Observations of pore‐scale growth patterns of carbon dioxide hydrate using X‐ray computed microtomography

Natural and artificial gas hydrates with internal pores of nano to centimeters and weak grain-cementation have been widely reported, while the detailed formation process of grain-cementing hydrates remains poorly identified. Pore-scale morphology of carbon dioxide (CO2) hydrate formed in a partially brine-saturated porous medium was investigated via X-ray computed microtomography (X-ray CMT). Emphasis is placed on the pore-scale growth patterns of gas hydrate, including the growth of dendritic hydrate crystals on preformed hydrate and water-wetted grains, porous nature of the hydrate phase, volume expansion of more than 200% during the water-to-hydrate phase transformation, preference of unfrozen water wetting hydrophilic minerals, and the relevance to a weak cementation effect on macroscale physical properties. The presented pore-scale morphology and growth patterns of gas hydrate are expected in natural sediment settings where free gas is available for hydrate formation, such as active gas vents, gas seeps, mud volcanoes, permafrost gas hydrate provinces, and CO2 injected formation for the sake of geologic carbon storage; and in laboratory hydrate samples synthesized from partially brine-saturated sediments or formed from water-gas interfaces.

[1]  Tae Sup Yun,et al.  Compressional and shear wave velocities in uncemented sediment containing gas hydrate , 2005 .

[2]  E. Peltzer,et al.  Deep sea NMR: Methane hydrate growth habit in porous media and its relationship to hydraulic permeability, deposit accumulation, and submarine slope stability , 2003 .

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

[4]  D. Peters,et al.  Gumusut-Kakap Project: Geohazard Characterisation and Impact on Field Development Plans , 2008 .

[5]  M. E. Mackay,et al.  Origin of bottom-simulating reflectors: Geophysical evidence from the Cascadia accretionary prism , 1994 .

[6]  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.

[7]  C. Ruppel,et al.  Thermal Conductivity Measurements in Porous Mixtures of Methane Hydrate and Quartz Sand , 2002 .

[8]  Tae Sup Yun,et al.  Mechanical properties of sand, silt, and clay containing tetrahydrofuran hydrate , 2007 .

[9]  J. Carlos Santamarina,et al.  Hydrate formation and growth in pores , 2012 .

[10]  A. Myerson Handbook of Industrial Crystallization , 2002 .

[11]  G. Massoth,et al.  Oregon Subduction Zone: Venting, Fauna, and Carbonates , 1986, Science.

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

[13]  J. C. Santamarina,et al.  Parametric study of the physical properties of hydrate-bearing sand, silt, and clay sediments: 1. Electromagnetic properties , 2010 .

[14]  William F. Waite,et al.  Physical properties and rock physics models of sediment containing natural and laboratory-formed methane gas hydrate , 2004 .

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

[16]  Yun Wook Choo,et al.  Geomechanical and Thermal Responses of Hydrate-Bearing Sediments Subjected to Thermal Stimulation: Physical Modeling Using a Geotechnical Centrifuge , 2013 .

[17]  Ross Anderson,et al.  CO2 hydrates could provide secondary safety factor in subsurface sequestration of CO2. , 2010, Environmental science & technology.

[18]  T. Kwon,et al.  Effect of CO2 hydrate formation on seismic wave velocities of fine‐grained sediments , 2013 .

[19]  Johannes Kulenkampff,et al.  Pore space hydrate formation in a glass bead sample from methane dissolved in water , 2005 .

[20]  J. C. Santamarina,et al.  Parametric study of the physical properties of hydrate‐bearing sand, silt, and clay sediments: 2. Small‐strain mechanical properties , 2010 .

[21]  R. Rothwell,et al.  Low-sea-level emplacement of a very large Late Pleistocene ‘megaturbidite’ in the western Mediterranean Sea , 1998, Nature.

[22]  Yukio Nakata,et al.  Mechanical behavior of gas‐saturated methane hydrate‐bearing sediments , 2013 .

[23]  Carolyn A. Koh,et al.  MACROSCOPIC INVESTIGATION OF HYDRATE FILM GROWTH AT THE HYDROCARBON/WATER INTERFACE , 2007 .

[24]  K. Kvenvolden Methane hydrate — A major reservoir of carbon in the shallow geosphere? , 1988 .

[25]  Gye-Chun Cho,et al.  Evolution of Compressional Wave Velocity during CO2 Hydrate Formation in Sediments , 2009 .

[26]  Gye-Chun Cho,et al.  Submarine Slope Failure Primed and Triggered by Bottom Water Warming in Oceanic Hydrate-Bearing Deposits , 2012 .

[27]  B. Trout,et al.  Computations of diffusivities in ice and CO2 clathrate hydrates via molecular dynamics and Monte Carlo simulations , 2002 .

[28]  M. Maslin,et al.  Sea-level –and gas-hydrate–controlled catastrophic sediment failures of the Amazon Fan , 1998 .

[29]  C.R.I. Clayton,et al.  Influence of gas hydrate morphology on the seismic velocities of sands , 2009 .

[30]  R. Kayen,et al.  Pleistocene slope instability of gas hydrate‐laden sediment on the Beaufort sea margin , 1991 .

[31]  Tae Sup Yun,et al.  Physical properties of hydrate‐bearing sediments , 2009 .

[32]  T. Ebinuma,et al.  Microscopic observations of formation processes of clathrate-hydrate films at an interface between water and carbon dioxide , 1999 .

[33]  Gregory F. Moore,et al.  Temporal and spatial evolution of a gas hydrate-bearing accretionary ridge on the Oregon continental margin , 1999 .

[34]  Stephen H. Kirby,et al.  Peculiarities of Methane Clathrate Hydrate Formation and Solid-State Deformation, Including Possible Superheating of Water Ice , 1996, Science.

[35]  C. Clayton,et al.  A laboratory investigation into the seismic velocities of methane gas hydrate‐bearing sand , 2005 .

[36]  Timothy J Kneafsey,et al.  Thermal dissociation behavior and dissociation enthalpies of methane-carbon dioxide mixed hydrates. , 2011, The journal of physical chemistry. B.

[37]  William F. Waite,et al.  Hydrate morphology: Physical properties of sands with patchy hydrate saturation , 2012 .

[38]  Hitoshi Koide,et al.  DEEP SUB-SEABED DISPOSAL OF CO2 THE MOST PROTECTIVE STORAGE - , 1997 .

[39]  J. Santamarina,et al.  P-wave monitoring of hydrate-bearing sand during CH4–CO2 replacement , 2011 .

[40]  Izuo Aya,et al.  Solubility of CO 2 and density of CO 2 hydrate at 30 MPa , 1997 .

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

[42]  T. Buanes,et al.  Storage of CO2 in natural gas hydrate reservoirs and the effect of hydrate as an extra sealing in cold aquifers , 2007 .

[43]  Kurt Zenz House,et al.  Permanent carbon dioxide storage in deep-sea sediments , 2006, Proceedings of the National Academy of Sciences.

[44]  R. Ohmura,et al.  Formation, growth and dissociation of clathrate hydrate crystals in liquid water in contact with a hydrophobic hydrate-forming liquid , 1999 .

[45]  W. Waite,et al.  Methane hydrate formation in partially water-saturated Ottawa sand , 2004 .

[46]  Wolfgang Fink,et al.  Three‐Dimensional Multiphase Segmentation of X‐Ray CT Data of Porous Materials Using a Bayesian Markov Random Field Framework , 2012 .

[47]  T. Kwon,et al.  Destabilization of Marine Gas Hydrate-Bearing Sediments Induced by a Hot Wellbore: A Numerical Approach , 2010 .

[48]  Pierre Cochonat,et al.  Effect of gas hydrates melting on seafloor slope instability , 2003 .

[49]  J. Santamarina,et al.  Hydrate adhesive and tensile strengths , 2011 .

[50]  Y. Mori,et al.  Clathrate-hydrate film growth along water/hydrate-former phase boundaries—numerical heat-transfer study , 2006 .

[51]  J. Santamarina,et al.  Hydrate growth in granular materials: implication to hydrate bearing sediments , 2011 .

[52]  Tae Sup Yun,et al.  Observations related to tetrahydrofuran and methane hydrates for laboratory studies of hydrate‐bearing sediments , 2007 .