Description: Low temperature alteration of oceanic basement rocks is characterized by net gain of sulfur, which commonly yields low d34S values, suggesting involvement of microbial sulfate reduction. In order to test whether secondary sulfide minerals are consistent with a biogenic source, we apply high precision multiple sulfur isotope analysis to bulk rock sulfide and pyrite isolates from two contrasting types of altered oceanic basement rocks, namely serpentinized peridotites and altered basalts. Samples from two peridotite sites (Iberian Margin and Hess Deep) and from a basalt site on the eastern flank of the Juan de Fuca Ridge yield overlapping d34S values ranging from 0 per mil to -44 per mil. In contrast, sulfides in the basalt site are characterized by relatively low D33S values ranging from -0.06 per mil to 0.04 per mil, compared to those from peridotite sites (0.00 per mil to 0.16 per mil). The observed D33S signal is significant considering the analytical precision of 0.014 per mil (2 sigma). We present a batch reaction model that uses observed d34S and D33S relationships to quantify the effect of closed system processes and constrain the isotope enrichment factor intrinsic to sulfate reduction. The estimated enrichment factors as large as 61 per mil and 53 per mil, for peridotite and basalt sites respectively, suggest the involvement of microbial sulfate reduction. The relatively high D33S values in the peridotite sites are due to sulfate reduction in a closed system environment, whereas negative D33S values in the basalt site reflect open system sulfate reduction. A larger extent of sulfate reduction during alteration of peridotite to serpentinite is consistent with its higher H2 production capacity compared to basalt alteration, and further supports in-situ microbial sulfate reduction coupled with H2 production during serpentinization reactions.

Description: Author Posting. © American Geophysical Union, 2008. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Journal of Geophysical Research 113 (2008): B08S07, doi:10.1029/2007JB005451.

Description: We present major, volatile, and trace elements for quenched glasses from the Fonualei Spreading Center, a nascent spreading system situated very close to the Tofua Volcanic Arc (20 km at the closest), in the northeast Lau Basin. The glasses are basalts and basaltic andesites and are inferred to have originated from a relatively hot and depleted mantle wedge. The Fonualei Spreading Center shows island arc basalt (IAB) affinities, indistinguishable from the Tofua Arc. Within the Fonualei Spreading Center no geochemical trends can be seen with depth to the slab and/or distance to the arc, despite a difference in depth to the slab of 〉50 km. Therefore we infer that all the subduction-related magmatism is captured by the back arc as the adjacent arc is shut off. There is a sharp contrast between the main spreading area of the Fonualei Spreading Center (FSC) and its northernmost termination, the Mangatolu Triple Junction (MTJ). The MTJ samples are characteristic back-arc basin basalts (BABB). We propose that the MTJ and FSC have different mantle sources, reflecting different mantle origins and/or different melting processes. We also document a decrease in mantle depletion from the south of the FSC to the MTJ, which is the opposite to what has been documented for the rest of the Lau Basin where depletion generally increases from south to north. We attribute this reverse trend to the influx of less depleted mantle through the tear between the Australian and the Pacific plates, at the northern boundary of the Lau Basin.

Description: NSK acknowledges the support of an A.E. Ringwood Scholarship from the RSES.

Description: Author Posting. © Elsevier B.V., 2009. This is the author's version of the work. It is posted here by permission of Elsevier B.V. for personal use, not for redistribution. The definitive version was published in Geochimica et Cosmochimica Acta 73 (2009): 6847-6867, doi:10.1016/j.gca.2009.08.013.

Description: S K edge XANES and Mn, W and Ni XANES and EXAFS spectra of silicate glasses synthesised at 1400° C and 1 bar with compositions in the CaO-MgO-Al2O3-SiO2-S plus MnO, NiO, or WO3 systems were used to investigate sulphur speciation in silicate glasses. S K-edge spectra comprised a composite peak with an edge between 2470 and 2471.4 eV, which was attributed to S2-, and a peak of variable height with an edge at 2480.2 to 2480.8 eV, which is consistent with the presence of S6+. The latter peak was attributed to sample oxidation during sample storage. W-rich samples produced an additional lower energy peak at 2469.8 eV that is tentatively attributed to the existence of S 3p orbitals hybridised with the W 5d states. Deconvolution of the composite peak reveals that the composite peak for Mn-bearing samples fits well to a model that combines three Lorentzians at 2473.1, 2474.9 and 2476.2 eV with an arctan edge step. The composite peak for W-bearing samples fits well to the same combination plus an additional Lorentzian at 2469.8 eV. The ratio of the proportions of the signal accounted for by peaks at 2473.1eV and 2476.2eV correlates with Mn:Ca molar ratios, but not with W:Ca ratios. Spectra from Ni-bearing samples were qualitatively similar but S levels were too low to allow robust quantification of peak components. Some part of the signal accounted for by the 2473.1 eV peak was therefore taken to record the formation of Mn-S melt species, while the 2469.8 peak is interpreted to record the formation of W-S melt species. The 2474.9 eV and 2476.2 eV peaks were taken to be dominated by Ca-S and Mg-S interactions. However, a 1:1 relationship between peak components and specific energy transitions is not proposed. This interpretation is consistent with known features of the lower parts of the conduction band in monosulphide minerals and indicates a similarity between sulphur species in the melts and the monosulphides. S XANES spectra cannot be reproduced by a combination of the spectra of the component element monosulphides. Mn-, W- and Ni- XANES and EXAFS for synthetic glasses without sulphide exsolution did not show any sensitivity to the presence of sulphur, which is unsurprising as S:O ratios were sufficiently low that metals would be mostly co-ordinated by O. Mn EXAFS spectra were consistent with divalent Mn in 5 co-ordinated Mn-O melt species. W spectra were consistent with tetrahedrally co-ordinated hexavalent W, most likely in scheelite-like melt species, and Ni spectra were consistent with [4] co-ordinated divalent Ni. These results indicate lower coordinations for bothWand Ni than those inferred by some previous workers. Cation coordination may reflect the proportion of non-bridging oxygens, which is lower in the Ca-rich and Al-poor samples investigated here than for previous studies.

Description: This work was performed with 814 support from the Australian Synchrotron Research Program (ASRP), which is funded by the 815 Commonwealth of Australia under the Major National Research Facilities Program.

Description: This study aims to explore the extent and controls of silicon isotope fractionation in hot spring systems of the Geysir geothermal area (Iceland), a setting where sinter deposits are actively formed. The δ30Si values of dissolved silica measured in the spring water and sampling sites along outflowing streams, covering a temperature range between 20 and 100 °C, were relatively constant around +0.2‰, whereas the δ30Si signatures of associated opaline sinters from the streambeds were between −0.1‰ and −4.0‰, becoming progressively more negative in the downstream parts of the aprons. Here, the deposited sinters represent some of the most 30Si depleted abiotically produced terrestrial materials documented to date. Compared to the data reported for Icelandic basalts, considered to be the source of the silicon, the δ30Si values of the fluids and sinter deposits are higher and lower, respectively. The resulting values for apparent solid–water isotope fractionation (Δ30Sisolid–water) decreased with decreasing temperature from ca. −0.7‰ at ∼80 °C to −3.7‰ at ∼20 °C, locally down to −4.4‰. This temperature relationship was reproducible in each of the investigated hot spring systems and is qualitatively consistent with recent findings in laboratory experiments on kinetic fractionation for a flowing fluid. However, the apparent fractionation magnitudes observed in the field are ca. −2‰ more negative and thus significantly larger. We infer that solid–water silicon isotope fractionation during deposition of amorphous silica from a flowing fluid correlates inversely with temperature, but is essentially a function of the precipitation rate, such that the fractionation factor decreases with increasing rate. As an important corollary, the effective fractionation behavior during precipitation of silica from saturated solutions is a system-dependent feature, which should be taken into account when using silicon isotopes for paleo-environmental reconstructions.

Description: Subduction of oceanic crust and the formation of volcanic arcs above the subduction zone are important components in Earth’s geological and geochemical cycles. Subduction consumes and recycles material from the oceanic plates, releasing fluids and gases that enhance magmatic activity, feed hydrothermal systems, generate ore deposits and nurture chemosynthetic biological communities. Among the first lavas to erupt at the surface from a nascent subduction zone are a type classified as boninites. These lavas contain information about the early stages of subduction, yet because most subduction systems on Earth are old and well-established, boninite lavas have previously only been observed in the ancient geological record. Here we observe and sample an active boninite eruption occurring at 1,200 m depth at the West Mata submarine volcano in the northeast Lau Basin, southwest Pacific Ocean. We find that large volumes of H2O, CO2 and sulphur are emitted, which we suggest are derived from the subducting slab. These volatiles drive explosive eruptions that fragment rocks and generate abundant incandescent magma-skinned bubbles and pillow lavas. The eruption has been ongoing for at least 2.5 years and we conclude that this boninite eruption is a multi-year, low-mass-transfer-rate eruption. Thus the Lau Basin may provide an important site for the long-term study of submarine volcanic eruptions related to the early stages of subduction.