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The geochemical variations of magmas across and along supra-subduction zones (SSZ) have been commonly attributed to profound changes in the phase and chemical compositions of the mantle source and subduction-derived melt and fluid fluxes, as well as the physical parameters (e.g. depth, temperature, oxygen fugacity etc) of slab dehydration, mineral breakdown and melting. Here we test the variability of the Late Quaternary primitive magmas in the southern and northern parts of the meridionally oriented Eastern Volcanic Belt (EVB) of Kamchatka, with a slab depth varying from 60 to 160 km. Eight high-Mg (Mg# > 60 mol%) basalts were characterized for major, trace and platinum-group element (PGE) abundances, as well as the compositions of olivine phenocrysts and olivine-hosted spinel inclusions. The basalts in our study are geochemically typical of SSZ magmas and contain similar liquidus assemblages of forsteritic olivine (Mg# 78–92 mol%), low-Ti Cr-spinel and clinopyroxene. Although the absolute abundances of major and trace elements, and their ratios, in the basalts fluctuate to some extent, the observed variability cannot be correlated with any of considered parameters in the geometry of the Kamchatka SSZ and conditions of melting. This unexpected result led to the evaluation of the platinumgroup element (PGE) systematics against the lithophile and chalcophile trace element geochemistry and the compositions of phenocrysts. Total whole-rock PGE content varies from 2.3 to 11.7 ppb, whereas the normalized PGE concentration patterns are typical for supra-subduction zones magmas and broadly similar in all studied samples. They are enriched in Rh, Pd and Pt relative to mid-ocean ridge basalts (MORB) and have nearly identical concentrations of Ir-group PGE. The only parameter that correlates well with PGE contents is the average Mg# of olivine phenocrysts from 84 to 90.3 mol%. This is interpreted to result from minor cryptic fractionation of sulfide melt, together with pri

Cu-rich magnesioferrite was found in vesicular basaltic trachyandesite in one of lava tubes (Duplex) that formed during the 2012–2013 eruption of the Tolbachik volcano, Kamchatka. This mineral is commonly associated with hematite, tenorite, halite, sylvite, and Ca-rich silicates (mainly, esseneite and Na-rich melilite) in high-temperature (800–1000 ◦ C) reactionary zones (up to 100 µm) covering vesicular rocks and lava stalactites in the Duplex tube. The mineral relationships of this assemblage indicate the following crystallization sequence: Ca-rich silicates + hematite → Cu-rich magnesioferrite → tenorite → chlorides. This formed due to the reaction of hot gases containing Cu, alkalis, and Cl with solidified lava rock. The composition of magnesioferrite varies strongly in CuO (5.8–17.3 wt %; cuprospinel end-member—15–47 mol %), whereas the contents of other oxides are minor, indicating the main isomorphic substitution is Mg 2+ ↔ Cu 2+ . Compositions with maximal CuO content nominally belong to Mg-rich cuprospinel: (Cu 0.48 Mg 0.41 Mn 0.09 Zn 0.02 Ca 0.02 ) (Fe 3+ 1.94 Al 0.03 Ti 0.02 )O 4 . Increasing CuO content of the Duplex Cu-rich magnesioferrite is reflected in Raman spectra by moderate right shifting bands at ≈700–710 and 200–210 cm −1 and the appearance of an additional band at 596 cm −1 . This supports the main isomorphic scheme and may indicate a degree of inversion in the spinel structure. © 2018 by the authors. Licensee MDPI, Basel, Switzerland.

The extent to which water and halogens have primordial origins in the Earth's mantle, or are dominated by seawater-derived components introduced by subduction, remains a matter of debate. 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 global mid-ocean ridges and ocean islands. 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 serpentinised lithospheric mantle associated with dehydrated oceanic crust.

Sulfide melt inclusions entrapped in primitive olivine phenocrysts can be used to understand the compositions of early sulfide melts that may ultimately contribute to magmatic sulfide ore deposits. Sulfide globules hosted in olivine (86–92 mol% Fo) from the Tolbachik basalt (the 1941 eruption) are characterized in terms of their major and trace element abundances using electron microscopy and LA–ICP–MS analysis. Distribution of major elements within individual sulfide globules varies from homogeneous to heterogeneous. Phases include monosulfide solid solution (MSS) and intermediate solid solution (ISS) intergrowths and exsolved low-temperature minerals such as pyrrhotite, pentlandite, chalcopyrite and cubanite. Trace elements (platinum-group elements — PGE, Ag, Te, Au, Pb and Bi) are also present in solid solution in sulfide phases and as micron-sized particles (“nuggets”). Such nuggets of dominantly Au, Pt, Au–Pd and Pd–Te are contained randomly within sulfide matrices or, more commonly, at phase boundaries. Nuggets are also attached to outer surfaces of sulfide globules. Concentrations of PGE in sulfides follow a log normal distribution over four orders of magnitude. The highest measured noble metal concentrations in the analyzed globules (436 ppm Au + PGE) are 13.3 ppm Au, 115 ppm Pt and 299 ppm Pd, whereas 40% of globules have < 15 ppm of noble metals. Gold and PGE concentrations correlate, suggesting these elements were concentrated by the same process(es). We propose that a number of anomalous concentrations of one or several noble metals in the analyzed globules can be best explained by entrapment of Au–PGE-rich particles (solid or liquid) from the silicate melt. Although the individual Tolbachik sulfide globules have variable PGE abundances, their mean composition resembles those of major PGE-sulfide ore deposits (e.g., Norilsk, Sudbury, Platreef and Merensky Reef).

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.