CHAPTER 2
State of the Science: Recent Advances and Current Challenges in Methane Hydrate Research

In recent years, a number of significant advances in methane hydrate research have been enabled by the Department of Energy (DOE) Program. A variety of ambitious field programs have advanced state-of-the-art core sampling, geophysical surveys, and experimental production testing. Substantial scientific knowledge has also been accrued through a number of diverse laboratory investigations and modeling studies. These and several international research initiatives have moved the field forward to the point where concentrated methane hydrate accumulations have been identified, and production concepts have been put forward based on existing oil and gas production methods, modified for the unique properties and reactions of methane hydrate. The state of knowledge of methane hydrate behavior in the environment has also been advanced through consideration of methane hydrate degassing induced by natural geologic processes.

This chapter reviews recent, critical, international, and domestic advances in methane hydrate research and identifies some of the remaining challenges to realizing the goal of commercial methane hydrate production. These challenges form a basis for Chapter 3, which discusses the research



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CHAPTER 2 State of the Science: Recent Advances and Current Challenges in Methane Hydrate Research In recent years, a number of significant advances in methane hydrate research have been enabled by the Department of Energy (DoE) Program. A variety of ambitious field programs have advanced state-of-the-art core sampling, geophysical surveys, and experimental production testing. Substantial scien- tific knowledge has also been accrued through a number of diverse laboratory investigations and modeling studies. These and several international research initiatives have moved the field forward to the point where concentrated meth- ane hydrate accumulations have been identified, and production concepts have been put forward based on existing oil and gas production methods, modi- fied for the unique properties and reactions of methane hydrate. The state of knowledge of methane hydrate behavior in the environment has also been advanced through consideration of methane hydrate degassing induced by natural geologic processes. This chapter reviews recent, critical, international, and domestic ad- vances in methane hydrate research and identifies some of the remaining challenges to realizing the goal of commercial methane hydrate production. These challenges form a basis for Chapter 3, which discusses the research 1

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R E A L I Z I N G M E T H A N E H y D R A T E P R O D U C T I O N I N T H E U .S . projects currently supported by the Program, including their achievements and the remaining knowledge gaps. METHANE HyDRATE RESoURCE ASSESSMENT The “goal” in methane hydrate research and development is the identi- fication and quantification of technically and economically recoverable natural gas from methane hydrate occurrences. Because of the paucity of reliable field data, past research focused on the basic documentation of the existence and regional locations of global methane hydrate occur- rences. More recently, a number of new quantitative estimates of in-place methane hydrate volumes have been undertaken using petroleum systems concepts developed for conventional oil and natural gas exploration. When combined with field investigations to establish the physical properties of methane hydrate deposits in different geologic settings, a basis has also been established for considering production methods and recoverability. Global Methane Hydrate Estimates over the past 30 years a number of researchers have compiled global in- ventories of the total potential volumes of natural gas occurring as methane hydrate (Kvenvolden, 1988, 1993; Milkov, 2004). These estimates have garnered much interest and served to stimulate consideration of methane hydrate as a possible global energy resource. However, the utility and ap- plication of these estimates are limited because they range over several orders of magnitude and the knowledge and data upon which the predic- tions have been made remain largely speculative and with correspond- ingly large uncertainties. For example, early methane hydrate resource determinations in the 1980s and 1990s relied mainly on indirect evidence such as bottom-simulating reflectors (BSRs) identified in marine seismic surveys, or on estimates of the portion of the methane hydrate stability field that might reasonably contain methane hydrate from microbial and thermogenic sources. In the past 15 years a number of dedicated methane hydrate drilling campaigns have been undertaken around the world (see 

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State of the Science Figure 1.1), allowing researchers to refine their geologic models and im- prove their interpretations of geophysical data. Whereas some early global estimates of methane occurring as methane hydrate were as high as 1018 m3 (~35 million trillion cubic feet [TCF] methane at standard pressure and temperature [STP] conditions), estimates by Milkov (2004) decreased the range to 1-5 × 1015 m3 (~35,000-177,000 TCF). But later estimates by Klauda and Sandler (2005) are much larger (1.2 × 1017 m3 or 4,200,000 TCF), demonstrating that even recent estimates range over several orders of magnitude. However, even the lowest global resource estimates are 2 to 10 times greater than global estimates of the conventional natural gas endowment of 4.4 × 1014 m3 (~16,000 TCF) of reserves and technically recoverable undiscovered resources (Ahlbrandt, 2002; IEA, 2006). Recall- ing that the United States in 2008 consumed 6.5 × 1011 m3 (23 TCF; see Chapter 1) of natural gas, the global estimates of volumes of methane in methane hydrate are significant. Although the global methane hydrate resource inventories illustrate the importance of methane hydrate as a component of the global carbon cycle, their utility to address the energy potential of methane hydrate is limited. The majority of the enormous global methane hydrate inventory occurs as dispersed concentrations over large areas and therefore recovery of the methane, for the most part, is unfavorable technically and economically. Conversely, areas with concentrated methane hydrate deposits that may be the appropriate candidates for economic development are more limited in size. Boswell and Collett (2006) reviewed the challenge of appraising the energy potential of the large but uncertain global inventories of methane hydrate and introduced the resource pyramid concept which qualitatively appraises the distribution of the global methane hydrate resource and evaluates which type of deposit holds the greatest economic potential for development (Figure 2.1). They conclude that the deposits that are most concentrated and hold greatest potential for exploitation occur in sandstone reservoirs in the Arctic and deepwater marine environments. 

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R E A L I Z I N G M E T H A N E H y D R A T E P R O D U C T I O N I N T H E U .S . In-place resources (tcfg) Reservoir type 100’s Arctic sands 1,000’s to 10,000’s Marine sands ?? Fractured muds Mounds Harder to recover 100,000’s Undeformed muds Lower resource concentrations Increasing deposit volumes FIGURE 2.1 The methane hydrate resource “pyramid” concept qualitatively appraises the distribution of the global methane hydrate resource by the size and type of the occur- rence (deposit) and evaluates which of those hold the greatest economic potential for development. Resources near the top of the pyramid (Arctic and marine sands) are of higher reservoir quality and estimated percentage of recoverable resource, although they represent a smaller in-place resource volume than reservoirs at the bottom of the pyramid that include fine-grained sediments (silts, shales, and muds). Despite their large sedimentary volume, methane hydrate tends to occur in low concentrations in fine-grained sediments, making the recovery of s Figure 2.1.epmethane from methane hydrate more difficult and a less economic prospect. In comparison, the occurrences of methane hydrate in Arctic sandstones placed at the top of the pyramid are located near existing infrastructure and are more likely candidates for economic development in the near future. SOURCE: After Boswell (2009). Recent Methane Hydrate Resource Assessments Considerable effort has been devoted recently to carrying out more focused methane hydrate resource appraisals in specific regions by applying, with some modifications, quantitative methods commonly used for apprais- ing conventional oil and natural gas deposits. This approach is consistent 

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State of the Science BOX 2.1 The Methane Hydrate Resource as a “Petroleum System” Recent field investigations conducted over the past decade in the offshore (i.e., Gulf of Mexico, Cascadia margin, Nankai Trough, India) as well as onshore (Mackenzie Delta of Canada and the Alaska North Slope) have shown that the occurrence of methane hydrate can be interpreted in the context of a “petroleum system,” in a manner similar to that used to evaluate conventional hydrocarbon occurrences. The methane hydrate system contains all the elements of a conventional petroleum system with consideration of the source of gas (thermogenic or microbial), possible migration pathways, and nature of the reservoir sediments, traps, and seals. The unique attributes of the methane hydrate petroleum system include the dominant controls of pressure and temperature on its stability and the differences in the manifestation of methane hydrate as a solid rather than gaseous form. This introduces unique considerations of trapping and/or sealing processes and consideration of temporal aspects because the pressure-temperature field may change with time. Typically, marine occurrences of methane hydrate are found at relatively shallow depths ≤ 500 meters below seafloor whereas methane hydrate in permafrost-dominated areas is found ≤ 1,200 meters below the surface (see also Box 1.1). with the increasing knowledge of the geologic and reservoir controls over methane hydrate occurrences (see also Chapter 3) and the recognition of the applicability of petroleum system approaches that consider the source of gas, migration pathways, reservoir potential, and seals as the basis for establishing regional accumulation models (see Box 2.1). Recent U.S. Methane Hydrate Resource Assessments Gulf of Mexico Using the extensive industry database of exploratory wells and two- dimensional (2D) and three-dimensional (3D) seismic surveys, the 

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R E A L I Z I N G M E T H A N E H y D R A T E P R O D U C T I O N I N T H E U .S . Minerals Management Service (MMS) completed a preliminary methane hydrate resource assessment in the Gulf of Mexico1 (Frye, 2008). This MMS-funded and -directed work is part of the interagency collaboration on methane hydrate research, and has both contributed to and derived input from the Program’s Gulf of Mexico joint industry project ( JIP)2 (see also Chapter 4). The assessment employs a spatial mass balance model and benefits from a long history of industry exploration and production activity in the Gulf of Mexico. Working in collaboration with industry and other research agencies, MMS has developed an extensive drilling database and more than 400,000 km2 of seismic information (of which about half is 3D data) for the assessment. Although these data were not collected with methane hydrate targets in mind, the data nonetheless provided a substantial basis for model inputs such as geologic setting with respect to the methane hydrate stability field, percentage of sand, as well as consid- erations of the gas sources, migration pathways, and trapping mechanisms. The assessment also considers possible seafloor indicators such as chemo- synthetic communities and carbonates that may be associated with areas of higher probability for methane hydrate occurrences at depth. Using these attributes, the model first calculates gas generation through time, and then reallocates the distribution of gas based on a migration model. The MMS resource assessment model is based on the geologic char- acteristics of 200,000 cells that measure 2.32 km2 each, allowing for an assessed area of approximately 450,000 km2. The total volume of in-place methane in methane hydrate is calculated to range from about 11,000 TCF to 34,000 TCF with a mean estimate of 21,000 TCF (315 to 975 × 1012 m3; mean estimate of 607 × 1012 m3). Anticipating that the production poten- tial may depend on the type of confining sediment in which the methane hydrate occurs, this estimate is further subdivided to a predicted mean of about 6,700 TCF (190 × 1012 m3) occurring in association with sandstone reservoirs (shown in Figure 2.2) and about 14,700 TCF (417 × 1012 m3) in association with shale and fractured reservoirs. Significant accumulations http://www.mms.gov/revaldiv/GasHydrateAssessment.htm. 1 http://www.netl.doe.gov/technologies/oil-gas/publications/Hydrates/pdf/MethaneHydrate_ 2 2007Brochure.pdf; the JIP is managed by Chevron . 

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State of the Science are predicted near the margins of minibasins and at the front of the Sigsbee Escarpment at the southern margin of the salt in the Gulf of Mexico (Fig- ure 2.2). Importantly, the estimates represent in-place resources and do not include either technically or economically recoverable resources. The MMS anticipates using the methods and experiences from the Gulf of Mexico assessment as a framework to evaluate the entire U.S. outer Continental Shelf including Alaska, Atlantic, and Pacific margins. A phased approach is anticipated. The first effort will assess the in-place methane hydrate resources; subsequently, the gas volumes that could be technically recovered will be evaluated; the last phase will consider eco- nomically recoverable resources. Alaska North Slope A methane hydrate resource assessment was released in November 2008 by the U.S. Geological Survey (USGS), covering the terrestrial methane hydrate beneath the Alaska North Slope (Collett et al., 2008; Figure 2.3). This work was supported primarily by the USGS with some contributions from DoE as part of the interagency cooperation on methane hydrate research (see Chapter 4 for further discussion). The assessment uses a petro- leum systems approach (see Box 2.1). This USGS assessment is the first to estimate the amount of methane in the methane hydrate resource that can be technically recovered using conventional hydrocarbon production techniques. Research supported by the DoE program was central to this assessment as field research enabled through the BPXA-managed Alaska North Slope project3 provided a well-constrained case history of a North Slope accumulation, and reservoir simulation studies established a basis for predicting recoverability (Figure 2.3). The USGS assessment also carefully considered the results of the Mallik 2002 production research well pro- gram in the Mackenzie Delta (see Figure 1.1 for location) and preliminary results from a subsequent program in 2007 and 2008 (e.g., see Box 2.5). Among the various techniques for production, the USGS suggests that http://www.netl.doe.gov/technologies/oil-gas/FutureSupply/MethaneHydrates/projects/ 3 DoEProjects/Alaska-41332.html; this cooperative agreement is managed by BP Exploration Alaska, Inc. (BPXA). 

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 Figure 2.2.eps landscape

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FIGURE 2.2 Map view of mean in-place volumes of methane in methane hydrate in the Gulf of Mexico. Color values represent per cell accumulations of methane in methane hydrate (in trillion cubic meters [TCM]), with more than 200,000 cells in the model (although not all of the cells were found to have methane hydrate). 1 TCM or 1 × 109 m3 = 35.3 TCF. The areal distribution of the in-place volume is heavily influenced by the geometry of the input datasets. Large areas void of any significant methane hydrate accumulation (dark blue) are present across the salt minibasin province that comprises much of the upper continental margin slope. These areas often coincide with very shallow salt features that occupy the bulk of, and sometimes the entire, methane hydrate stability zone. Also, areas that offered a thick sedimentary section, such as the deep minibasins and much of the abyssal plain, provide an abundant supply of microbial methane from the generation model. The sand-rich cone of the Mississippi Fan is evident due to enhanced methanogenesis and methane generation in sandy sedimen- tary sections. Larger accumulations of methane hydrate (yellow, red) are present along structurally positive areas that often form at the margins of minibasins and along the front of the Sigsbee Escarpment (where the primary southernmost boundary of the dark blue area meets the light blue area). SOURCE: Matt Frye, Minerals Management Service, 2009, http://www. mms.gov/revaldiv/GasHydrateAssessment.htm. 

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0

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FIGURE 2.3 The Northern Alaska Methane Hydrate Total Petroleum System (TPS) shows the limit of the methane hydrate stability zone in northern Alaska (red outline). Within this zone, the U.S. Geological Survey (USGS) assessment predicts the total mean undiscovered technically recoverable methane from methane hydrate to be approximately 85 TCF based on the cumulative mean estimates from three assessment units, the Sagavanirkok Formation, the Tuluvak–Schrader Bluff–Prince Creek Formation, and the Nanushuk Formation. The Mt. Elbert and Barrow localities are identified. Note the concentration of industry well coverage near Prudhoe and Harrison Bay. The Eileen and Tarn methane hydrate accumulation trends were identified in earlier USGS studies. The Mt. Elbert prospect is drilled in the Eileen trend. SOURCE: Adapted after Collett et al. (2008); http://pubs.usgs.gov/fs/2008/3073/. 1

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R E A L I Z I N G M E T H A N E H y D R A T E P R O D U C T I O N I N T H E U .S . flow to the producing well. The volume of produced water associated with methane hydrate production will directly impact the design of the well completion (i.e. downhole pump selection) but also be a consideration in terms of ancillary environmental issues related to water disposal. Secondary Gas Migration An important environmental consideration in any gas field is the risk of gas migration away from the production well infrastructure interacting with other geologic strata at depth or reaching the surface. In both cases a critical consideration is the seal integrity or the overlying permeability barrier above the production interval in the near well bore and also away from the well bore. For most methane hydrate deposits, the nature of the seals may differ significantly from traditional hydrocarbon reservoirs. In some settings, methane hydrate itself or a permafrost layer may act as a seal and trap free gas below (Grauls, 2001). The relatively shallow depths of methane hydrate occurrences also may mean that secondary sealing by the overlying sediment may only be weakly developed. At present the mobil- ity of the gas and water released from methane hydrate decomposition is unknown, including their potential to migrate to the surface (e.g., Xu and Ruppel, 1999; Judd and Hovland, 2007). Migrating methane can also reform into methane hydrate within the cold ocean bottom waters and form on top of the bottom-hole well assembly, potentially compromising the blow-out prevention systems. Large pieces of methane hydrate have been observed to raft away from the seafloor because of their low density with respect to seawater (~0.91 g/cm3; Paull et al., 2003a). Erosion of the seafloor around wellheads could compromise these structures (Figure 2.7). STATE oF THE RESEARCH FIELD The level of progress and sophistication in methane hydrate research has been advancing at an exponential rate (Figure 2.8). As outlined in this chapter, observations, data, and analysis acquired from multidisciplinary 

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State of the Science 350 0 3010 300 0 Number of publications 250 0 200 0 1297 150 0 100 0 461 50 0 95 172 37 14 2 4 5 0 1 2 3 4 5 6 7 8 9 10 Century decade FIGURE 2.8 Level of international publication activity in the field of methane hydrate research over the past century shows a continuouss Figure 2.8.ep increase in interest and results, with a surge of activity during the past decade. SOURCE: E. Dendy Sloan. field activities on- and offshore and from laboratory experiments and modeling have advanced the understanding of the behavior and properties of methane hydrate and the potential to produce methane from methane hydrate accumulations. Although these advances in knowledge testify to the great interest in the potential of methane hydrate to serve as a future energy source, they belie the need for considerably more information on methane hydrate including its behavior in nature, during drilling, and in production settings, and the approaches needed to identify and reliably produce methane from this type of occurrence. Chapter 3 reviews the re- search projects that the Program has supported during the past 5 years in pursuit of some of these outstanding issues. 

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R E A L I Z I N G M E T H A N E H y D R A T E P R O D U C T I O N I N T H E U .S . REFERENCES Ahlbrandt, T. S. 2002. Future petroleum energy resources of the world. International Geology Review 44:1092-1104. Archer, D., B. Buffett, and V. Brovkin. 2008. ocean methane hydrates as a slow tipping point in the global carbon cycle. P roceedings of the National Academy of Sciences of the United States of America. Available online at http://www.pnas.org/content/early/2008/11/18/0800885105.full.pdf+html. Accessed october 15, 2009. Archie, G. E. 1942. The electrical resistivity log as an aid in determining some reservoir character- istics. Transactions of the American Institute of Mining, Metallurgical, and Petroleum Engineers 146:54-62. Backus, M., P. Murray, B. Hardage, and R. Graebner. 2006. High-resolution multi-component seismic imaging of deepwater gas hydrate systems. Leading Edge 25(5):578-596. Bellefleur, G., M. Riedel, and T. Brent. 2006. Seismic characterization and continuity analysis of gas-hydrate horizons near Mallik research wells, Mackenzie Delta, Canada. Leading Edge 25(5):599-604. Bhatnagar, G., W. G. Chapman, G. J. Hirasaki, and G. R. Dickens. 2008. Effect of overpressure on gas hydrate distribution. Proceedings of the Sixth International Conference on Gas Hydrates (ICGH 00) Vancouver, British Columbia, July 6-10. Available online at http://www.netl.doe.gov/technolo- gies/oil-gas/publications/2008_ICGH/ICGH_5604_42960.pdf. Accessed January 2, 2010. Bily, C., and J. W. L. Dick. 1974. Naturally occurring gas hydrates in the Mackenzie Delta, N.W.T: Bulletin of Canadian Petroleum Geology 22(3):340-352. Boetius, A., K. Ravenschlag, C. J. Schubert, D. Rickert, F. Widdel, A. Gieseke, R. Amann, B. B. Jørgensen, U. Witte, and o. Pfannkuche. 2000. A marine microbial consortium apparently mediating anaerobic oxidation of methane. Nature 407:623-626. Borowski, W. S., and C. K. Paull. 1997. The gas hydrate detection problem: Recognition of shallow- subbottom gas hazards in deep-water areas. In P roceedings of the Offshore Technology Conference oTC-8297, 6 pp. Boswell, R. 2009. Is gas hydrate energy within reach�� Science 325(5943):957-958. Boswell, R., and T. Collett. 2006. The gas hydrate resource pyramid. Fire in the Ice Methane Hydrate Newsletter Fall. Available online at http://www.netl.doe.gov/technologies/oil-gas/FutureSupply/ MethaneHydrates/newsletter/newsletter.htm. Accessed october 15, 2009. Bowen, R., S. R. Dallimore, M. M. Côté, J. F. Wright, and T. D. Lorenson. 2008. Geomorphology and gas release from pockmark features in the Mackenzie Delta, Northwest Territories, Canada. Pp. 171-176 in P roceedings of Ninth International Conference on Permafrost, D. L. Kane and K. M. Hinkel, eds. Fairbanks, Alaska: Institute of Northern Engineering. Collett, T. S. 2002. Energy resource potential of natural gas hydrates. AAPG Bulletin 86(11):1971- 1992. Collett, T. S., and S. R. Dallimore. 2002. Detailed analysis of gas hydrate induced drilling and pro- duction hazards. In P roceedings of the Fourth International Conference on Gas Hydrates, yokahama, Japan, April 19-23. 8 pp. 

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State of the Science Collett, T. S., and G. D. Ginsburg. 1998. Gas hydrates in the Messoyakha gas field of the West Siberian Basin: A re-examination of the geologic evidence. International Journal of Offshore Polar Engineering 8:22-29. Collett, T. S., W. F. Agena, M. W. Lee, M. V. zyrianov, K. K. Bird, T. C. Charpentier, D. W. Houseknect, T. R. Klett, R. M. Pollastro, and C. J. Schenk. 2008. Assessment of gas hydrate resources on the North Slope, Alaska. U.S. Geological Survey Fact Sheet 2008-3073. 4 pp. Reston, VA: U.S. Geological Survey. Dai, J., F. Snyder, D. Gillespie, A. Koesoemadinata, and N. Dutta. 2008. Exploration for gas hydrates in the deepwater, northern Gulf of Mexico: Part I. A seismic approach based on geologic model, inversion, and rock physics principles. Marine and Petroleum Geology 25:830-844. Dallimore, S. R., and T. S. Collett. 2005. Summary and implications of the Mallik 2002 Gas Hydrate Production Research Well Program. In Scientific Results from the Mallik 00 Gas Hydrate Produc- tion Research Well Program, Mackenzie Delta, Northwest Territories, Canada, S. R. Dallimore and T. S. Collett, eds. Bulletin 585. ottawa, ontario: Geological Survey of Canada. Dallimore, S. R., T. Uchida, and T. S. Collett. 1999. JAPEX/JNoC/GSC Mallik 2L-38 gas hydrate re- search well: overview of science program. Pp. 11-18 in Scientific Results from JAPEX/JNOC/GSC Mallik L- Gas Hydrate Research Well, Mackenzie Delta, Northwest Territories, Canada. Geological Survey of Canada, Bulletin 544. ottawa, ontario: Geological Survey of Canada. Dallimore, S. R., J. F. Wright, F. M. Nixon, M. Kurihara, K. yamamoto, T. Fujii, K. Fujii, M. Numasawa, M. yasuda, and y. Imasato. 2008. Geologic and porous media factors affecting the 2007 pro- duction response characteristics of the JoGMEC/NRCAN/AURoRA Mallik Gas Hydrate Production Research Well. Proceedings of the Sixth International Conference on Gas Hydrates (ICGH 00), Vancouver, British Columbia, Canada, July 6-10, 10 pp. Available online at https://circle. ubc.ca/bitstream/handle/2429/2232/5829.pdf��sequence=1. Accessed January 2, 2010. Davis, E. E., H. Villinger, R. D. MacDonald, R. D. Meldrum, and J. Grigel. 1997. A robust rapid- response probe for measuring bottom-hole temperatures in deep-ocean boreholes. Marine Geo- physical Researches 19:267-281. Dickens, G. R. 1999. The blast in the past. Nature 401:752-753. Dillon, W. P., J. W. Nealon, M. H. Taylor, M. L. Lee, R. M. Drury, and C. H. Anton. 2001. Seafloor collapse and methane venting associated with gas hydrate on the Blake Ridge: Causes and impli - cations to seafloor stability and methane release. Pp. 211-233 in Natural Gas Hydrates, Occurrence, Distribution and Detection, C. K. Paull and W. B. Dillon, eds. AGU Geophysical Monograph 124. Washington, DC: American Geophysical Union. Ershov, E. D., and V. S. yakushev. 1992. Experimental research on gas hydrate decomposition in frozen rocks. Cold Regions Science and Technology 20(2):147-156. Frye, M. 2008. Gas Hydrate Resource Evaluation: U.S. outer Continental Shelf. Presentation to the Committee on Assessment of the Department of Energy’s Methane Hydrate Research and Development Program: Evaluating Methane Hydrates as a Future Energy Resource. Golden, Co, December 3. Fujii, T., T. Saeki, T. Kobayashi, T. Inamori, M. Hayashi, o. Takano, T. Takayama, T. Kawasaki, S. Nagakubo, M. Nakamizu, and K. yokoi. 2008. Resource assessment of methane hydrate in the eastern Nankai Trough, Japan. Pp. 1-15 in P roceedings of Offshore Technology Conference, Houston, Texas, May 5-8. doi:10.4043/19310-MS. 

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