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Oxygen and sulfur isotope systematics of sulfate produced during abiotic and bacterial oxidation of sphalerite and elemental sulfur

Studies of metal sulfide oxidation in acid mine drainage (AMD) systems have primarily focused on pyrite oxidation, although acid soluble sulfides (e.g., ZnS) are predominantly responsible for the release of toxic metals. We conducted a series of biological and abiotic laboratory oxidation experiments with pure and Fe-bearing sphalerite (ZnS & Zn 0.88 Fe 0.12 S), respectively, in order to better understand the effects of sulfide mineralogy and associated biogeochemical controls of oxidation on the resultant δ 34 S and δ 18 O values of the sulfate produced. The minerals were incubated in the presence and absence of Acidithiobacillus ferrooxidans at an initial solution pH of 3 and with water of varying δ 18 O values to determine the relative contributions of H 2 O-derived and O 2 -derived oxygen in the newly formed sulfate. . Experiments were conducted under aerobic and anaerobic conditions using O 2 and Fe(III) aq as the oxidants, respectively. Aerobic incubations with A. ferrooxidans , and S o as the sole energy source were also conducted. The δ 34 S SO 4 "> δ34SSO4 values from both the biological and abiotic oxidation of ZnS and ZnS Fe by Fe(III) aq produced sulfur isotope fractionations ( ε 34 S SO 4 - ZnS "> ε34SSO4-ZnS ) of up to −2.6‰, suggesting the accumulation of sulfur intermediates during incomplete oxidation of the sulfide. No significant sulfur isotope fractionation was observed from any of the aerobic experiments. Negative sulfur isotope enrichment factors ( ε 34 S SO 4 - ZnS "> ε34SSO4-ZnS ) in AMD systems could reflect anaerobic, rather than aerobic pathways of oxidation. During the biological and abiotic oxidation of ZnS and ZnS Fe by Fe(III) aq all of the sulfate oxygen was derived from water, with measured ε 18 O SO 4 - H 2 O "> ε18OSO4-H2O values of 8.2 ± 0.2‰ and 7.5 ± 0.1‰, respectively. Also, during the aerobic oxidation of ZnS Fe and S o by A . ferrooxidans , all of the sulfate oxygen was derived from water with similar measured ε 18 O SO 4 - H 2 O "> ε18OSO4-H2O values of 8.1 ± 0.1‰ and 8.3 ± 0.3‰, respectively. During biological oxidation of ZnS by O 2 , an estimated 8% of sulfate–oxygen was derived from O 2 , which is enriched in 18 O relative to water, thus resulting in a larger apparent ε 18 O SO 4 - H 2 O "> ε18OSO4-H2O value of 9.5‰. Based on the data presented we hypothesize that the similar ε 18 O SO 4 - H 2 O "> ε18OSO4-H2O values of ∼8‰ from all of the aerobic and anaerobic experiments result from a common rate-limiting step that involves oxygen isotopic exchange between a sulfite ( SO 3 - "> SO3- ) intermediate and H 2 O. Our results indicate that the δ 18 O SO 4 "> δ18OSO4 values cannot be used to distinguish biological and abiotic, nor aerobic versus anaerobic, pathways of sphalerite oxidation. However, the ε 18 O SO 4 - H 2 O "> ε18OSO4-H2O values of ∼8‰ measured here are distinctly higher than ε 18 O SO 4 - H 2 O "> ε18OSO4-H2O values of ∼4‰ previously reported for pyrite oxidation indicating the influence of sulfide mineralogy on measured δ 18 O SO 4 "> δ18OSO4 values.

Geochimica et Cosmochimica Acta↗

Temperature-dependent variations in mineralogy, major element chemistry and the stable isotopes of boron, lithium and chlorine resulting from hydration of rhyolite glass: Constraints from hydrothermal experiments at 150 to 350°C and 25 MPa

Rhyolite-hosted hydrothermal systems in the continental crust contain valuable energy and mineral resources that make them of special interest across several scientific disciplines. Despite extensive research on these systems, the temperature-dependence of chemical reactions between host rocks and aqueous-rich fluids and the mineralogical transformations resulting from these reactions are not well quantified. To expand our understanding of the controlling processes operating in these systems, we carried out seven laboratory experiments in which rhyolite was reacted with deionized water at 150 °C to 350 °C and 25 MPa. An additional experiment at 200 °C was carried out to examine the effect of dissolved CO 2 on the reactions. The overarching goal of this experimental study was to provide new insights on the temperature-dependence of water-rock interaction in continental hydrothermal systems. We applied a wide range of chemical, isotopic and mineralogical methods to analyze the reacted rhyolite and waters, and the major observations are: (1) the rhyolite progressively hydrates with increasing temperature between 150 °C to a maximum of 8.2 wt% H 2 O at 275 °C; hydration then decreases until 350 °C in conjunction with the destruction of the rhyolite glass and crystallization of secondary mineral phases; (2) the ratio of molecular water (H 2 O m ) to hydroxyl (OH − ) of the water that is dissolved in the reacted rhyolite decreases from ∼7 at 150 °C to ∼4 at 250 °C; (3) the main secondary minerals formed are the zeolite ferrierite (T ≥ 275 °C); biotite, albite and cristobalite mainly form at higher experimental temperatures (T ≥ 300 °C); (4) the reacted waters are nearly saturated with respect to amorphous silica; (5) at temperatures ≥ 275 °C nearly all the chlorine is leached into solution; (6) fluorine leaching from the rhyolite gradually increases between 150 °C and 250 °C, but then gradually decreases at higher temperatures and is incorporated into a secondary mineral phase; (7) dissolved CO 2 in the water enhances alkali metal cation leaching from the rhyolite; and (8) calculated Na-K and silica geothermometer temperatures differ from the experimental temperatures by varying amounts. In addition, apart from some small lithium isotope fractionation at temperatures ≤ 250 °C, the stable isotopes of boron, lithium and chlorine do not fractionate during rhyolite-water reactions, and the stable isotope compositions of these species in the reacted water are similar to those in the reactant rhyolite. These results provide new insights for a broad range of applications, including quantifying processes involving rhyolite glass hydration (obsidian hydration dating, perlite formation and discriminating secondary from magmatic water in rhyolitic matrix-glass of volcanic pyroclasts), for geothermal energy and mineral deposit exploration and for monitoring volcanoes.

Geochimica et Cosmochimica Acta↗

Hydrothermal diamond anvil cell for XAFS studies of first-row transition elements in aqueous solutions up to supercritical conditions

A hydrothermal diamond anvil cell (HDAC) has been modified by drilling holes with a laser to within 150 ??m of the anvil face to minimize the loss of X-rays due to absorption and scatter by diamond. This modification enables acquisition of K-edge X-ray absorption fine structure (XAFS) spectra from first-row transition metal ions in aqueous solutions at temperatures ranging from 25??C to 660??C and pressures up to 800 MPa. These pressure-temperature (P-T) conditions are more than sufficient for carrying out experimental measurements that can provide data valuable in the interpretation of fluid inclusions in minerals found in ore-forming hydrothermal systems as well as other important lithospheric processes involving water. (C) 2000 Elsevier Science B.V. All rights reserved.

Conference Paper↗

Geochemical factors controlling dissolved elemental mercury and methylmercury formation in Alaskan wetlands of varying trophic status

Transformations of aqueous inorganic divalent mercury (Hg(II)i) to volatile dissolved gaseous mercury (Hg(0)(aq)) and toxic methylmercury (MeHg) governs mercury bioavailability and fate in northern ecosystems. This study quantified concentrations of aqueous mercury species (Hg(II)i, Hg(0)(aq), MeHg) and relevant geochemical constituents in pore waters of eight Alaskan wetlands that differ in trophic status (i.e., bog-to-fen gradient) to gain insight on processes controlling dark Hg(II)i reduction and Hg(II)i methylation. Regardless of wetland trophic status, positive correlations were observed between pore water Hg(II)i and dissolved organic carbon (DOC) concentrations. The concentration ratio of Hg(0)(aq) to Hg(II)i exhibited an inverse relationship to Hg(II)i concentration. A ubiquitous pathway for Hg(0)(aq) formation was not identified based on geochemical data, but we surmise that dissolved organic matter (DOM) influences mercury retention in wetland pore waters by complexing Hg(II)i and decreasing the concentration of volatile Hg(0)(aq) relative to Hg(II)i. There was no evidence of Hg(0)(aq) abundance directly limiting mercury methylation. The concentration of MeHg relative to Hg(II)i was greatest in wetlands of intermediate trophic status, and geochemical data suggest mercury methylation pathways vary between wetlands. Our insights on geochemical factors influencing aqueous mercury speciation should be considered in context of the long-term fate of mercury in northern wetlands.

Environmental Science & Technology↗

Lead and strontium isotopes and related trace elements as genetic tracers in the Upper Cenozoic rhyolite-basalt association of the Yellowstone Plateau volcanic field

Supported by various field geologic and petrologic data, the contents of Pb, U, Th, Rb, and Sr and the isotopic compositions of Pb and Sr for upper Cenozoic volcanic rocks of the Yellowstone Plateau volcanic field are consistent with the hypothesis of derivation of the basaltic and rhyolitic magmas by partial melting of distinct source regions in the upper mantle and lower crust, respectively. All the basalt samples analyzed but one have systematically lower values of 207 Pb/ 204 Pb and 87 Sr/ 86 Sr than the rhyolites. The values of 206 Pb/ 204 Pb are smaller, and 87 Sr/ 86 Sr are mostly larger than known values in oceanic basalts. In all but one case, the values of 207 Pb/ 204 Pb are higher than expected from an extrapolation of known values in oceanic basalts to less radiogenic values of 206 Pb/ 204 Pb. Because there are no xenoliths, phenocrysts are only moderate to sparse in abundance, REE patterns are low and flat at the radiogenic end of lead isotopic compositions, several values of Rb/Sr are low, and 80% of the basalt samples form a well-developed secondary isochron separate from the rhyolites, we favor an interpretation for basalt genesis wherein isotopic signatures of most mafic magmas were attained in a continental ‘keel’ of mantlelike character about 2.6 b.y. old or somewhat older attached to the crust, and these signatures were unaltered by magma passage through the crust. At the very least, the current data continue to cast serious doubt as to the inevitability of crustal contamination for basaltic magma intruding the continental environment and postulate that much can be learned about the mantle under continents through the study of continental basalts. One basalt unit with an unusually low value of 207 Pb/ 204 Pb and an 87 Ar/ 86 Ar less than 0.704 may represent subcontinental ‘keel’-derived magma that rose unaltered to the surface. Our data also are not consistent with formation of this rhyolite-basalt association primarily by such processes as crystal fractionation, separation of immiscible silicate liquids from a common parental magma, or fractional melting of a homogeneous source. Rather as a conceptual model, we envision large mafic intrusions to have been injected into the lower crust resulting in rhyolite generation through partial anatexis of the adjacent wall rocks which probably had a 206 Pb/ 204 Pb < 17 and 87 Sr/ 86 Sr > 0.709; a model that has much in common with that proposed by Holmes (1931). All the other hypotheses listed have the necessary added complication that either the basalt or the rhyolite or both become contaminated after the two magma types separated, have problems accounting for the lack of igneous rocks of intermediate compositions or production of such large volumes of rhyolitic material (∼5000 km 3 ), and fail to explain why rhyolitic magma is not a more common occurrence in the ocean basin. We appeal to bouyancy of rhyolites to generate a barrier for basalt magma migration and account for the great preponderance of rhyolite relative to basalt at the surface. Furthermore, the complex isotopic picture in the rhyolites indicates that many of these magmas interacted with the upper crustal geologic units that they traversed. The interactions involved diverse processes, probably including reacton with hydrothermal fluids or hydrothermally altered rocks at high levels as well as by contamination with Phanerozoic sedimentary and Precambrian crystalline rocks at deeper levels. At the very least, we feel our study adds a cautionary note to the currently increasingly popular hypothesis that differentiation of basalt or gabbro magmas to rhyolite or granite (as distinct from tonalite or dacite) is a common occurrence and is therefore an important continential building process. Models for formation of rhyolite and granite predominantly by reworking of crust (anatexis) must still be considered. The primitive Archean mantle of the region was characterized by higher Rb/Sr, U/Pb, and Th/U values than are typical of modern suboceanic mantle. The mantle residuum within the continental subcrustal lithosperic ‘keel’ that resulted from the Archean crustal differentiation event probably was depleted in Rb/Sr and U/Pb, and the crust was correspondingly enriched in these ratios. The crust probably was further differentiated by an Archean high-grade metamorphism, during or after the primary event, into a granulitic lower crust depleted in U/Pb and Rb/Sr and a lower-grade upper crust enriched in these ratios.

Journal of Geophysical Research Solid Earth↗