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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. 

Strain localization is central to the transition between continental rifting and seafloor spreading. In the East African Rift System (EARS), there is an emerging understanding of the link between extensional pulses and magmatic episodes. We investigate modern magmatism located within the Turkana Depression and its relationship with the distribution of extensional strain. We probe the source of magmatism at South Island volcano using bulk rock, melt inclusion and olivine geochemical data and find that the magmas are derived from sub-lithospheric sources equivalent to magmatism in the more mature sectors of the rift. The depth extent of the magmatic plumbing system of South Island is constrained using vapour saturation pressures derived from bubble-corrected H 2 O and CO 2 concentrations in melt inclusions and the results indicate a magmatic system resembling modern axial volcanic systems observed in other parts of the EARS. The zone of focused axial magmatism that South Island represents has evolved contemporaneously with a region of focused axial faulting that has accommodated the majority of regional Holocene extension and subsidence at this latitude. We conclude that at South Island there has been a migration of magmatic and tectonic strain towards the modern zone of focused intrusion along this portion of the EARS. Supplementary material: S1–S2 image files, data table files S3–S6 and caption file S7 are available at https://doi.org/10.6084/m9.figshare.c.6026627 

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 The degassing of CO₂and S from arc volcanoes is fundamentally important to global climate, eruption forecasting, ore deposits, and the cycling of volatiles through subduction zones. However, all existing thermodynamic/empirical models have difficulties reproducing CO₂‐H₂O‐S trends observed in melt inclusions and provide widely conflicting results regarding the relationships between pressure and CO₂/SO₂in the vapor. In this study, we develop an open‐source degassing model, Sulfur_X, to track the evolution of S, CO₂, H₂O, and redox states in melt and vapor in ascending mafic‐intermediate magma. Sulfur_X describes sulfur degassing by parameterizing experimentally derived sulfur partition coefficients for two equilibria: RxnI. FeS (m) + H₂O (v)  H₂S (v) + FeO (m), and RxnII. CaSO₄(m)  SO₂(v) + O₂(v) + CaO (m), based on the sulfur speciation in the melt (m) and co‐existing vapor (v). Sulfur_X is also the first to track the evolution offO₂and sulfur and iron redox states accurately in the system using electron balance and equilibrium calculations. Our results show that a typical H₂O‐rich (4.5 wt.%) arc magma with high initial S⁶⁺/ΣS ratio (>0.5) will degas much more (∼2/3) of its initial sulfur at high pressures (>200 MPa) than H₂O‐poor ocean island basalts with low initial S⁶⁺/ΣS ratio (<0.1), which will degas very little sulfur until shallow pressures (<50 MPa). The pressure‐S relationship in the melt predicted by Sulfur_X provides new insights into interpreting the CO₂/S_Tratio measured in high‐T volcanic gases in the run‐up to the eruption. 

Inclusions of basaltic melt trapped inside of olivine phenocrysts during igneous crystallization provide a rich, crystal-scale record of magmatic processes ranging from mantle melting to ascent, eruption, and quenching of magma during volcanic eruptions. Melt inclusions are particularly valuable for retaining information on volatiles such as H 2 O and CO 2 that are normally lost by vesiculation and degassing as magma ascends and erupts. However, the record preserved in melt inclusions can be variably obscured by postentrapment processes, and thus melt inclusion research requires careful evaluation of the effects of such processes. Here we review processes by which melt inclusions are trapped and modified after trapping, describe new opportunities for studying the rates of magmatic and volcanic processes over a range of timescales using the kinetics of post-trapping processes, and describe recent developments in the use of volatile contents of melt inclusions to improve our understanding of how volcanoes work. ▪  Inclusions of silicate melt (magma) trapped inside of crystals formed by magma crystallization provide a rich, detailed record of what happens beneath volcanoes. ▪  These inclusions record information ranging from how magma forms deep inside Earth to its final hours as it ascends to the surface and erupts. ▪  The melt inclusion record, however, is complex and hazy because of many processes that modify the inclusions after they become trapped in crystals. ▪  Melt inclusions provide a primary archive of dissolved gases in magma, which are the key ingredients that make volcanoes erupt explosively.