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.

Mixed Layer formation and restratification in presence of mesoscale and submesoscale turbulence

Recent realistic high resolution modeling studies show a net increase of submesoscale activity in fall and winter when the mixed layer depth is at its maximum. This submesoscale activity increase is associated with a reduced deepening of the mixed layer. Both phenomena can be related to the development of mixed layer instabilities, which convert available potential energy into submesoscale eddy kinetic energy and contribute to a fast restratification by slumping the horizontal density gradient in the mixed layer. In the present work, the mixed layer formation and restratification was studied by uniformly cooling a fully turbulent zonal jet in a periodic channel at different resolutions, from eddy resolving (10 km) to submesoscale permitting (2 km). The effect of the submesoscale activity, highlighted by these different horizontal resolutions, was quantified in terms of mixed layer depth, restratification rate and buoyancy fluxes. Contrary to many idealized studies focusing on the restratification phase only, this study addresses a continuous event of mixed layer formation followed by its complete restratification. The robustness of the present results was established by ensemble simulations. The results show that, at higher resolution, when submesoscale starts to be resolved, the mixed layer formed during the surface cooling is significantly shallower and the total restratification almost three times faster. Such differences between coarse and fine resolution models are consistent with the submesoscale upward buoyancy flux, which balances the convection during the formation phase and accelerates the restratification once the surface cooling is stopped. This submesoscale buoyancy flux is active even below the mixed layer. Our simulations show that mesoscale dynamics also cause restratification, but on longer time scales. Finally, the spatial distribution of the mixed layer depth is highly heterogeneous in the presence of submesoscale activity, prompting the question of whether it is possible to parameterize submesoscale effects and their effects on the marine biology as a function of a spatially-averaged mixed layer depth.