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This study evaluates changes in copper (Cu) speciation that occur in sulfate-dominated basaltic and andesitic magmas equilibrated at oxygen fugacities (fO2’s) above the nickel-nickel oxide (NNO) buffer. Cu K-edge microfocused X-ray absorption fine structure spectroscopy (XAFS) data are presented from both natural and synthetic silicate glasses. Natural samples analyzed include olivine-hosted melt inclusions from tephra of mafic cinder cones in the Lassen segment of the Cascade arc (USA) and from the Michoacan-Guanajuato volcanic field (Mexico) as representative samples from melts equilibrated at fO2 > NNO. A comparison with melts equilibrated at fO2 < NNO is provided by analysis of olivine-hosted melt inclusions from Kīlauea Volcano. Data are also presented from copper- and sulfur-bearing synthetic hydrous andesitic glasses synthesized over a range of fO2, from roughly NNO-2 to NNO+2. The Cu spectroscopy data from the natural and synthetic glasses show two dominant Cu species, Cu1+ oxides (referred to here as Cu-O) and Cu1+ sulfides (referred to here broadly as Cu-S, but not precluding Cu-Fe-S species). The relative proportion of each species present correlates with the relative concentration of dissolved sulfide in the melt. Synthetic sulfur-bearing glasses equilibrated at NNO-1.2 were found to contain exclusively Cu-S species. Sulfur-bearing experimental glasses equilibrated at NNO-0.5 give calculated Cu-O/(Cu-O + Cu-S), defined here as the “Cu-O fraction”, of < 0.10, whereas sulfur-bearing glasses synthesized at NNO+0.6 and NNO+1.8 give calculated Cu-O fraction > 0.96. Natural melt inclusions from Lassen and Kīlauea show a bimodal distribution in Cu-O fraction, with overlapping ranges, of 0.14-0.77 for Lassen and 0.18- 0.78 for Kīlauea. Michoacan-Guanajuato inclusions yield Cu-O fractions of 0.68-0.91. The difference in the calculated proportions of Cu-O to Cu-S species appear correlated with available sulfide in the melt. As relative S2- concentrations decrease, the dissolved Cu species in the melt evolves from dominantly Cu-S to Cu-O. This includes melts equilibrated at fO2’s where S6+ is the dominant S species. At intermediate sulfide abundances both species appear to coexist. Thermodynamic modeling of the Cu speciation in these silicate melts suggests that speciation of Cu as a CuFeS2 melt species (akin to chalcopyrite or intermediate solid solution) most accurately predicts the measured Cu species. The modeling suggests that aFeO in the silicate melt, fO2 and melt S2- (expressed as fS2) are the most important parameters controlling the proportions of Cu-O vs. Cu-S species. Our results provide a new perspective for understanding Cu solubility, transport, and partitioning in magmatic systems. 

These data correspond to the article “Deep Nitrogen Fluxes and Sources Constrained by Arc Lava Phenocrysts” by Hudak et al. submitted to Geophysical Research Letters. Table S1 includes N-He-Ar data for FIs in phenocrysts from mafic are lavas and tephras. Table S2 contains the corrected N2/3He data used for volcanic arc N flux calculations and the arc-averaged mean N arc flux. Table S3 summarizes previous literature estimates of N fluxes and the data used for those calculations. Table S4 provides the N concentrations, He concentrations, N isotope compositions of the mantle, sediments, and altered oceanic crust, as well as sediment thicknesses. Finally, Table S5 gives information about the sources of the mineral separates used for these analyses. 

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. 

Abstract Nitrogen (N) dominates Earth's atmosphere (78% N₂) but occurs in trace abundances in silicate minerals, making it a sensitive tracer of recycled surface materials into the mantle. The mechanisms controlling N transfer between terrestrial reservoirs remain uncertain because low N abundances in mineral‐hosted fluid inclusions (FIs) are difficult to measure. Using new techniques, we analyzed N and He isotope compositions and abundances in olivine‐ and pyroxene‐hosted FIs from arc volcanoes in Southern Chile, Cascadia, Central America, and the Southern Marianas. These measurements enable an estimate of the global flux of N outgassing from arcs (4.0 × 10¹⁰ mol/yr). This suggests that Earth is currently in a state of net N ingassing, with roughly half of subducted N returned to the mantle. Additionally, the N outgassing flux of individual arcs correlates with the thickness of subducting pelagic sediment, suggesting that N cycling in the modern solid Earth is largely controlled by sediment subduction.