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.

Modelling the biogeochemical cycles of elements limiting primary production in the English channel .1. Role of thermohaline stratification

This paper presents the general framework of an ecological model of the English Channel. The model is a result of combining a physical sub-model with a biological one. in the physical submodel, the Channel is divided into 71 boxes and water fluxes between them are calculated automatically. A 2-layer, vertical thermohaline model was then linked with the horizontal circulation scheme. This physical sub-model exhibits thermal stratification in the western Channel during spring and summer and haline stratification in the Bay of Seine due to high flow rates from the river. The biological sub-model takes 2 elements, nitrogen and silicon, into account and divides phytoplankton into diatoms and dinoflagellates. Results from this ecological model emphasize the influence of stratification on chlorophyll a concentrations as well as on primary production. Stratified waters appear to be much less productive than well-mixed ones. Nevertheless, when simulated production values are compared with literature data, calculated production is shown to be underestimated. This could be attributed to a lack of refinement of the 2-layer box-model or processes omitted from the biological model, such as production by nanoplankton.