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  1. Abstract

    Subduction is a key component of Earth's long‐term sulfur cycle; however, the mechanisms that drive sulfur from subducting slabs remain elusive. Isotopes are a sensitive indicator of the speciation of sulfur in fluids, sulfide dissolution‐precipitation reactions, and inferring fluid sources. To investigate these processes, we report δ34S values determined by secondary ion mass spectroscopy in sulfides from a global suite of exhumed high‐pressure rocks. Sulfides are classified into two petrogenetic groups: (1) metamorphic, which represent closed‐system (re)crystallization from protolith‐inherited sulfur, and (2) metasomatic, which formed during open system processes, such as an influx of oxidized sulfur. The δ34S values for metamorphic sulfides tend to reflect their precursor compositions: −4.3 ‰ to +13.5 ‰ for metabasic rocks, and −32.4 ‰ to −11.0 ‰ for metasediments. Metasomatic sulfides exhibit a range of δ34S from −21.7 ‰ to +13.9 ‰. We suggest that sluggish sulfur self‐diffusion prevents isotopic fractionation during sulfide breakdown and that slab fluids inherit the isotopic composition of their source. We estimate a composition of −11 ‰ to +8 ‰ for slab fluids, a significantly smaller range than observed for metasomatic sulfides. Large fractionations during metasomatic sulfide precipitation from sulfate‐bearing fluids, and an evolving fluid composition during reactive transport may account for the entire ~36 ‰ range of metasomatic sulfide compositions. Thus, we suggest that sulfates are likely the dominant sulfur species in slab‐derived fluids.

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  2. Abstract

    Volatile element concentrations measured in melt inclusions are a key tool used to understand magma migration and degassing, although their original values may be affected by different re-equilibration processes. Additionally, the inclusion-bearing crystals can have a wide range of origins and ages, further complicating the interpretation of magmatic processes. To clarify some of these issues, here we combined olivine diffusion chronometry and melt inclusion data from the 2008 eruption of Llaima volcano (Chile). We found that magma intrusion occurred about 4 years before the eruption at a minimum depth of approximately 8 km. Magma migration and reaction became shallower with time, and about 6 months before the eruption magma reached 3–4 km depth. This can be linked to reported seismicity and ash emissions. Although some ambiguities of interpretation still remain, crystal zoning and melt inclusion studies allow a more complete understanding of magma ascent, degassing, and volcano monitoring data.

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  3. Abstract Bromine is a key halogen element in the quantification of volcanic volatiles, but analytical difficulties in measuring its very low abundances have prevented progress in understanding its behavior and its role in volcanic emissions. We present a new data set of bromine, chlorine, and fluorine concentrations in melt inclusions and matrix glasses for two rhyolitic super-eruptions from the Toledo and Valles calderas, New Mexico, USA. We show that before eruption, Br and Cl were efficiently partitioned from the gas-saturated magma into a separate fluid phase, and we calculate the mass of halogens in the fluid phase. We further demonstrate that syn-eruptive magma degassing was negligible during the super-eruptions, so that the main source of halogen emissions must have been the fluid phase. If the fluid phase were erupted, the large mass of Br and Cl could have severely impacted the atmospheric chemistry upon eruption. 
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  4. Abstract Whether and how subduction increases the oxidation state of Earth's mantle are two of the most important unresolved questions in solid Earth geochemistry. Using data from the southern Cascade arc (California, USA), we show quantitatively for the first time that increases in arc magma oxidation state are fundamentally linked to mass transfer of isotopically heavy sulfate from the subducted plate into the mantle wedge. We investigate multiple hypotheses related to plate dehydration and melting and the rise and reaction of slab melts with mantle peridotite in the wedge, focusing on electron balance between redox-sensitive iron and sulfur during these processes. These results show that unless slab-derived silicic melts contain much higher dissolved sulfur than is indicated by currently available experimental data, arc magma generation by mantle wedge melting must involve multiple stages of mantle metasomatism by slab-derived oxidized and sulfur-bearing hydrous components. 
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  6. Abstract The solubility of CO2 in hydrous basaltic andesite was examined in fO2-controlled experiments at a temperature of 1125 °C and pressures between 310–1200 MPa. Concentrations of dissolved H2O and CO2 in experimental glasses were determined by ion microprobe calibrated on a subset of run glasses analyzed by high-temperature vacuum manometry. Assuming that the solubility of H2O in mafic melt is relatively well known, estimates of XH2Ofluid and PH2Ofluid in the saturating fluid were modeled, and by difference, values for XCO2fluid and PCO2fluid were obtained (XCO2 ~0.5–0.9); fCO2 could be then calculated from the fluid composition, temperature, and pressure. Dissolved H2O over a range of 2.3–5.5 wt% had no unequivocal influence on the dissolution of CO2 at the pressures and fluid compositions examined. For these H2O concentrations, dissolved CO2 increases with fCO2 following an empirical power-law relation: dissolved CO2 (ppmw) = 14.9−3.5+4.5[fCO2 (MPa)]0.7±0.03. The highest-pressure results plot farthest from this equation but are within its 1 standard-error uncertainty envelope. We compare our experimental data with three recent CO2-H2O solubility models: Papale et al. (2006); Iacono-Marziano et al. (2012); and Ghiorso and Gualda (2015). The Papale et al. (2006) and Iacono-Marizano et al. (2012) models give similar results, both over-predicting the solubility of CO2 in a melt of the Pavlof basaltic andesite composition across the fCO2 range, whereas the Ghiorso and Gualda (2015) model under-predicts CO2 solubility. All three solubility models would indicate a strong enhancement of CO2 solubility with increasing dissolved H2O not apparent in our results. We also examine our results in the context of previous high-pressure CO2 solubility experiments on basaltic melts. Dissolved CO2 correlates positively with mole fraction (Na+K+Ca)/Al across a compositional spectrum of trachybasalt-alkali basalt-tholeiite-icelandite-basaltic andesite. Shortcomings of current solubility models for a widespread arc magma type indicate that our understanding of degassing in the deep crust and uppermost mantle remains semi-quantitative. Experimental studies systematically varying concentrations of melt components (Mg, Ca, Na, K, Al, Si) may be necessary to identify solubility reactions, quantify their equilibrium constants, and thereby build an accurate and generally applicable solubility model. 
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