Microstructures of structure I and II gas hydrates from the Gulf of Mexico

Gas hydrate samples from various locations in the Gulf of Mexico (GOM) differ considerably in their microstructure. Distinct microstructure characteristics coincide with discrete crystallographic structures, gas compositions and calculated thermodynamic stabilities. The crystallographic structures were established by X-ray diffraction, using both conventional X-ray sources and high-energy synchrotron radiation. The microstructures were examined by cryo-stage Field-Emission Scanning Electron Microscopy (FE-SEM). Good sample preservation was warranted by the low ice fractions shown from quantitative phase analyses. Gas hydrate structure II samples from the Green Canyon in the northern GOM had methane concentrations of 70–80% and up to 30% of C2–C5 of measured hydrocarbons. Hydrocarbons in the crystallographic structure I hydrate from the Chapopote asphalt volcano in the southern GOM was comprised of more than 98% methane. Fairly different microstructures were identified for those different hydrates: Pores measuring 200–400 nm in diameter were present in structure I gas hydrate samples; no such pores but dense crystal surfaces instead were discovered in structure II gas hydrate. The stability of the hydrate samples is discussed regarding gas composition, crystallographic structure and microstructure. Electron microscopic observations showed evidence of gas hydrate and liquid oil co-occurrence on a micrometer scale. That demonstrates that oil has direct contact to gas hydrates when it diffuses through a hydrate matrix.

[1]  R. Sassen,et al.  Gas hydrate and crude oil from the Mississippi Fan Foldbelt, downdip Gulf of Mexico Salt Basin: significance to petroleum system , 2001 .

[2]  Michael F. Vardaro,et al.  Thermal and visual time-series at a seafloor gas hydrate deposit on the Gulf of Mexico slope , 2005 .

[3]  William P. Dillon,et al.  Economic Geology of Natural Gas Hydrate , 2006 .

[4]  J. Brooks,et al.  Asphalt Volcanism and Chemosynthetic Life in the Campeche Knolls, Gulf of Mexico , 2004, Science.

[5]  W. Kuhs,et al.  Hydrate phase transformations imposed by gas exchange , 2007 .

[6]  W. Durham,et al.  Scanning Electron Microscope Imaging of Grain Structure and Phase Distribution within Gas-Hydrate-Bearing Intervals from JAPEX/JNOC/GSC et al Mallik 5L-38: What Can We Learn From Comparisons With Laboratory-Synthesized Samples? , 2005 .

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

[8]  W. Kuhs,et al.  The formation of meso‐ and macroporous gas hydrates , 2000 .

[9]  Volkhard Spiess,et al.  A conceptual model for hydrocarbon accumulation and seepage processes around Chapopote asphalt site, southern Gulf of Mexico: From high resolution seismic point of view , 2008 .

[10]  K. Kvenvolden Gas hydrates—geological perspective and global change , 1993 .

[11]  D. Staykova,et al.  Structural studies of gas hydrates , 2003 .

[12]  L. Cathles,et al.  A kinetic model for the pattern and amounts of hydrate precipitated from a gas steam: Application to the Bush Hill vent site, Green Canyon Block 185, Gulf of Mexico , 2003 .

[13]  G. Dickens,et al.  A blast of gas in the latest Paleocene: simulating first-order effects of massive dissociation of oceanic methane hydrate. , 1997, Geology.

[14]  Doroteya K. Staykova,et al.  Formation of Porous Gas Hydrates from Ice Powders: Diffraction Experiments and Multistage Model , 2003 .

[15]  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 .

[16]  M. Torres,et al.  Gas Hydrates in Marine Sediments , 2006 .

[17]  G. Bohrmann Report and preliminary results of R/V Meteor Cruise M67/2a and 2b, Balboa - Tampico - Bridgetown, 15 March - 24 April, 2006. Fluid seepage in the Gulf of Mexico. , 2008 .

[18]  Klas Lackschewitz,et al.  Proceedings of the Ocean Drilling Program , 2002 .

[19]  T. Collett Energy resource potential of natural gas hydrates , 2002 .

[20]  James P. Kennett,et al.  Methane hydrates in Quaternary climate change : the clathrate gun hypothesis , 2003 .

[21]  J. Brooks,et al.  Gas hydrate that breaches the sea floor on the continental slope of the Gulf of Mexico , 1994 .

[22]  W. Durham,et al.  Temperature, pressure, and compositional effects on anomalous or , 2003 .

[23]  N. Ross Chapman,et al.  Complex gas hydrate from the Cascadia margin , 2007, Nature.

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

[25]  Stephen H. Kirby,et al.  Scanning Electron Microscopy investigations of laboratory-grown gas clathrate hydrates formed from melting ice, and comparison to natural hydrates , 2004 .

[26]  J. Brooks,et al.  Organic geochemistry of sediments from chemosynthetic communities, Gulf of Mexico slope , 1994 .

[27]  H. Klein,et al.  First determination of gas hydrate crystallite size distributions using high‐energy synchrotron radiation , 2007 .

[28]  Edward T. Peltzer,et al.  Gas hydrate measurements at Hydrate Ridge using Raman spectroscopy , 2007 .

[29]  J. Brooks,et al.  Thermogenic Gas Hydrates in the Gulf of Mexico , 1984, Science.

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

[31]  J. Greinert,et al.  Authigenic carbonates from the Cascadia subduction zone and their relation to gas hydrate stability , 1998 .

[32]  Gerhard Bohrmann,et al.  Appearance and preservation of natural gas hydrate from Hydrate Ridge sampled during ODP Leg 204 drilling , 2007 .

[33]  Brian H. Toby,et al.  EXPGUI, a graphical user interface for GSAS , 2001 .

[34]  L. Cathles,et al.  The geochemical signatures of variable gas venting at gas hydrate sites , 2004 .

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

[36]  C. C. Humphris Salt Movement on Continental Slope, Northern Gulf of Mexico: 2. The Concepts , 1979 .

[37]  D. Archer,et al.  Global inventory of methane clathrate: sensitivity to changes in the deep ocean , 2004 .

[38]  J. Charlou,et al.  A comparative Raman spectroscopic study of natural gas hydrates collected at different geological sites , 2007 .

[39]  T. Hirano,et al.  Occurrence, structure, and composition of natural gas hydrate recovered from the Blake Ridge, northwest Atlantic , 2000 .

[40]  Jeffery B. Klauda,et al.  Global Distribution of Methane Hydrate in Ocean Sediment , 2005 .

[41]  G. Bohrmann,et al.  The Impact of Porous Microstructures of Gas Hydrates On Their Macroscopic Properties , 2004 .

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

[43]  I. MacDonald,et al.  Gas hydrate and chemosynthetic biota in mounded bathymetry at mid-slope hydrocarbon seeps: Northern Gulf of Mexico , 2003 .

[44]  W. Kuhs Physics and Chemistry of Ice , 2007 .

[45]  Vello A. Kuuskraa,et al.  Hydrates contain vast store of world gas resources , 1998 .

[46]  Werner F. Kuhs,et al.  Microstructure of gas hydrates in porous media , 2007 .

[47]  W. Borowski,et al.  Gas hydrate growth, methane transport, and chloride enrichment at the southern summit of Hydrate Ridge, Cascadia margin off Oregon , 2004 .

[48]  J. Greinert,et al.  Sea Floor Methane Hydrates at Hydrate Ridge, Cascadia Margin , 2001 .

[49]  E. D. Sloan,et al.  Clathrate hydrate growth and inhibition , 1998 .

[50]  G. Bohrmann,et al.  In situ hydrocarbon concentrations from pressurized cores in surface sediments, Northern Gulf of Mexico , 2007 .

[51]  M. G. Sarwar Murshed,et al.  Natural gas hydrate investigations by synchrotron radiation X‐ray cryo‐tomographic microscopy (SRXCTM) , 2008 .

[52]  Martin P. A. Jackson,et al.  Salt-Related Fault Families and Fault Welds in the Northern Gulf of Mexico , 1999 .

[53]  E. A. Payzant,et al.  LOW TEMPERATURE X-RAY DIFFRACTION STUDIES OF NATURAL GAS HYDRATE SAMPLES FROM THE GULF OF MEXICO , 2008 .