Comparison of Rhizon Sampling and Whole Round Squeezing for Marine Sediment Porewater

The collection and chemical analysis of sedimentary porewater is central to many marine studies. Porewater alkalinity,dissolved inorganic carbon (DIC), sulfate, nitrate, and other dissolved ions are used to identify and determine rates of geochemical reactions and microbial respiration pathways, such as sulfate reduction and denitrification (Froelich et al., 1979; Berner, 1980; Gieskes et al., 1986; D’Hondt et al., 2004; Schulz, 2006; Martin and Sayles, 2007). Ammonium is critical for understanding microbial respiration and the nitrogen cycle (Blackburn, 1988). Chloride is used to reconstruct ocean salinity variations, constrain flow rates, and estimate gas hydrate concentrations (Paull et al., 1996; Adkins et al., 2002; Spivack et al., 2002). Each of these studies requires the recovery of porewater that is not compromised by sampling artifacts

Sulfate-reducing ammonium oxidation: A thermodynamically feasible metabolic pathway in subseafloor sediment

Biogeochemical fluxes and Gibbs energies in sedimentary porewaters point to the existence of sulfate-reducing ammonium oxidation. This process has not been previously inferred in natural environments. Porewater profiles in the Bay of Bengal (Indian Ocean) demonstrate that significant ammonium disappears at the ammonium-sulfate interface. Loss of ammonium at this horizon greatly exceeds possible nitrogen demand by biomass production. In situ Gibbs energies of reaction (ΔG) in Bay of Bengal and Greenwich Bay (Rhode Island) sediments indicate that sulfate-reducing ammonium oxidation is energy yielding. Relatively small and constant but consistently negative ΔG values for this reaction in both locations match the thermodynamic signature of anaerobic microbial respiration. The ΔG results and the substantial ammonium loss suggest that sulfate-reducing ammonium oxidation occurs in Bay of Bengal sediment. The Greenwich Bay ΔG results suggest that the process may also occur in anoxic sediment where the ammonium concentration profile shows no net loss of ammonium. © 2009 Geological Society of America

(Table S1) Stable carbon isotope composition of dissolved inorganic carbon and Ion activity product of dolomite of IODP Exp 323 sites

We studied microbially mediated diagenetic processes driven by carbon mineralization in subseafloor sediment of the northeastern Bering Sea Slope to a depth of 745 meters below seafloor (mbsf). Sites U1343, U1344 and U1345 were drilled during Integrated Ocean Drilling Program (IODP) Expedition 323 at water depths of 1008 to 3172 m. They are situated in the high productivity “Green Belt” region, with organic carbon burial rates typical of the high-productivity upwelling domains on western continental margins. The three sites show strong geochemical similarities. The downward sequence of microbially mediated processes in the sediment encompasses (1) organoclastic sulfate reduction, (2) anaerobic oxidation of methane (AOM) coupled to sulfate reduction, and (3) methanogenesis. The sediment contains two distinct zones of diagenetic carbonate formation, located at the sulfate–methane transition zone (SMTZ) and between 300 and 400 mbsf. The SMTZ at the three sites is located between 6 and 9 mbsf. The upward methane fluxes into the SMTZ are similar to fluxes in SMTZs underlying high-productivity surface waters off Chile and Namibia. Our Bering Sea results show that intense organic carbon mineralization drives high ammonium and dissolved inorganic carbon (DIC) production rates (> 4.2 mmol/m**3/y1) in the uppermost 10 mbsf and strongly imprints on the stable carbon isotope composition of DIC, driving it to a minimum value of -27 per mil (VPDB) at the SMTZ. Pore-water calcium and magnesium profiles demonstrate formation of diagenetic Mg-rich calcite in the SMTZ. Below the SMTZ, methanogenesis results in 13C-enrichment of pore-water DIC, with a maximum value of +11.9 per mil. The imprint of methanogenesis on the DIC carbon isotope composition is evident down to a depth of 150 mbsf. Below this depth, slow or absent microbially mediated carbon mineralization leaves DIC isotope composition unaffected. Ongoing carbonate formation between 300 and 400 mbsf strongly influences pore-water DIC and magnesium concentration profiles. The linked succession of organic carbon mineralization and carbonate dissolution and precipitation patterns that we observe in the Bering Sea Slope sediment may be representative of passive continental margin settings in high-productivity areas of the world's ocean

Coupled organic and inorganic carbon cycling in the deep subseafloor sediment of the northeastern Bering Sea Slope (IODP Exp. 323)

We studied microbially mediated diagenetic processes driven by carbon mineralization in subseafloor sediment of the northeastern Bering Sea Slope to a depth of 745 meters below seafloor (mbsf). Sites U1343, U1344 and U1345 were drilled during Integrated Ocean Drilling Program (IODP) Expedition 323 at water depths of 1008 to 3172 m. They are situated in the high productivity "Green Belt" region, with organic carbon burial rates typical of the high-productivity upwelling domains on western continental margins. The three sites show strong geochemical similarities. The downward sequence of microbially mediated processes in the sediment encompasses (1) organoclastic sulfate reduction, (2) anaerobic oxidation of methane (AOM) coupled to sulfate reduction, and (3) methanogenesis. The sediment contains two distinct zones of diagenetic carbonate formation, located at the sulfate–methane transition zone (SMTZ) and between 300 and 400 mbsf. The SMTZ at the three sites is located between 6 and 9 mbsf. The upward methane fluxes into the SMTZ are similar to fluxes in SMTZs underlying high-productivity surface waters off Chile and Namibia. Our Bering Sea results show that intense organic carbon mineralization drives high ammonium and dissolved inorganic carbon (DIC) production rates (> 4.2 mmol m⁻³3 y⁻¹) in the uppermost 10 mbsf and strongly imprints on the stable carbon isotope composition of DIC, driving it to a minimum value of − 27‰ (VPDB) at the SMTZ. Pore-water calcium and magnesium profiles demonstrate formation of diagenetic Mg-rich calcite in the SMTZ. Below the SMTZ, methanogenesis results in ¹³C-enrichment of pore-water DIC, with a maximum value of + 11.9‰. The imprint of methanogenesis on the DIC carbon isotope composition is evident down to a depth of 150 mbsf. Below this depth, slow or absent microbially mediated carbon mineralization leaves DIC isotope composition unaffected. Ongoing carbonate formation between 300 and 400 mbsf strongly influences pore-water DIC and magnesium concentration profiles. The linked succession of organic carbon mineralization and carbonate dissolution and precipitation patterns that we observe in the Bering Sea Slope sediment may be representative of passive continental margin settings in high-productivity areas of the world's ocean.11 page(s