Gas hydrate systems at Hydrate Ridge offshore Oregon inferred from molecular and isotopic properties of hydrate-bound and void gases

Abstract We report and discuss molecular and isotopic properties of hydrate-bound gases from 55 samples and void gases from 494 samples collected during Ocean Drilling Program (ODP) Leg 204 at Hydrate Ridge offshore Oregon. Gas hydrates appear to crystallize in sediments from two end-member gas sources (deep allochthonous and in situ) as mixtures of different proportions. In an area of high gas flux at the Southern Summit of the ridge (Sites 1248–1250), shallow (0–40 m below the seafloor [mbsf]) gas hydrates are composed of mainly allochthonous mixed microbial and thermogenic methane and a small portion of thermogenic C2+ gases, which migrated vertically and laterally from as deep as 2- to 2.5-km depths. In contrast, deep (50–105 mbsf) gas hydrates at the Southern Summit (Sites 1248 and 1250) and on the flanks of the ridge (Sites 1244–1247) crystallize mainly from microbial methane and ethane generated dominantly in situ. A small contribution of allochthonous gas may also be present at sites where geologic and tectonic settings favor focused vertical gas migration from greater depth (e.g., Sites 1244 and 1245). Non-hydrocarbon gases such as CO2 and H2S are not abundant in sampled hydrates. The new gas geochemical data are inconsistent with earlier models suggesting that seafloor gas hydrates at Hydrate Ridge formed from gas derived from decomposition of deeper and older gas hydrates. Gas hydrate formation at the Southern Summit is explained by a model in which gas migrated from deep sediments, and perhaps was trapped by a gas hydrate seal at the base of the gas hydrate stability zone (GHSZ). Free gas migrated into the GHSZ when the overpressure in gas column exceeded sealing capacity of overlaying sediments, and precipitated as gas hydrate mainly within shallow sediments. The mushroom-like 3D shape of gas hydrate accumulation at the summit is possibly defined by the gas diffusion aureole surrounding the main migration conduit, the decrease of gas solubility in shallow sediment, and refocusing of gas by carbonate and gas hydrate seals near the seafloor to the crest of the local anticline structure.

[1]  M. Vanneste,et al.  Sublacustrine mud volcanoes and methane seeps caused by dissociation of gas hydrates in Lake Baikal , 2002 .

[2]  B. M. Didyk,et al.  24. ISOTOPE COMPOSITIONS OF GASES IN SEDIMENTS FROM THE CHILE CONTINENTAL MARGIN1 , 1995 .

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

[4]  C. Ruppel,et al.  Permeability evolution during the formation of gas hydrates in marine sediments , 2003 .

[5]  K. Kvenvolden,et al.  Methane and other Hydrocarbon Gases in Marine Sediment , 1983 .

[6]  S. Qadri,et al.  Novel results on structural investigations of natural minerals of clathrate hydrates , 2004 .

[7]  M. Zoback,et al.  Stress, pore pressure, and dynamically constrained hydrocarbon columns in the South Eugene Island 330 field, northern Gulf of Mexico , 2001 .

[8]  Hitoshi Tomaru,et al.  Ethane enrichment and propane depletion in subsurface gases indicate gas hydrate occurrence in marine sediments at southern Hydrate Ridge offshore Oregon , 2004 .

[9]  F. Anselmetti,et al.  Proceedings of the Ocean Drilling Program. Initial Reports , 2002 .

[10]  B. Buffett,et al.  A steady state model for marine hydrate formation: Constraints on methane supply from pore water sulfate profiles: STEADY STATE HYDRATE MODEL , 2003 .

[11]  G. Rehder,et al.  Correction to “Noble gases and radiocarbon in natural gas hydrates” by Gisela Winckler, Werner Aeschbach‐Hertig, Johannes Holocher, Rolf Kipfer, Ingeborg Levin, Christian Poss, Gregor Rehder, Erwin Suess, and Peter Schlosser , 2002 .

[12]  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 .

[13]  H. Chung,et al.  Origin of gaseous hydrocarbons in subsurface environments: Theoretical considerations of carbon isotope distribution , 1988 .

[14]  L. A. Barnard,et al.  Gas Hydrates of the Blake Outer Ridge Site 533, Deep Sea Drilling Project Leg 76 , 1983 .

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

[16]  J. K. Perry,et al.  Mathematical modeling of stable carbon isotope ratios in natural gases † † We dedicate this paper to Bill Sackett on the occasion of his 70th birthday. , 2000 .

[17]  R. Littke,et al.  Hydrocarbon gas in the Costa Rica subduction zone: primary composition and post-genetic alteration , 2002 .

[18]  Gerald R. Dickens,et al.  Modeling the Global Carbon Cycle with a Gas Hydrate Capacitor: Significance for the Latest Paleocene Thermal Maximum , 2013 .

[19]  J. Greinert,et al.  Gas hydrate destabilization: enhanced dewatering, benthic material turnover and large methane plumes at the Cascadia convergent margin , 1999 .

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

[21]  M. Hovland,et al.  Gas hydrate and sedimant gas composition, Hole 892A , 1995 .

[22]  Harry H. Roberts,et al.  Massive vein-filling gas hydrate: relation to ongoing gas migration from the deep subsurface in the Gulf of Mexico , 2001 .

[23]  Hitoshi Tomaru,et al.  Three-dimensional distribution of gas hydrate beneath southern Hydrate Ridge: Constraints from ODP Leg 204 , 2004 .

[24]  R. Amann,et al.  Activity, Distribution, and Diversity of Sulfate Reducers and Other Bacteria in Sediments above Gas Hydrate (Cascadia Margin, Oregon) , 2003 .

[25]  R. Sassen,et al.  Bacterial methane oxidation in sea-floor gas hydrate: Significance to life in extreme environments , 1998 .

[26]  W. Borowski,et al.  Effects of core retrieval and degassing on the carbon isotope composition of methane in gas hydrate - and free gas - bearing sediments from the blake ridge , 2000 .

[27]  M. E. Mackay Structural variation and landward vergence at the toe of the Oregon accretionary prism , 1995 .

[28]  C. Goldfinger,et al.  Geophysical constraints on the surface distribution of authigenic carbonates across the Hydrate Ridge region, Cascadia margin , 2003 .

[29]  A. Hine,et al.  Hydrogen sulfide–hydrates and saline fluids in the continental margin of South Australia , 2000 .

[30]  E. Faber,et al.  Empirical carbon isotope/maturity relationships for gases from algal kerogens and terrigenous organic matter, based on dry, open-system pyrolysis , 1996 .

[31]  Ian R. MacDonald,et al.  Evidence of structure-H hydrate, Gulf of Mexico Continental slope , 1994 .

[32]  Gregor Rehder,et al.  Distribution and height of methane bubble plumes on the Cascadia Margin characterized by acoustic imaging , 2003 .

[33]  William W. Sager,et al.  Geophysical signatures of mud mounds at hydrocarbon seeps on the Louisiana continental slope, northern Gulf of Mexico , 2003 .

[34]  G. Ginsburg,et al.  Water segregation in the course of gas hydrate formation and accumulation in submarine gas-seepage fields , 1997 .

[35]  W. Borowski,et al.  7. ISOTOPIC COMPOSITION OF CH 4 , CO 2 SPECIES, AND SEDIMENTARY ORGANIC MATTER WITHIN SAMPLES FROM THE BLAKE RIDGE: GAS SOURCE IMPLICATIONS 1 , 2000 .

[36]  G. Claypool,et al.  Modeling thermogenic gas generation using carbon isotope ratios of natural gas hydrocarbons , 1995 .

[37]  T. Lorenson Gas composition and isotopic geochemistry of cuttings, core, and gas hydrate from the JAPEX/JNOC/GSC Mallik 2L-38 gas hydrate research well , 1999 .

[38]  W. Dean,et al.  Anomalous 13C enrichment in modern marine organic carbon , 1985, Nature.

[39]  C. Clayton Carbon isotope fractionation during natural gas generation from kerogen , 1991 .

[40]  J. Curiale,et al.  26. GAS HYDRATES IN SEDIMENTS OF HOLES 497 AND 498A, DEEP SEA DRILLING PROJECT LEG 67 , 2006 .

[41]  U. Fehn,et al.  Dating of pore waters with (129)I: relevance for the origin of marine gas hydrates , 2000, Science.

[42]  R. Amann,et al.  Activity, distribution, and diversity of sulfate reducers and other bacteria above gas hydrate (Cascadia Margin, OR). , 2003 .

[43]  W. Borowski,et al.  Co-existence of gas hydrate, free gas, and brine within the regional gas hydrate stability zone at Hydrate Ridge (Oregon margin): evidence from prolonged degassing of a pressurized core , 2004 .

[44]  R. Sassen,et al.  Thermogenic vent gas and gas hydrate in the Gulf of Mexico slope: Is gas hydrate decomposition significant? , 2001 .

[45]  M. Hovland,et al.  Organic geochemistry of gases, fluids, and hydrates at the Cascadia Margin accretionary margin , 1995 .

[46]  T. McDonald,et al.  Gas Hydrates of the Middle America TrenchDeep Sea Drilling Project Leg 84 , 1985 .

[47]  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 .

[48]  Raymond W. Lee,et al.  Macrofaunal community structure and sulfide flux at gas hydrate deposits from the Cascadia convergent margin, NE Pacific , 2002 .

[49]  A. Milkov Global estimates of hydrate-bound gas in marine sediments: how much is really out there? , 2004 .

[50]  W. Dean,et al.  Depletion of 13C in Cretaceous marine organic matter: Source, diagenetic, or environmental sigal? , 1986 .

[51]  T. Lorenson,et al.  Gas content and composition of gas hydrate from sediments of the southeastern North American continental margin , 2000 .

[52]  Alla Yu Lein,et al.  Geological, geochemical, and microbial processes at the hydrate-bearing Håkon Mosby mud volcano: a review , 2004 .

[53]  Jan Kihle,et al.  Adaptation of fluorescence excitation-emission micro-spectroscopy for characterization of single hydrocarbon fluid inclusions , 1995 .

[54]  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 .

[55]  S. W. Taylor,et al.  Bacteriogenic Ethane in Near-Surface Aquifers: Implications for Leaking Hydrocarbon Well Bores , 2000 .

[56]  T. Lorenson,et al.  Chemistry, isotopic composition, and origin of a methane-hydrogen sulfide hydrate at the Cascadia subduction zone , 1998 .

[57]  R. Huene,et al.  Initial reports of the deep sea drilling project: National Science Foundation, Washington, D.C., 1969, 672 pp., U.S. $ 10.25 , 1971 .

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

[59]  G. Claypool,et al.  Introduction to Shipboard Organic Geochemistry on the JOIDES Resolution , 2001 .

[60]  Michael J. Whiticar,et al.  Carbon and hydrogen isotope systematics of bacterial formation and oxidation of methane , 1999 .

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

[62]  Keith A. Kvenvolden,et al.  A review of the geochemistry of methane in natural gas hydrate , 1995 .

[63]  K. Kvenvolden,et al.  32. GAS HYDRATES OF THE PERUVIAN OUTER CONTINENTAL MARGIN1 , 1990 .

[64]  G. Rehder,et al.  Noble gases and radiocarbon in natural gas hydrates , 2002 .