Description: International Ocean Discovery Program (IODP) Expedition 352 recovered a high-fidelity record of volcanism related to subduction initiation in the Bonin fore-arc. Two sites (U1440 and U1441) located in deep water nearer to the trench recovered basalts and related rocks; two sites (U1439 and U1442) located in shallower water further from the trench recovered boninites and related rocks. Drilling in both areas ended in dolerites inferred to be sheeted intrusive rocks. The basalts apparently erupted immediately after subduction initiation and have compositions similar to those of the most depleted basalts generated by rapid sea-floor spreading at mid-ocean ridges, with little or no slab input. Subsequent melting to generate boninites involved more depleted mantle and hotter and deeper subducted components as subduction progressed and volcanism migrated away from the trench. This volcanic sequence is akin to that recorded by many ophiolites, supporting a direct link between subduction initiation, fore-arc spreading, and ophiolite genesis.

Description: Highlights • Magmatic chlorine-excess is a highly sensitive tracer of hydrothermal contamination. • Red Sea magmas show Cl-excess more extreme than even fast spreading ridges. • High-Cl Red Sea environment produces high-Cl hydrothermally altered crust and magmatic Cl-excess. • (Ultra)slow-spreading ridge magmas can assimilate hydrothermally altered crust. • Magmatic Cl-excess can guide hydrothermal prospection in the Red Sea. Abstract Newly formed oceanic crust is initially cooled by circulating seawater, although where this occurs and over what regions fluids enter the crust is still unclear. Differences in the chlorine (Cl) concentrations between mid-ocean ridge basalt and seawater potentially make Cl a sensitive tracer for this hydrothermal circulation, allowing assimilation of hydrothermal fluids or hydrothermally altered crust by rising magma to be traced by measuring excess Cl in erupted lavas. Such excess Cl has been found in basalts from fast-spreading ridges (Cl concentrations up to 1200 ppm), but not so far on ultraslow- and slow-spreading ridges, where lower Cl values in the basalts (~ 50–200 ppm) make variations harder to measure. The Red Sea, with its relatively saline bottom water (40–42‰, cf. 35‰ salinity in open ocean water), the presence of axial brine pools (up to 270‰ salinity) and thick evaporite sequences flanking the young rift provides an ideal opportunity to study the incorporation of hydrothermal Cl at an ultraslow- to slow-spreading ridge (max. 1.6 cm/yr). Both absolute Cl concentrations (up to 1300 ppm) and ratios of Cl to elements of similar mantle incompatibility (e.g. K, Nb) are much higher in Red Sea basalts than for average ultraslow- and slow-spreading ridges. An origin of these Cl-excesses by seafloor weathering or syn-eruptive contamination can be excluded, as can mineral/melt fractionation during melting or crystallisation, based on trace element data. Instead, the incorporation of Cl at depth derived from hydrothermal circulation either by direct assimilation of hydrothermal fluids or through mixing of magma with partial melts of the hydrothermally altered crust is indicated. We see no influence of local spreading rate, the intensity of seafloor fracturing or the calculated depth of last crystal fractionation on Cl-excess. Seafloor areas with clear evidence of present or recent hydrothermal activity (brine pool temperatures above ambient, presence of hydrothermal sediments) always show Cl-excess in the local basalts and there is a positive correlation between Cl-excess and intensity of local volcanism (as determined by the percentage of local seafloor showing volcanic bathymetric forms). From this we conclude that Cl-excess in basalts is related to high crustal temperatures and hydrothermal circulation and so can be used to prospect for active or recently extinct hydrothermal systems. Samples recovered within 5 km of a seafloor evaporite outcrop show particularly high Cl-excesses, suggesting addition of Cl from the evaporites to the inflow fluids and that this may be the length scale over which hydrothermal recharge occurs.

Description: Melt inclusions in olivine are source of unique information about primitive mantle melts. Here we report results of an experimental study aimed at evaluating the ability of olivine to isolate chemically melt inclusions from the host magma after their entrapment. We demonstrate that nearly ‘dry’ melt inclusions from Galapagos Plateau basalt can gain up to 2.5 wt.% of water if they are placed for 2 days in a water-bearing melt at 200 MPa and 1140 °C. The major element composition of melt inclusions also changed significantly, as a result of a re-equilibration with the olivine host mineral, whereas no significant changes were detected for incompatible trace elements. Our results indicate that inclusions in olivine can rapidly and selectively exchange water with the matrix melt, probably, through combination of proton diffusion and molecular water transport along dislocations in olivine. The fast water transport explains element fractionation, which is not predictable from the theory of magmatic processes. An efficient re-equilibration of melt inclusions with matrix melt can explain the decoupling of water and incompatible trace elements (e.g., H2O vs. K2O) reported for suites of primitive inclusions from mid-ocean-ridge setting and island arcs. Rare cases of well preservation of initial water content in suites of co-genetic inclusions imply very short residence time (a few hours) of the olivine phenocrysts in magma with contrasting water content during fractionation and transport to the surface and rapid quenching upon eruption

Description: Highlights • New experiments with melt inclusions in olivine at 1200 °C and 300 MPa. • Coupled behavior H2O and SiO2 in inclusions during re-hydration and dehydration. • SiO2 mobility results from formation/destruction of metal vacant olivine. • SiO2-undersaturated arc melt inclusions may originate by dehydration. • New method to assess initial H2O in dehydrated inclusions. Abstract Primary subduction-related magmas build up modern continental crust and counterbalance massive recycling of crustal material into the deep mantle occurring at this tectonic setting. Melt inclusions in Mg-rich olivine are believed to be the best probes of primary subduction-related melts. However, unexpectedly, most of such inclusions are SiO2-undersaturated, in contrast to predominantly SiO2-saturated island-arc rocks. The origin of these melts has been explained by melting of amphibole-bearing pyroxenites in the lower crust or upper mantle. The current models fail, however, to explain the high abundance of SiO2-undersaturated melts as well as their compositional difference with host rocks for the major elements but not for incompatible trace elements. Here we report results from the investigation of rocks and melt inclusions in olivine from Klyuchevskoy volcano in Kamchatka. We show that experimental re-hydration of SiO2-undersaturated melt inclusions in olivine Fo85−90 at 300 MPa pressure and 1200 °C causes a concomitant enrichment of melt in H2O and SiO2 so that re-hydrated inclusions (4–5 wt% H2O) become as silica-saturated as primitive Klyuchevskoy rocks. An experimental dehydration of previously re-hydrated inclusions also resulted in coupled depletion of melt in H2O and SiO2. The estimated stoichiometry of SiO2 and H2O gain/loss is consistent with dissolution/crystallization of metal-defect olivine on inclusion walls. The migration mechanism of water is controlled by hydrogen diffusion in the octahedral metal (Mg, Fe) vacancies through olivine structure as confirmed by FTIR spectroscopy. We conclude that the previously reported SiO2-undersaturated composition of many melt inclusions from hypersthene-normative island-arc rocks can be explained by the coupled loss of up to several weight percent of H2O and SiO2 from the initially trapped primitive SiO2-saturated hydrous melts. Thus, SiO2-undersaturated melt inclusions may not be representative of primitive island-arc magmas. The discovery of the coupled SiO2 and H2O loss from inclusions allowed us to propose a method for reconstruction of the initial water content even for completely dehydrated inclusions. The results of this study may indicate that the majority of primitive island-arc inclusions have not preserved their initial H2O content, and that primary arc melts contain on average ≥4 wt% H2O. The higher H2O concentration in primary arc melts implies the existence of a ‘crustal filter’ controlling the water content, which can be preserved in melt inclusions, and also the lower mantle melting temperatures and higher output H2O fluxes in subduction zones than previously estimated based on direct determination of H2O in potentially dehydrated melt inclusions.

Description: Phase equilibria simulations were performed on naturally quenched basaltic glasses to determine crystallization conditions prior to eruption of magmas at the Mid-Atlantic Ridge (MAR) east of Ascension Island (7–11°S). The results indicate that mid-ocean ridge basalt (MORB) magmas beneath different segments of the MAR have crystallized over a wide range of pressures (100–900 MPa). However, each segment seems to have a specific crystallization history. Nearly isobaric crystallization conditions (100–300 MPa) were obtained for the geochemically enriched MORB magmas of the central segments, whereas normal (N)-MORB magmas of the bounding segments are characterized by polybaric crystallization conditions (200–900 MPa). In addition, our results demonstrate close to anhydrous crystallization conditions of N-MORBs, whereas geochemically enriched MORBs were successfully modeled in the presence of 0·4–1 wt% H2O in the parental melts. These estimates are in agreement with direct (Fourier transform IR) measurements of H2O abundances in basaltic glasses and melt inclusions for selected samples. Water contents determined in the parental melts are in the range 0·04–0·09 and 0·30–0·55 wt% H2O for depleted and enriched MORBs, respectively. Our results are in general agreement (within ±200 MPa) with previous approaches used to evaluate pressure estimates in MORB. However, the determination of pre-eruptive conditions of MORBs, including temperature and water content in addition to pressure, requires the improvement of magma crystallization models to simulate liquid lines of descent in the presence of small amounts of water.

Description: Here we present a confocal Fe K-edge μ-XANES method (where XANES stands for X-ray absorption near-edge spectroscopy) for the analysis of Fe oxidation state in heterogeneous and one-side-polished samples. The new technique allows for an analysis of small volumes with high spatial 3D resolution of 〈100 µm3. The probed volume is restricted to that just beneath the surface of the exposed object. This protocol avoids contamination of the signal by the host material and minimizes self-absorption effects. This technique has been tested on a set of experimental glasses with a wide range of Fe3+  ΣFe ratios. The method was applied to the analysis of natural melt inclusions trapped in forsteritic to fayalitic olivine crystals of the Hekla volcano, Iceland. Our measurements reveal changes in Fe3+  ΣFe from 0.17 in basaltic up to 0.45 in dacitic melts, whereas the magnetite–ilmenite equilibrium shows redox conditions with Fe3+  ΣFe ≤0.20 (close to FMQ, fayalite–magnetite–quartz redox equilibrium) along the entire range of Hekla melt compositions. This discrepancy indicates that the oxidized nature of glasses in the melt inclusions could be related to the post-entrapment process of diffusive hydrogen loss from inclusions and associated oxidation of Fe in the melt. The Fe3+  ΣFe ratio in silicic melts is particularly susceptible to this process due to their low FeO content, and it should be critically evaluated before petrological interpretation.