Iron Transformation Pathways and Redox Micro-Environments in Seafloor Sulfide-Mineral Deposits: Spatially Resolved Fe XAS and delta Fe-57/54 Observations

Hydrothermal sulfide chimneys located along the global system of oceanic spreading centers are habitats for microbial life during active venting. Hydrothermally extinct, or inactive, sulfide deposits also host microbial communities at globally distributed sites. The main goal of this study is to describe Fe transformation pathways, through precipitation and oxidation-reduction (redox) reactions, and examine transformation products for signatures of biological activity using Fe mineralogy and stable isotope approaches. The study includes active and inactive sulfides from the East Pacific Rise 9 degrees 50'N vent field. First, the mineralogy of Fe(III)-bearing precipitates is investigated using microprobe X-ray absorption spectroscopy (RXAS) and X-ray diffraction (mu XRD). Second, laser-ablation (LA) and micro-drilling (MD) are used to obtain spatially-resolved Fe stable isotope analysis by multicollector-inductively coupled plasma-mass spectrometry (MC-ICP-MS). Eight Fe -bearing minerals representing three mineralogical classes are present in the samples: oxyhydroxides, secondary phyllosilicates, and sulfides. For Fe oxyhydroxides within chimney walls and layers of Si-rich material, enrichments in both heavy and light Fe isotopes relative to pyrite are observed, yielding a range of delta Fe-57 values up to 6 parts per thousand. Overall, several pathways for Fe transformation are observed. Pathway 1 is characterized by precipitation of primary sulfide minerals from Fe(II)aq-rich fluids in zones of mixing between vent fluids and seawater. Pathway 2 is also consistent with zones of mixing but involves precipitation of sulfide minerals from Fe(II)aq generated by Fe(III) reduction. Pathway 3 is direct oxidation of Fe(II) aq from hydrothermal fluids to form Fe(III) precipitates. Finally, Pathway 4 involves oxidative alteration of pre-existing sulfide minerals to form Fe(III). The Fe mineralogy and isotope data do not support or refute a unique biological role in sulfide alteration. The findings reveal a dynamic range of Fe transformation pathways consistent with a continuum of micro-environments having variable redox conditions. These micro-environments likely support redox cycling of Fe and S and are consistent with culture-dependent and -independent assessments of microbial physiology and genetic diversity of hydrothermal sulfide deposits.

VESPA cruise report. Volcanic Evolution of South Pacific Arcs. n/o L’Atalante, Nouméa – Nouméa, 22 May - 17 June 2015

VESPA was a successful 25 day research cruise on R/V l'Atalante that took place in May and June 2015. The main aim was to acquire new rock samples from extinct volcanoes on the Norfolk, Loyalty and Three Kings ridges, which connect New Caledonia and New Zealand. This was in order to test various hypotheses of Late Cretaceous-Miocene SW Pacific tectonic development relating to (i) nature and duration of magmatism on the ridges; (ii) timing of subduction initiation east of northern Zealandia; (iii) postulated subduction polarity changes. A total of 3400 km of 'sismique rapide' shallow reflection seismic data were acquired and processed onboard. The seismic lines provided a very useful structural-stratigraphic framework for the rock dredging. Combined with multibeam bathymetry data they allowed intelligent targeting of acoustic basement (lavas) and specific seismic reflectors (sedimentary strata) on rocky slopes and fault scarps. Different stratigraphic levels of the Loyalty and Three Kings Ridge volcanic piles were sampled by dredging at different water depths on the Cook Fracture Zone and Cagou Trough fault scarps. By the end of the cruise, 43 dredges had been attempted and 36 of them yielded igneous or sedimentary rocks potentially useful to the VESPA project. Onboard use of a portable X-ray fluorescence unit confirmed the presence of intraplate (but no arc) volcanoes on the Norfolk Ridge and presence of arc, intraplate and shoshonitic volcanoes on the Loyalty and Three Kings Ridges. A total of 770 kg of rock was retained for post-cruise analysis in New Caledonia, France and New Zealand. Future work will include micropaleontological dating of sedimentary rocks, U-Pb and Ar-Ar isotopic dating of igneous rocks, and whole rock geochemical and tracer isotope analyses. We are optimistic that many of the initial research hypotheses will be able to be tested.