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411.
Claudia L. Caldeira Virginia S.T. Ciminelli Kwadwo Osseo-Asare 《Geochimica et cosmochimica acta》2010,74(6):1777-1789
The mechanism of pyrite oxidation in carbonate-containing alkaline solutions at 80 °C was investigated with the help of rate experiments, thermodynamic modeling and diffuse reflectance infrared spectroscopy (DRIFTS). Pyrite oxidation rate increased with pH and was enhanced by addition of bicarbonate/carbonate ions. The carbonate effect was found to be limited to moderately alkaline conditions (pH 8-11). Metastable Eh-pH diagrams, at 25 °C, indicate that soluble iron-carbonate complexes (FeHCO3−, FeCO30, Fe(CO3)(OH)− and FeCO32−) may coexist with pyrite in the pH range of 6-12.5. Above pH 11 and 13, the Fe(II) and Fe(III) hydroxocomplexes, respectively, become stable, even in the presence of carbonate/bicarbonate ions. Surface-bound carbonate complexes on iron were also identified with DRIFTS as products of pyrite oxidation in addition to iron oxyhydroxides and soluble sulfate species. The conditions under which thermodynamic and DRIFTS analyses indicate the presence of carbonate compounds also correspond to those in which the fastest rate of pyrite oxidation in carbonate solutions was observed. Following the Singer-Stumm model for pyrite oxidation in acidic solutions, it is assumed that Fe(III) is the preferred pyrite oxidant under alkaline conditions. We propose that carbonate ions facilitate the electron transfer from soluble iron(II)-carbonate to O2, increase the iron solubility, and provide buffered, favorable alkaline conditions at the reaction front, which in turn favors the overall kinetics of pyrite oxidation. Therefore, the electron transfer from sulfur atoms to O2 is facilitated by the formation of the cycle of Fe(II)-pyrite/Fe(III)-carbonate redox couple at the pyrite surface. 相似文献
412.
413.
Lina Seybold Claudia A. Trepmann Stefan Hölzl Kilian Pollok Falko Langenhorst Fabian Dellefant Melanie Kaliwoda 《Meteoritics & planetary science》2023,58(9):1287-1305
Shock-related calcite twins are characterized in calcite-bearing metagranite cataclasites within crystalline megablocks of the Ries impact structure, Germany, as well as in cores from the FBN1973 research drilling. The calcite likely originates from pre-impact veins within the Variscan metagranites and gneisses, while the cataclasis is due to the Miocene impact. Quartz in the metagranite components does not contain planar deformation features, indicating low shock pressures (<7 GPa). Calcite, however, shows a high density (>1/μm) of twins with widths <100 nm. Different types of twins (e-, f-, and r-twins) crosscutting each other can occur in one grain. Interaction of r- and f-twins results in a-type domains characterized by a misorientation relative to the host with a misorientation angle of 35°–40° and a misorientation axis parallel to an a-axis. Such a-type domains have not been recorded from deformed rocks in nature before. The high twin density and activation of different twin systems in one grain require high differential stresses (on the order of 1 GPa). Twinning of calcite at high differential stresses is consistent with deformation during impact cratering at relatively low shock pressure conditions. The twinned calcite microstructure can serve as a valuable low shock barometer. 相似文献