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    Deep biosphere

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    The geochemistry and geomicrobiology of relict hydrothermal sulphide deposits

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    The diagenetic re-mineralisation of seafloor-sulphide deposits and the role of microbes in the metal-exchange processes were investigated in metalliferous sediments from the Alvin relict hydrothermal zone in the TAG area at 26º8'N (Mid-Atlantic Ridge). The solid-phase and concomitant pore water concentrations of AI, Si,Ca, Ctot, Corg, S, Fe, Mn, Cu, Zn, P, V, Co, U, Mo, Au, Ag and REEs were measured in a 230 cm long gravity core from the southern periphery of the relict vent field. These measurements were complemented by detailed analysis of bacterial abundance and specific activity. The altered sulphidic sediments are capped with a ~30cm thick layer of carbonate-rich (~60% CaCO3), Fe-stained sediments. Two distinct sulphide layers, interbedded with Fe-oxysilicates, and overlain by a thin layerof Fe/Mn oxyhydroxides, were found in this core. The dominant mineral-phase in both sulphide layers, which originate from mass-wasting of mound sediments, is pyrite with some goethite. Reaction of the exposed metal-sulphides in the upper sulphide layer with seawater has produced a thin layer of secondary atacamite, which is enriched in Au. Primary sphalerite is dissolved in the upper sulphide layer and re-precipitation as secondary sphalerite directly above and below. U continues to be scavenged from the porewater, producing marked enrichments on oxidised sulphide rims. The re-mineralisation processes identified in this core are in close analogy to the large-scale zone-refining that has been described for the active TAG mound and ancient ore-deposits. REE/Fe ratios clearly distinguish between plume derived sediments in the carbonate cap and slumped material from the hydrothermal mound. The REE signature of bulk sediments and clay phases imply multiple stages of alteration by diffuse fluids in the upper sulphide layer and intermediate layer, whereas the lower sulphide layer is not affected. Alteration by reactive low-temperature hydrothermal fluids is also inferred to be responsible for the observed diagenetic overprinting of trace-metal distributions in the upper sulphide layer. The intermediate layer is rich in nontronite, which has been precipitated in situ from diffuse fluids. The presence of Mn- and Fe-reducing bacteria coincide with elevated pore water concentrations of Mn and Fe, indicating direct involvement of bacteria in the cycling of these metals. Total counts of viable cells and general activity measurements show that although bacterial populations are relatively small, they are healthy and well adapted to this potentially toxic environment. The existence of active microbial communities in metalliferous sediments may therefore provide a continuum of bacterial populations between high and low temperature hydrothermal systems, thus representing an important transitional stage in the hydrothermal ecosystem. Microbial reduction and oxidation of S was observed throughout the core, indicating that microorganisms are particularly active in terms of S-cycling. For deep-sea sediments extremely high sulphate reduction rates (67 nmol/cm3/d) were measured in the iron-stained carbonate cap. In the absence of significant organic carbon (~0.2 %) this strongly suggests the synthesis of alternative electron-donors by chemolithotrophic bacteria to support the observed high rates of heterothrophic activity in these sediments

    Pore-fluid Fe isotopes reflect the extent of benthic Fe redox recycling: evidence from continental shelf and deep-sea sediments

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    Pore-fluid Fe isotopes may be a unique tracer of sediment respiration by dissimilatory Fe reducing bacteria, but to date, pore-fluid Fe isotope measurements have been restricted to continental shelf settings. Here, we present δ56Fe values of pore fluids from two distinct sedimentary settings: (1) a riverine-dominated site on the northern California margin (Eel River shelf; 120 m water depth) and (2) biogenic opal-rich volcaniclastic deep-sea sediments from the Southern Ocean (north and south of the Crozet Plateau; 3000–4000 m water depth). The Fe isotope compositions of Crozet region pore fluids are significantly less fractionated (δ56Fe = +0.12‰ to –0.01‰) than the Eel River shelf (δ56Fe = –0.65‰ to –3.40‰) and previous studies of pore-fluid Fe isotopes, relative to average igneous rocks. Our data represent the first measurements of Fe isotope compositions in pore fluids from deep-sea sediments. A comparison of pore-fluid δ56Fe with the relative abundance of highly labile Fe in the reactive sedimentary Fe pool demonstrates that the composition of Fe isotopes in the pore fluids reflects the different extent of sedimentary Fe redox recycling between these sites

    The role of prokaryotes in subsurface weathering of hydrothermal sediments: a combined geochemical and microbiological investigation

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    A detailed geochemical and microbiological study of a ~2 m sediment core from the inactive Alvin mounds within the TAG hydrothermal field was conducted to examine, for the first time, the role of prokaryotes in subsurface weathering of hydrothermal sediments. Results show that there has been substantial post depositional remobilisation of metal species and diagenetic overprinting of the original high-temperature hydrothermal minerals, and aspects have involved prokaryotic processes. Prokaryotic enumeration demonstrates the presence of a population smaller than the average for deep sea sediments, probably due to the low organic carbon content, but not inhibited by (and hence adapted to) the metal rich environment. There was a small but significant increase in population size associated with the active redox boundary in an upper metal sulphide layer (50-70 cm) around which active metal remobilisation was concentrated (Cu, Au, Cd, Ag, U, Zn and Zn). Hence, subsurface prokaryotes were potentially obtaining energy from metal metabolism in this near surface zone. Close association of numbers of culturable Mn and Fe reducing prokaryotes with subsurface Fe2+ and Mn2+ pore water profiles suggested active prokaryotic metal reduction at depth in core CD102/43 (to ~175 cm). In addition, a prokaryotic mechanism, which is associated with bacterial sulphate reduction, is invoked to explain the U enrichment on pyrite surfaces and Zn and Pb remobilisation in the upper sediment. Although prokaryotic populations are present throughout this metalliferous sediment, thermodynamic calculations indicated that the inferred low pH of pore waters and the suboxic/anoxic conditions limits the potential energy available from Fe(II) oxidation, which may restrict prokaryotic chemolithotrophic biomass. This suggests that intense prokaryotic Fe oxidation and weathering of seafloor massive sulphide deposits may be restricted to the upper portion of the deposit that is influenced by near neutral pH and oxic seawater unless there is significant subsurface fluid flow

    The role of prokaryotes in supergene alteration of submarine hydrothermal sulfides

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    We combine mineralogical, stable isotope and organic biomarker data to understand the role of prokaryote activity in supergene reactions within submarine hydrothermal sulfidic sediments. Data are presented for two adjacent cores from the periphery of the inactive Alvin hydrothermal mound. The limit of oxygenated seawater penetration into the sulfidic sediments is expressed as a sharp peak in solid phase Cu (atacamite and secondary Cu sulfides) associated with supergene alteration of the sulfide pile. Total prokaryote numbers are low throughout the upper few metres of sediment relative to published data for deep-sea sites. However, there is a statistically significant enrichment of prokaryote numbers at the redox front that coincides with abundant Fe oxide filaments and a unique distribution of microbial biomarkers. The dominance of quaternary-branched alkanes in the oxidized transition zone immediately above the redox front (and their absence below) suggests a significant role of the source organisms in iron or sulfide oxidation under the more circumneutral conditions associated with the redox transition zone. The morphology of the Fe oxide filaments preserved within late stage silica and gypsum mineralization is consistent with a biogenic origin of the filaments. Gypsum sulfur isotopes are in equilibrium with fluids that are derived from quantitative sulfide oxidation and gypsum nucleation is inferred to be biologically induced. These new data suggest that supergene alteration of sulfidic sediments generates sharp redox and pH gradients that stimulate prokaryotic activity, in particular iron and sulfide oxidisers, which in turn govern the distribution of secondary mineral phases and the abundance of redox sensitive trace metals

    The effect of plume processes on the Fe-isotope composition of hydrothermally derived Fe in the deep ocean as inferred from the Rainbow vent site, Mid-Atlantic Ridge, 36,14'N

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    The Rainbow hydrothermal vent site, which is the largest known point source for dissolved Fe delivered to the deep North Atlantic ocean, has remained invariant in its Fe isotope composition over at least the past 16,000 years, based on analysis of metalliferous sediments beneath the plume. Because of the conservative behavior of Fe in the Rainbow plume, 56Fe values of particles in the neutrally buoyant plume (?0.18±0.05‰) and underlying sediments (?0.19±0.05‰) are indistinguishable from the 56Fe values of the high-temperature fluid sources (?0.23±0.04‰). Particles from the near-vent, buoyant stage of the plume, however, have higher 56Fe values (+0.15‰ to +1.20‰) relative to the original vent fluid, consistent with fractionation during oxidation of Fe(II)aq to Fe(III)aq. Isotope compositions become invariant in the plume once all Fe(II)aq is fully oxidized, preserving the original composition of the vent fluid. The constant Fe isotope compositions of the vent fluids over time implies that changes in seawater Fe isotope composition of the North Atlantic ocean, as they are recorded in Fe–Mn crusts, requires changes in the relative fluxes of Fe to the ocean
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