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.

Statistical Analysis of Sea Surface Temperature and Chlorophyll-a Concentration Patterns in the Gulf of Tadjourah (Djibouti)

The sea surface temperature (SST) and chlorophyll-a concentration (CHL-a) were analysed in the Gulf of Tadjourah from two set of 8-day composite satellite data, respectively from 2008 to 2012 and from 2005 to 2011. A singular spectrum analysis (SSA) shows that the annual cycle of SST is strong (74.3% of variance) and consists of warming (April-October) and cooling (November-March) of about 2.5C than the long-term average. The semi-annual cycle captures only 14.6% of temperature variance and emphasises the drop of SST during July-August. Similarly, the annual cycle of CHL-a (29.7% of variance) depicts high CHL-a from June to October and low concentration from November to May. In addition, the first spatial empirical orthogonal function (EOF) of SST (93% of variance) shows that the seasonal warming/cooling is in phase across the whole study area but the southeastern part always remaining warmer or cooler. In contrast to the SST, the first EOF of CHL-a (54.1% of variance) indicates the continental shelf in phase opposition with the offshore area in winter during which the CHL-a remains sequestrated in the coastal area particularly in the south-east and in the Ghoubet Al-Kharab Bay. Inversely during summer, higher CHL-a quantities appear in the offshore waters. In order to investigate processes generating these patterns, a multichannel spectrum analysis was applied to a set of oceanic (SST, CHL-a) and atmospheric parameters (wind speed, air temperature and air specific humidity). This analysis shows that the SST is well correlated to the atmospheric parameters at an annual scale. The windowed cross correlation indicates that this correlation is significant only from October to May. During this period, the warming was related to the solar heating of the surface water when the wind is low (April-May and October) while the cooling (November-March) was linked to the strong and cold North-East winds and to convective mixing. The summer drop in SST followed by a peak of CHL-a, seems strongly correlated to the upwelling. The second EOF modes of SST and CHL-a explain respectively 1.3% and 5% of the variance and show an east-west gradient during winter that is reversed during summer. This work showed that the seasonal signals have a wide spatial influence and dominate the variability of the SST and CHL-a while the east-west gradient are specific for the Gulf of Tadjourah and seem induced by the local wind modulated by the topography.