Description: The extent to which water and halogens in Earth’s mantle have primordial origins, or are dominated by seawater-derived components introduced by subduction is debated. About 90% of non-radiogenic xenon in the Earth’s mantle has a subducted atmospheric origin, but the degree to which atmospheric gases and other seawater components are coupled during subduction is unclear. Here we present the concentrations of water and halogens in samples of magmatic glasses collected from mid-ocean ridges and ocean islands globally. We show that water and halogen enrichment is unexpectedly associated with trace element signatures characteristic of dehydrated oceanic crust, and that the most incompatible halogens have relatively uniform abundance ratios that are different from primitive mantle values. Taken together, these results imply that Earth’s mantle is highly processed and that most of its water and halogens were introduced by the subduction of serpentinized lithospheric mantle associated with dehydrated oceanic crust.

Description: A new model of sulfur solubility in mafic and/or ultramafic silicate magmas, which accounts for the effects of pressure, temperature, oxygen fugacity, major element, and Ni contents in the silicate melt and the coexisting sulfide liquid, is presented in this paper. The model postulates the existence of positively charged Fe-Ni sulfide complexes in the melt of a general formula (Fe y Ni 1–y ) z S 2(z–1)+ , which are formed as a result of complexation reactions between the sulfide-forming ions (Fe 2+ , Ni 2+ , S 2– ) and (Fe,Ni)S species in the silicate liquid. The new model can explain both the anomalously high S solubility in iron-enriched silicate systems and the "parabola-like" dependence of S contents in silicate melts on their Fe content. The proposed mechanism of sulfide solubility was calibrated on a dataset of 213 anhydrous experimental glasses (both Ni free and Ni bearing) and 53 S-saturated MORB glasses, and incorporated into a new version of the COMAGMAT (v. 5) magma crystallization model. The COMAGMAT-5 model can estimate sulfur concentration at sulfide saturation (SCSS) in a wide range of experimental and natural compositions, including Fe/Ni variations in silicate melts and coexisting sulfides. Despite relatively low concentrations, nickel is shown to have a pronounced effect on S solubility, causing significant variations in the onset of sulfide immiscibility in melts with otherwise similar major element compositions. An application example of the new SCSS model to "B-1 magma" proposed as parent for the Lower and Lower Critical zones of the Rustenburg Layered Suite, Bushveld Complex, is discussed.

Description: We measured oxygen isotope compositions of 34 adakites, high-Mg andesites, and lavas suspected to contain abundant slab and sediment melts from the Western and Central Aleutians, the Andes, Panama, Fiji, Kamchatka, Setouchi (Japan), and the Cascades. This suite covers much of the diversity of arc lavas previously hypothesized to contain abundant ‘slab’ melts. Measured and calculated values of δ18O for olivine phenocrysts in these samples vary between 4.88‰ and 6.78‰, corresponding to calculated melt values of 6.36‰ to 8.17‰. Values of δ18O for these samples are correlated with other geochemical parameters having petrogenetic significance, including Sr/Y, La/Yb, 87Sr/86Sr, and 143Nd/144Nd. Archetypical adakites from Adak Island (Central Aleutian) and Cook Island (Andean Austral zone), previously interpreted to be nearly pure melts of basaltic and gabbroic rocks in subducting slabs, have values of δ18O slightly higher than those of normal mid-ocean-ridge basalts, and in oxygen isotope equilibrium with typical mantle peridotite (i.e., their subtle 18O enrichment reflects their Si-rich compositions and low liquidus temperatures, not 18O-rich sources). Other primitive adakites from Panama and Fiji show only subtle sub-per mil enrichments in the source. This finding appears to rule out the hypothesis that end-member adakites are unmodified partial melts of basaltic rocks and/or sediments in the top (upper 1–2 km) of the subducted slab, which typically have δ18O values of ca. 9–20‰, and also appears to rule out them being partial melts of hydrothermally altered gabbros from the slab interior, which typically have δ18O values of ca. 2–5‰. One explanation of this result is that adakites are mixtures of partial melts from several different parts of the slab, so that higher- and lower-δ18O components average out to have no net difference from average mantle. Alternatively, adakites might be initially generated with more extreme δ18O values, but undergo isotopic exchange with the mantle wedge before eruption. Finally, adakites might not be slab melts at all, and instead come from differentation and/or partial melting processes near the base of the arc crust in the over-riding plate. High-Mg andesites and Setouchi lavas are commonly higher in δ18O than equilibrium with the mantle, consistent with their containing variable amounts of partial melts of subducted sediments (as we conclude for Setouchi lavas), slab-derived aqueous fluid (as we conclude for the Cascades) and/or crustal contaminants from the over-riding plate (as we conclude for Kamchatka).

Description: The Kapai Slate is a continuous, pyrite-rich carbonaceous shale horizon within the St. Ives Au district that is spatially related to high-grade Au mineralization. In situ laser ablation-inductively coupled mass spectrometry (LA-ICPMS) trace element analyses, in situ sensitive high resolution ion microprobe, stable isotope (SHRIMP-SI) S isotope analyses, and optical microscopy pyrite texture analyses were used to examine the different pyrite types in the Kapai Slate and Au deposits. These data were also used to confirm that the trace element signature of sedimentary pyrite can be preserved in rocks that underwent upper to mid-greenschist facies metamorphism and significant hydrothermal overprint. The data were further utilized to gain a more detailed understanding of the ocean conditions during deposition of the Kapai Slate and determine whether some of the Au and S in the St. Ives district could have been sourced from the Kapai Slate. Seven different types of pyrite were identified: fine-grained sedimentary pyrite (Py 1 ), nodular sedimentary pyrite (Py 2 ), remobilized sedimentary pyrite (Py 3 ), coarse-grained, inclusions poor late pyrite (Py 4 ), inclusion-rich magnetite series pyrite (Py 5 ), ore stage pyrite (Py 6 ), and pyrite associated with the mafic units (Py 7 ). Each type of pyrite was found to have distinctive trace element compositions and S isotope signatures. The results of the LA-ICPMS analyses provide evidence for early trace element enrichment in the Kapai Slate sedimentary pyrite (median values of 158 ppm Ni, 387 ppm Co, 82 ppm Cu, 727 ppm As, 1.91 ppm Mo, 13 ppm Se, 0.25 ppm Au, 7.72 ppm Te and 3.36 ppm Ag for Py 1 and 223 ppm Ni, 158 ppm Co, 99 ppm Cu, 856 ppm As, 1.27 ppm Mo, 10.2 ppm Se, 0.57 ppm Au, 10.09 ppm Te, and 6.62 ppm Ag for Py 2 ). Concentrations of Ni and Co are low, relative to other late Archean sedimentary pyrite (median of 813 and 465 ppm, respectively) and Mo levels are near that of the euxinic shales of the similar-aged Jeerinah Formation in the Hamersley Basin, Western Australia. These data suggest that the Kapai Slate was deposited in an anoxic to euxinic basin with relatively low biological productivity. The 33 S and 34 S signatures of the sedimentary pyrite suggest two different sources of S. Positive 34 S and negative 33 S signatures indicate bacterial reduction of SO 4 2– from seawater, whereas positive 34 S and positive 33 S signatures indicate an elemental S 8 source, indicating the pyrite formed later during diagenesis. This S isotope signature is consistent with a transition between a near-sediment environment to a more distal environment source. Analyses of the ore-phase pyrite yield weakly positive 33 S values. This suggests there was a minor contribution of sedimentary S to the more significant oxidized ore-forming fluids, which is consistent with a small contribution of Au from a sedimentary source. Approximations of the degree of sedimentary pyrite destruction in the pyrrhotite/pyrite dominated zones and pyrrhotite/magnetite/pyrite zones of the northern part of the St. Ives district were used to calculate the amount of Au released from the early sedimentary pyrite. The calculation suggests that a minor, though possibly locally significant, amount of Au could have been sourced from the Kapai Slate.