mn(IV), Fe(III) and Co(III), into oxide-based lattices is a plausible explanation.

NASA Center ARC↗

Oxidation Of Manganese At Kimberley, Gale Crater: More Free Oxygen In Mars' Past?

High Mn concentrations provide unique indicators of water-rich environments and their redox state. Very high-potential oxidants are required to oxidize Mn to insoluble, high-valence oxides that can precipitate and concentrate Mn in rocks and sediments; these redox potentials are much higher than those needed to oxidize Fe or S. Consequently, Mn-rich rocks on Earth closely track the rise of atmospheric oxygen. Given the association between Mn-rich rocks and the redox state of surface environments, observations of anomalous Mn enrichments on Mars raise similar questions about redox history, solubility and aqueous transport, and availability as a metabolic substrate. Our observations suggest that at least some of the high Mn present in Gale crater occurs in the form of Mn-oxides filling veins that crosscut sand-stones, requiring post-depositional precipitation as highly oxidizing fluids moved through the fractured strata after their deposition and lithification.

Lanza, N. L.↗

Kinetic and Thermodynamic Characterization of the Cobalt and Manganese Oxyhydroxide Cores Formed in Horse Spleen Ferritin

Horse spleen ferritin (HoSF) containing 800-1500 cobalt or 250-1200 manganese atoms as Co(O)OH and Mn(O)OH mineral cores within the HoSF interior (Co-HoSF and Mn-HoSF) was synthesized, and the chemical reactivity, kinetics of reduction, and the reduction potentials were measured. Microcoulometric and chemical reduction of HoSF containing the M(O)OH mineral core (M = Co or Mn) was rapid and quantitative with a reduction stoichiometry of 1.05+/-0.10 e/M forming a stable M(OH)2 mineral core. At pH 9.0, ascorbic acid (AH2), a two-electron reductant, effectively reduced the mineral cores; however, the reaction was incomplete and rapidly reached equilibrium. The addition of excess AH2 shifted the reaction to completion with a M(3+)/AH2 stoichiometry of 1.9-2.1, consistent with a single electron per metal atom reduction. The rate of reaction between M(0)OH and excess AH2 was measured by monitoring the decrease in mineral core absorbance with time. The reaction was first order in each reactant with second-order rate constants of 0.53 and 4.74/M/min, respectively, for Co- and Mn-HoSF at pH 9.0. From the variation of absorbance with increasing AH2 concentration, equilibrium constants at pH 9.0 of 5.0+/-1.9 for Co-HoSF and 2.9+/-0.9 for Mn-HoSF were calculated for 2M(O)OH + AH2 = 2M(OH)2 f D, where AH2 and D are ascorbic acid and dehydroascorbic acid, respectively. Consistent with these equilibrium constants, the standard potential for the reduction of Co(III)-HoSF is 42 mV more positive than that of the ascorbic acid reaction, while the standard potential of Mn(III)-HoSF is 27 mV positive relative to AH2. Fe(2+) in solution with Co- and Mn-HoSF under anaerobic conditions was oxidized to form Fe(O)OH within the HoSF interior, resulting in partial displacement of the Co or Mn by iron.

Zhang, Bo↗

Iron-Manganese Redox Reactions in Endeavour Crater Rim Apron Rocks

The Mars Exploration Rover Opportunity has been exploring Noachian age rocks and outcrops on the rim of the 22 km diameter Endeavour crater since August 2011. The Cape York area is a low-lying rim of Endeavour that contains 3 distinct lithologies: 1) the stratigraphically lowest Matijevic fm of pre-impact lithology, 2) Shoemaker fm of impact breccias, and 3) the stratigraphically highest rim lithology Grasberg fm of post-impact sediments that drape the lower slopes of the rim. The sulfate-rich sediment of the Burns fm lies unconformably over the Grasberg fm. Ca-sulfate veins were discovered in Grasberg fm sediments; the sulfates precipitated from aqueous fluids flowing upward through these materials. Opportunity investigated the chemistry and morphology of outcrops in the Matijevic fm that have Fe(sup 3+)-rich smectite detected by orbital signatures returned by CRISM on MRO. Matijevic fm also contains "boxwork" fractures with chemistry consistent with an Al-rich smectite and veins that appear to be rich in Ca-sulfate. More recently on Cape Tribulation, Opportunity has characterized two S-, Mg- and Mn-rich rich rocks overturned and fractured by the rover's wheels on Cook Haven. Those rocks have been dubbed "Pinnacle Island" and "Stuart Island" and will be referred to as the "Island" rocks. The objectives of this study are to characterize the Fe and Mn contents in the Cape York materials, including the two Island rocks, and to provide a model for Mn mobilization and precipitation. Detailed geochemistry of Endeavour rim rocks is presented in a companion paper. Geochemical trends and elemental associations were obtained from data returned by the Alpha Particle X-ray Spectrometer (APXS) on Opportunity.

Ming, D. W.↗