Analysis of methane and sulfate flux in methane-charged sediments from the Mississippi Canyon, Gulf of Mexico

Abstract Sediment porewater geochemical data (SO4−2, CH4, DIC, δ13C-DIC and Cl−) were obtained from piston cores collected in Atwater Valley, Gulf of Mexico, prior to 2005 drilling to study gas hydrates in the region. The geochemical data were used for a study of shallow sediment CH4 cycling on a seafloor mound (mound F) where an apparent upward deflection of the bottom simulating reflector (BSR) suggested vertical fluid advection. Fifteen sediment cores, ranging from 300 to 800 cm long, were collected from locations on top of the mound and across a transect up to 3.5 km off the mound. The sulfate–methane transition (SMT) was determined in each core from porewater SO4−2 and CH4 concentration profiles and occurred at depths ranging from 0 to 410 cm below the seafloor (cmbsf). The shape of porewater SO4−2 profiles plotted against depth also varied from linear to non-linear along the transect. Diffusion rates estimated from linear SO4−2 concentration gradients ranged from −20.4 to −249.1 mmol m−2 a−1 with the greatest rate measured in sediments on the mound. The large variation in SMT depth and SO4−2 profiles along the transect indicates lateral differences in total vertical CH4 flux between locations. Results suggest steady-state and non-steady-state CH4 fluxes both on the mound and transitioning off the mound and likely differences in the relative contribution of fluid advection to local shallow sediment CH4 cycling. Cores collected from on the mound had high porewater headspace CH4 concentrations (up to 8.34 mM) coupled with elevated Cl− concentrations (up to 956.5 mM) at shallow depths suggesting that salt diapirism in deep sediments may be inhibiting hydrate stability and increasing vertical CH4 flux.

[1]  W. Borowski,et al.  In situ methane concentrations at Hydrate Ridge, offshore Oregon: New constraints on the global gas hydrate inventory from an active margin , 2003 .

[2]  R. Sassen,et al.  Archaeal lipid biomarkers and isotopic evidence of anaerobic methane oxidation associated with gas hydrates in the Gulf of Mexico , 2003 .

[3]  D. Valentine,et al.  New perspectives on anaerobic methane oxidation. , 2000, Environmental microbiology.

[4]  R. H. Goodwin,et al.  Geometry and Depositional Sequences of the Mississippi Canyon, Gulf of Mexico , 1989 .

[5]  R. Berner Sulfate reduction and the rate of deposition of marine sediments , 1978 .

[6]  S. Kasten,et al.  Active and buried authigenic barite fronts in sediments from the eastern Cape Basin , 2006 .

[7]  J. Wright,et al.  The measurement of marine geothermal heat flow by a multipenetration probe with digital acoustic telemetry and insitu thermal conductivity , 1979 .

[8]  E. Davis,et al.  A new reduction algorithm for marine heat flow measurements , 1987 .

[9]  D. Fornari,et al.  A photographic and acoustic transect across two deep-water seafloor mounds, Mississippi Canyon, northern Gulf of Mexico , 2008 .

[10]  Antje Boetius,et al.  The anaerobic oxidation of methane and sulfate reduction in sediments from Gulf of Mexico cold seeps , 2004 .

[11]  D. Hutchinson,et al.  Gas and gas hydrate distribution around seafloor seeps in Mississippi Canyon, Northern Gulf of Mexico, using multi-resolution seismic imagery , 2008 .

[12]  T. Treude,et al.  Anaerobic oxidation of methane and sulfate reduction along the Chilean continental margin , 2005 .

[13]  Paul J. Wallace,et al.  Proceedings of the Ocean Drilling Program, 164 Initial Reports , 1996 .

[14]  K. McClay,et al.  Structural evolution of the Frampton growth fold system, Atwater Valley-Southern Green Canyon area, deep water Gulf of Mexico , 2004 .

[15]  W. Borowski,et al.  Marine pore-water sulfate profiles indicate in situ methane flux from underlying gas hydrate , 1996 .

[16]  R. Berner,et al.  The role of sedimentary organic matter in bacterial sulfate reduction: The G model tested1 , 1984 .

[17]  Carolyn A. Koh,et al.  Clathrate hydrates of natural gases , 1990 .

[18]  Tae Sup Yun,et al.  Physical characterization of core samples recovered from Gulf of Mexico , 2006 .

[19]  Robert A. Berner,et al.  An idealized model of dissolved sulfate distribution in recent sediments , 1964 .

[20]  W. Borowski,et al.  Global and local variations of interstitial sulfate gradients in deep-water, continental margin sediments: Sensitivity to underlying methane and gas hydrates , 1999 .

[21]  T. Ferdelman,et al.  Sulfate reduction and methane oxidation in continental margin sediments influenced by irrigation (South-East Atlantic off Namibia) , 2000 .

[22]  Bo Barker Jørgensen,et al.  Diffusion coefficients of sulfate and methane in marine sediments: Influence of porosity , 1993 .

[23]  P. Hart,et al.  High-resolution seismic-reflection investigation of the northern Gulf of Mexico gas-hydrate-stability zone , 2002 .

[24]  C. Paull,et al.  Geochemical constraints on the distribution of gas hydrates in the Gulf of Mexico , 2005 .

[25]  S. Kasten,et al.  Deep sulfate reduction completely mediated by anaerobic methane oxidation in sediments of the upwelling area off Namibia , 1998 .

[26]  Wenyue Xu,et al.  Predicting the occurrence, distribution, and evolution of methane gas hydrate in porous marine sediments , 1999 .

[27]  Bo Barker Jørgensen,et al.  Anaerobic methane oxidation rates at the sulfate‐methane transition in marine sediments from Kattegat and Skagerrak (Denmark) , 1985 .

[28]  L. Cathles,et al.  Surface and subsurface manifestations of gas movement through a N-S transect of the Gulf of Mexico , 2005 .

[29]  Elizabeth S. Gordon,et al.  Controls on the distribution and accumulation of terrigenous organic matter in sediments from the Mississippi and Atchafalaya river margin , 2004 .

[30]  M. Torres,et al.  Fluid and chemical fluxes in and out of sediments hosting methane hydrate deposits on Hydrate Ridge, OR, I: Hydrological provinces , 2002 .

[31]  R. Hesse Pore water anomalies of submarine gas-hydrate zones as tool to assess hydrate abundance and distribution in the subsurface , 2003 .

[32]  Cor J. Peters,et al.  Occurrence of methane hydrate in saturated and unsaturated solutions of sodium chloride and water in dependence of temperature and pressure , 1983 .

[33]  Alexei V. Milkov,et al.  Preliminary assessment of resources and economic potential of individual gas hydrate accumulations in the Gulf of Mexico continental slope , 2003 .

[34]  P. Aharon,et al.  Microbial sulfate reduction rates and sulfur and oxygen isotope fractionations at oil and gas seeps in deepwater Gulf of Mexico , 2000 .

[35]  P. Aharon,et al.  Sulfur and oxygen isotopes of coeval sulfate–sulfide in pore fluids of cold seep sediments with sharp redox gradients , 2003 .

[36]  Hailong Lu,et al.  Experimental studies on the possible influences of composition changes of pore water on the stability conditions of methane hydrate in marine sediments , 2005 .

[37]  Robert A. Berner,et al.  Early Diagenesis: A Theoretical Approach , 1980 .

[38]  A. Boetius,et al.  Control of sulfate pore-water profiles by sedimentary events and the significance of anaerobic oxidation of methane for the burial of sulfur in marine sediments , 2003 .

[39]  W. Balsam,et al.  Gulf of Mexico sediment sources and sediment transport trends from magnetic susceptibility measurements of surface samples , 2006 .

[40]  R. Coffin,et al.  Methane Hydrate Exploration, Atwater Valley, Texas-Louisiana Shelf: Geophysical and Geochemical Profiles , 2006 .

[41]  Gerald R. Dickens,et al.  Heat and salt inhibition of gas hydrate formation in the northern Gulf of Mexico , 2005 .

[42]  S. Boehme,et al.  A MASS BALANCE OF 13C AND 12C IN AN ORGANIC-RICH METHANE-PRODUCING MARINE SEDIMENT , 1996 .

[43]  Olaf Pfannkuche,et al.  A marine microbial consortium apparently mediating anaerobic oxidation of methane , 2000, Nature.

[44]  S. Stewart Implications of passive salt diapir kinematics for reservoir segmentation by radial and concentric faults , 2006 .

[45]  R. Pancost,et al.  Biomarker Evidence for Widespread Anaerobic Methane Oxidation in Mediterranean Sediments by a Consortium of Methanogenic Archaea and Bacteria , 2000, Applied and Environmental Microbiology.

[46]  Alexei V. Milkov,et al.  Economic geology of offshore gas hydrate accumulations and provinces , 2002 .

[47]  Michael D. Max,et al.  Natural gas hydrate : in oceanic and permafrost environments , 2000 .

[48]  R. Coffin,et al.  Methane hydrate exploration on the mid Chilean coast: A geochemical and geophysical survey , 2007 .

[49]  P. Weimer,et al.  Structural geology and evolution of the Mississippi Fan fold belt, deep Gulf of Mexico , 1992 .

[50]  K. Kvenvolden Natural gas hydrate; introduction and history of discovery , 2003 .

[51]  Alexei V. Milkov,et al.  Estimate of gas hydrate resource, northwestern Gulf of Mexico continental slope , 2001 .

[52]  D. Hutchinson,et al.  Assessing sulfate reduction and methane cycling in a high salinity pore water system in the northern Gulf of Mexico , 2008 .

[53]  Klaus Wallmann,et al.  Fluid flow, methane fluxes, carbonate precipitation and biogeochemical turnover in gas hydrate-bearing sediments at Hydrate Ridge, Cascadia Margin: numerical modeling and mass balances , 2003 .

[54]  W. Reeburgh AN IMPROVED INTERSTITIAL WATER SAMPLER1 , 1967 .

[55]  G. Dickens,et al.  Barium cycling in shallow sediment above active mud volcanoes in the Gulf of Mexico , 2006 .

[56]  B. Dugan,et al.  Physical properties of sediments from Keathley Canyon and Atwater Valley, JIP Gulf of Mexico gas hydrate drilling program , 2008 .

[57]  David L. Valentine,et al.  Biogeochemistry and microbial ecology of methane oxidation in anoxic environments: a review , 2002, Antonie van Leeuwenhoek.

[58]  G. Dickens Sulfate profiles and barium fronts in sediment on the Blake Ridge: present and past methane fluxes through a large gas hydrate reservoir , 2001 .

[59]  M. Goni,et al.  A REASSESSMENT OF THE SOURCES AND IMPORTANCE OF LAND-DERIVED ORGANIC MATTER IN SURFACE SEDIMENTS FROM THE GULF OF MEXICO , 1998 .

[60]  N. Chapman,et al.  Decreased stability of methane hydrates in marine sediments owing to phase-boundary roughness , 2002, Nature.

[61]  J. M. Hayes,et al.  Comparative Analysis of Methane-Oxidizing Archaea and Sulfate-Reducing Bacteria in Anoxic Marine Sediments , 2001, Applied and Environmental Microbiology.

[62]  Walter S Borowski,et al.  8. MODEL, STABLE ISOTOPE, AND RADIOTRACER CHARACTERIZATION OF ANAEROBIC METHANE OXIDATION IN GAS HYDRATE-BEARING SEDIMENTS OF THE BLAKE RIDGE 1 , 2000 .