Description: Author Posting. © The Author(s), 2018. This is the author's version of the work. It is posted here under a nonexclusive, irrevocable, paid-up, worldwide license granted to WHOI. It is made available for personal use, not for redistribution. The definitive version was published in Geochimica et Cosmochimica Acta 230 (2018): 155-189, doi:10.1016/j.gca.2018.03.027.

Description: The Kane Megamullion oceanic core complex located along the Mid-Atlantic Ridge (23°30′N, 45°20′W) exposes lower crust and upper mantle directly on the ocean floor. We studied chalcophile elements and sulfides in the ultramafic and mafic rocks of the crust-mantle transition and the mantle underneath. We determined mineralogical and elemental composition and the Cu isotope composition of the respective sulfides along with the mineralogical and elemental composition of the respective serpentines. The rocks of the crust-mantle transition zone (i.e., plagioclase harzburgite, peridotite-gabbro contacts, and dunite) overlaid by troctolites are by one order of magnitude enriched in several chalcophile elements with respect to the spinel harzburgites of the mantle beneath. Whereas the range of Cu concentrations in spinel harzburgites is 7–69 ppm, the Cu concentrations are highly elevated in plagioclase harzburgites with a range of 90–209 ppm. The zones of the peridotite-gabbro contacts are even more enriched, exhibiting up to 305 ppm Cu and highly elevated concentrations of As, Zn, Ga, Sb and Tl. High Cu concentrations show pronounced correlation with bulk S concentrations at the crust-mantle transition zone implying an enrichment process in this horizon of the oceanic lithosphere. We interpret this enrichment as related to melt-mantle reaction, which is extensive in crust-mantle transition zones. In spite of the ubiquitous serpentinization of primary rocks, we found magmatic chalcopyrites [CuFeS2] as inclusions in plagioclase as well as associated with pentlandite [(Fe,Ni)9S8] and pyrrhotite [Fe1−xS] in polysulfide grains. These chalcopyrites show a primary magmatic δ65Cu signature ranging from −0.04 to +0.29 ‰. Other chalcopyrites have been dissolved during serpentinization. Due to the low temperature (〈300 °C) of circulating fluids chalcophile metals from primary sulfides have not been mobilized and transported away but have been trapped in smaller secondary sulfides and hydroxides. Combined with the Cu deposits documented in the crust-mantle transition zones of various ophiolite complexes, our results indicate that the metal enrichment, increased sulfide modes, and potentially formation of small sulfide deposits could be expected globally along the petrological Moho.

Description: This research was funded by a Diamond Grant of the Polish Ministry of Science and Higher Education (DI2012 2057 42 to J. Ciazela), and partly supported by grants of the U.S. National Science Foundation (OCE1434452 and OCE1637130 to H.J.B. Dick), and the German Science Foundation (Bo2941/4-1 to R. Botcharnikov).

Description: Author Posting. © The Author(s), 2017. This is the author's version of the work. It is posted here under a nonexclusive, irrevocable, paid-up, worldwide license granted to WHOI. It is made available for personal use, not for redistribution. The definitive version was published in Geology 45 (2017): 935-938, doi:10.1130/G39287.1.

Description: Gabbroic veins enclosed in mantle peridotite from ocean core complexes next to oceanic transform faults demonstrate sub-crustal crystallization of silicate minerals from a MORB-like melt. Cooler lithosphere there may also affect sulfide crystallization and the metal budget of the lower and upper crust but the related sulfide behavior is poorly understood. Here, we use chalcophile elements to trace sulfide crystallization in a suite of MORB's erupted at the Kane Megamullion south of the Kane Fracture Zone along the Mid-Atlantic Ridge. Cool lithosphere there is inferred from a low magma supply, and lithostratigraphic evidence for thin crust with abundant mantle rock exposed to the seafloor (Dick et al., 2008). We show that the concentrations of Cu, Zn, As, Ga, Pb, Sb and Tl in the Kane Megamullion MORB's rise linearly with melt differentiation expressed by decreasing MgO and Ni content. The low-pressure fractional crystallization within the crust thus occurs at sulfur-undersaturated conditions. Sulfur-undersaturated MORB's are unusual. At the Kane Megamullion, however, the thin crust allows melt to more extensively interact with the shallow and serpentinized mantle. We argue that sulfur and chalcophile elements have been lost from the melt due to sulfide crystallization during melt-rock reaction in the shallow mantle.

Description: This research was funded by a Diamond Grant of the Polish Ministry of Science and Higher Education (DI2012 2057 42 to Ciazela), and partially supported by the European Association of Geochemistry (Early Career Science Ambassador grant to Ciazela) and the National Science Foundation (grant #’s OCE1434452 and OCE1637130 to Dick).

Description: © The Author(s), 2018. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Nature Communications 9 (2018): 3500, doi:10.1038/s41467-018-05804-2.

Description: Subduction zone magmas are more oxidised on eruption than those at mid-ocean ridges. This is attributed either to oxidising components, derived from subducted lithosphere (slab) and added to the mantle wedge, or to oxidation processes occurring during magma ascent via differentiation. Here we provide direct evidence for contributions of oxidising slab agents to melts trapped in the sub-arc mantle. Measurements of sulfur (S) valence state in sub-arc mantle peridotites identify sulfate, both as crystalline anhydrite (CaSO4) and dissolved SO42− in spinel-hosted glass (formerly melt) inclusions. Copper-rich sulfide precipitates in the inclusions and increased Fe3+/∑Fe in spinel record a S6+–Fe2+ redox coupling during melt percolation through the sub-arc mantle. Sulfate-rich glass inclusions exhibit high U/Th, Pb/Ce, Sr/Nd and δ34S (+ 7 to + 11‰), indicating the involvement of dehydration products of serpentinised slab rocks in their parental melt sources. These observations provide a link between liberated slab components and oxidised arc magmas.

Description: We acknowledge financial support by the Australian Research Council (DE120100513 and DP120104240) and the ESRF for beam time (EC1061 and ES238).

Description: Silicate-sulfide liquid immiscibility in mantle-derived magmas has important control on the budget of siderophile and chalcophile metals, and is considered to be instrumental in the origin orthomagmatic sulfide deposits. Data on primitive sulfide melts in natural samples, even those representing most voluminous magmatism in oceanic rifts, are very scarce due to the small size and poor preservation of incipient sulfide melt globules. Here we present the first detailed report of the crystallized sulfides melts in the oceanic picrites of the (presumably) Cretaceous age Kamchatsky Mys ophiolite complex in Eastern Kamchatka (Far East Russia). Sulfide melts are present in three forms; (1) as inclusions in olivine (87.1–89.6 mol% Fo), (2) interstitial to the groundmass minerals (clinopyroxene, plagioclase, and Ti-magnetite) of studied picrites, and (3) as daughter phases in silicate melt inclusions hosted by olivine and Cr-spinel phenocrysts. The sulfide melt inclusions in olivine and the groundmass of studied rocks are composed of several sulfide phases that correspond to the monosulfide (Fe–Ni; Mss) and intermediate (Fe–Cu–Ni; Iss) solid solutions. Several 〈0.5 μm Pd–Sn, Pt–Ag, and Au–Ag phases are recorded within the matrix sulfides, commonly along phase boundaries and fractures. Major elements (S, Fe, Cu, Ni, Co), platinum group elements (PGE), and gold analyzed in the homogenized olivine-hosted sulfide melt inclusions, and phases identified in the matrix sulfides record the range of magmatic sulfide compositions. The most primitive sulfide liquids are notably enriched in Ni and Cu [(Ni+Cu)/Fe, at% 〉 0.5], continuously evolve with crystallization of (e.g., increasing Cu/Ni and Au/PGE) and demonstrate metal fractionation between Mss and Iss. Although the compositional systematics found in this study are consistent with those previously recorded, the compositions of individual sulfide phases are strongly affected by the noble metal (PGE, Au) “nuggets” that exsolve at subsolidus temperatures and form during serpentinization of the rocks. We conclude that the budget of noble metals in the studied picrites is controlled by sulfides, but the abundances of Pt and Au are influenced by mobility in post-magmatic alteration. Our data can be also used for modeling sulfide saturation at crustal pressures and understanding behavior of the noble metals in primitive oceanic magmas.

Description: Silicic Icelandic magmas are widely believed to contain low to moderate H2O content prior to degassing, and that their high explosivity mostly results from the interaction of the magmas with ice or meteoric water. Here we report the compositions of glass inclusions (SiO2=57–72 wt%, K2O=1.3–2.6 wt%) in Fe-rich olivines (Fo2–42) from the largest Holocene eruptions of Hekla volcano (H3 and H4) on Iceland, which preserved quenched melts with very high primary H2O contents (3.3–6.2 wt%). The silicic Hekla melts originate primarily by extensive (∼90%) crystal fractionation of H2O-poor (∼0.6 wt%) basalts and represent an end member in the systematics of terrestrial magmas because they originate at low fO2 (ΔQFM ∼−0.1 to −0.4) and have as high H2O contents as significantly more oxidized island-arc magmas (ΔQFM≥1). This demonstrates that H2O and ΔQFM do not correlate in silicic magmas from different tectonic settings, and that fO2, not H2O content, shows a major difference between silicic ocean-island (e.g., Icelandic) and island-arc magmas. Analysis of available experimental data suggests that high H2O activity and low fO2 expand the field of olivine stability in silicic melts. Low fO2 and low MgO content could also suppress crystallization of amphibole. On the basis of these results we propose that an anhydrous mineral assemblage bearing Fe-rich olivine in evolved volcanic and Skaergaard-type intrusive rocks does not imply low H2O in magmas prior to degassing but, in contrast to the commonly held view, is an indicator of H2O-rich silicic parental magmas crystallized at low fO2. Finally, the high H2O content in magma was a major driving force of the largest explosive eruptions of Hekla volcano and must be at least as important for driving silicic explosive volcanism on Iceland as magma–ice interaction.

Description: The Troodos igneous complex (Cyprus) is a ca. 90 Ma old, well preserved supra-subduction zone ophiolite. Troodos is unique in that it shows evidence of fluid-saturation throughout the complex, from its base (i.e. podiform chromitites) to its uppermost units – the upper pillow lavas (UPL). However, it is unclear what the source of dissolved water in UPL tholeiites is, with possibilities including shallow seawater infiltration, assimilation of altered Troodos oceanic crust, recycled serpentinized oceanic crust, or subducted pelagic sediments. In order to identify and characterize these components we have carried out a detailed high-resolution study on tholeiitic lavas on orbicular structures and glasses from the UPL in Troodos. Basaltic orbicules were measured for their Sr–Nd–Hf–Pb isotope compositions, and in situ for their B isotopes using LA-MC-ICP-MS. UPL orbicules display a very narrow range in ∊∊Nd and ∊∊Hf (+7 to +8 and +13 to +15, respectively) indicating melting of a depleted mantle source. Lead isotopes, specifically 207Pb/204Pb vs. 206Pb/204Pb, form a mixing array with pelagic sediments. Furthermore, high-resolution characterization of individual orbicules revealed that UPL tholeiites display strong variability in 87Sr/86Sr (0.7039–0.7060) at the outcrop scale. Samples display δ11δ11B between −8.2 (±±0.5)‰ and +5.9 (±±1.1)‰ with an average B content of ca. 5 μg/g. Contrary to expectation, altered orbicules and their associated hyaloclastite matrixes display lower δ11δ11B (down to −10‰) and higher B contents (max. 200 μg/g) when compared to fresh glass. Furthermore, the orbicules studied here show little or no evidence of interaction with seawater, which is supported by their trace element contents and isotope compositions. When all isotope systems are taken into account, UPL lavas reflect melting of a depleted mantle source that was overprinted by hydrous sediment melts, and potentially, fluid-like subduction components that in part originate from serpentinized oceanic crust. Subsequent low-temperature alteration then drove δ11δ11B to lower values coupled with increased B uptake due to its adsorption into palagonite.

Description: Highlights • Melt inclusions from Klyuchevskoy were homogenized at 1150 °C and PH2O=500 MPaPH2O=500 MPa. • High-P experiments can recover initial H2O and CO2 contents in dehydrated inclusions. • Isothermal (de)hydration results in linear trend of CO2 and H2O in inclusion glasses. • Parental Klyuchevskoy magmas contain ∼3800 ppm CO2 and 4–5 wt.% H2O. • At least 80% of CO2 is slab-derived in the Klyuchevskoy magmas with CO2/Nb ∼3000. Abstract Reliable evaluation of CO2 contents in parental arc magmas, which can be preserved in melt inclusions in phenocrysts, is required to verify the proposed efficiency of CO2 recycling at convergent margins. Quantification of bulk CO2 concentration in melt inclusions requires their complete homogenization. Using samples from lavas from the Bulochka vent of Klyuchevskoy Volcano (Kamchatka), we applied a novel experimental approach to homogenize and re-equilibrate naturally dehydrated (〈1 wt.% H2O) melt inclusions from high-Fo (85–91 mol.%) olivine. The experiments were performed at temperatures of 1150–1400 °C, pressures of up to 500 MPa, under dry to H2O-saturated conditions and with oxygen fugacity ranging from CCO to QFM+3.3. No homogenization was achieved at dry conditions. Complete dissolution of fluid bubbles (homogenization) in the melt inclusions was achieved at H2O pressures of 500 MPa and temperature of 1150 °C, when water content in the melt inclusions reached 4–5 wt.% H2O. The CO2 content in the homogenized inclusions is 3800±140 ppm3800±140 ppm and CO2/Nb = 3000 ± 420, which are the highest values reported so far for the typical middle-K primitive arc melts and fall within the range of values inferred from the magmatic flux and volcanic gas data for primary arc magma compositions. About 83% of the CO2 in Klyuchevskoy magmas is likely to be derived from the subducting slab and can be attributed to flux melting with a fluid having a CO2/H2O ratio of ∼0.06. The H2O and CO2 contents in the melt inclusions after hydrous experiments were found to correlate positively with each other and negatively with the volume of fluid bubble, reflecting increasing internal pressure in melt inclusions with increasing melt hydration. Therefore, similar trends observed in some natural sets of melt inclusions can be attributed to a partial dehydration of melts after entrapment, operating simultaneously with or following post-entrapment crystallization. Our study implies that the process of post-entrapment dehydration can be completely reversed under high pressure experimental conditions. If temperature, redox conditions and pressure of melt inclusion entrapment can be independently estimated, then our novel experimental approach (homogenization at high H2O pressure) can be used to reconstruct the initial CO2 content and also the entire composition of melt inclusions in olivine, including their initial H2O content, from any type of volcanic rock. With this approach volatiles in ancient lavas can also be determined, expanding our knowledge of volatile recycling further back in Earth history.