Methane-derived CO2 in pore fluids expelled from the Oregon subduction zone

Pore fluids extracted from near-surface sediments of the deformation front along the Oregon subduction zone have, in general, the dissolved nutrient pattern characteristic of bacterial sulfate reduction. However, in certain locations there are peculiar ammonium distributions and anomalously 13C-depleted dissolved ΣCO2. These carbon isotope and nutrient patterns are attributed to the concurrent microbially-mediated oxidation of sedimentary organic matter (POC) and methane (CH4) originating from depth. In contrast to the oxidation of sedimentary organic matter in the sulfate zone, utilization of methane as the carbon source by sulfate-reducing bacteria would generate only half as much total carbon dioxide for each mole of sulfate consumed and would not generate any dissolved ammonium. The isotopically light ΣCO2 released from methane oxidation depletes the total metabolic carbon dioxide pool. Therefore, NH4+, ΣCO2 and δ13C of interstitial carbon dioxide in these pore fluids distintcly reflect the combined contributions of each of the two carbon substrates undergoing mineralization; i.e. methane and sedimentary organic matter. By appropriately partitioning the nutrient and substrate relationships, we calculate that in the area of the marginal ridge of the Oregon subduction zone as much as 30% of the ΣCO2 in pore fluids may result from methane oxidation. The calculation also predicts that the carbon isotope signature of the carbon dioxide derived from methane is between −35‰ and −63‰ PDB. Such an isotopically light gas generated from within the accretionary complex could be the residue of a biogenic methane pool. Fluid advection is required to carry such methane from depth to the present near-surface sediments. This mechanism is consistent with large-scale, tectonically-induced fluid transport envisioned for accreted sediments of the world's convergent plate boundaries

Characterization of Sorbed Volatile Hydrocarbons from the Peru Margin, Leg 112, Sites 679, 680/681, 682, 684, and 686/687

Bacterial and thermogenic hydrocarbons are present in the sorbed-gas fraction of Peru margin sediments. At Ocean Drilling Program (ODP) Sites 681, 682, 684, and 686, bacterial gases are restricted to the early diagenetic zones, where dissolved sulfate has been exhausted and methanogenesis occurs. Methane migrating into the sulfate zone at Sites 681, 684, 686, and possibly 682, has been consumed anaerobically by methanotrophs, maintaining the low concentrations and causing an isotope shift in S13CCH4 to more positive values. Significant amounts of C2+ hydrocarbons occur at the shelf Sites 680/681, 684, and 686/687, where these hydrocarbons may be associated with hypersaline fluids. There is evidence at Site 679 that sorbed C2+ hydrocarbons may also have been transported by hypersaline fluids. This characteristic C2+ hydrocarbon signature in the sorbed-gas fractions of sediments at Site 679 is not reflected in data obtained using the conventional "free-," "canned-," or "headspace-gas1' procedures. The molecular and isotope compositions of the sorbed-gas fraction indicate that this gas may have a thermogenic source and may have spilled over with the hypersaline fluids from the Salaverry Basin into the Lima Basin. These traces of thermogenic hydrocarbon gases are over-mature (about 1.5% Ro) and are discordant with the less-mature sediments in which they are found. This observation supports the migration of these hydrocarbons, possibly from continental sources. Sorbed-gas analyses may provide important geochemical information, in addition to that of the free-gases. Sorbed-gases are less sensitive to activities in the interstitial fluids, such as methanogenesis and methanotrophy, and may faithfully record the migration of hydrocarbons associated with hypersaline fluids

Calculation of coercivity of magnetic nanostructures at finite temperatures

We report a finite temperature micromagnetic method (FTM) that allows for the calculation of the coercive field of arbitrary shaped magnetic nanostructures at time scales of nanoseconds to years. Instead of directly solving the Landau-Lifshitz-Gilbert equation, the coercive field is obtained without any free parameter by solving a non linear equation, which arises from the transition state theory. The method is applicable to magnetic structures where coercivity is determined by one thermally activated reversal or nucleation process. The method shows excellent agreement with experimentally obtained coercive fields of magnetic nanostructures and provides a deeper understanding of the mechanism of coercivity.Comment: submitted to Phys. Rev.

A [4Fe-4S]-Fe(CO)(CN)-L-cysteine intermediate is the first organometallic precursor in [FeFe] hydrogenase H-cluster bioassembly.

Biosynthesis of the [FeFe] hydrogenase active site (the 'H-cluster') requires the interplay of multiple proteins and small molecules. Among them, the radical S-adenosylmethionine enzyme HydG, a tyrosine lyase, has been proposed to generate a complex that contains an Fe(CO)2(CN) moiety that is eventually incorporated into the H-cluster. Here we describe the characterization of an intermediate in the HydG reaction: a [4Fe-4S][(Cys)Fe(CO)(CN)] species, 'Complex A', in which a CO, a CN- and a cysteine (Cys) molecule bind to the unique 'dangler' Fe site of the auxiliary [5Fe-4S] cluster of HydG. The identification of this intermediate-the first organometallic precursor to the H-cluster-validates the previously hypothesized HydG reaction cycle and provides a basis for elucidating the biosynthetic origin of other moieties of the H-cluster

Evaluating Molecular Cobalt Complexes for the Conversion of N_2 to NH_3

We report a molecular Co−N_2 complex that generates a greater-than-stoichiometric yield of NH_3 (>200% NH_3 per Co−N_2 precursor) via the direct reduction of N_2 with protons and electrons. A comparison of the featured Co−N_2 complex with structurally related Co−N_2 and Fe−N_2 species shows how remarkably sensitive the N_2 reduction performance of potential precatalysts is. As discussed, structural and electronic effects are relevant to Co/Fe−N_2 conversion activity, including π basicity, charge state, and geometric flexibility