Petrophysical Properties of Natural Gas Hydrates-Bearing Sands and Their Sedimentology in the Nankai Trough

Abstract. The Nankai Trough parallels the Japanese Island, where extensive BSRs have been interpreted from seismic reflection records. High resolution seismic surveys and drilling site-survey wells conducted by the MTI in 1997, 2001 and 2002 have revealed subsurface gas hydrate at a depth of about 290 mbsf (1235 mbsl) in the easternmost part of Nankai Trough. The MITI Nankai Trough wells were drilled in late 1999 and early 2000 to provide physical evidence for the existence of gas hydrate. During field operations, continuous LWD and wire-line well log data were obtained and numerous gas hydrate-bearing cores were recovered. Subsequence sedimentologic and geochemical analyses performed on the cores revealed important geologic controls on the formation and preservation of natural gas hydrate. This knowledge is crucial to predicting the location of other hydrate deposits and their eventual energy resource. Pore-space gas hydrates reside in sandy sediments from 205 to 268 mbsf mostly filling intergranular porosity. Pore waters chloride anomalies, core temperature depression and core observations on visible gas hydrates confirm the presence of pore-space hydrates within moderate to thick sand layers. Gas hydrate-bearing sandy strata typically were 10 cm to a meter thick. Gas hydrate saturations are typically between 60 and 90 % throughout most of the hydrate-dominant sand layers, which are estimated by well log analyses as well as pore water chloride anomalies.
It is necessary for evaluating subfurface fluid dlow behavious to know both porosity and permeability of gas hydrate-bearing sand to evaluate subsurface fluid flow behaviors. Sediment porosities and pore-size distributions were obtained by mercury porosimetry, which indicate that porosities of gas hydrate-bearing sandy strata are approximately 40 %. According to grain size distribution curves, gas hydrate is dominant in fine- to very fine-grained sandy strata.     

Subsurface Occurrence of Natural Gas Hydrate in the Nankai Trough Area: Implication for Gas Hydrate Concentration

Abstract. The Nankai Trough runs along the Japanese Islands, where extensive BSRs have been recognized in its forearc basins. High resolution seismic surveys and site-survey wells undertaken by the MITI have revealed the gas hydrate distribution at a depth of about 290 mbsf. The MITI Nankai Trough wells were drilled in late 1999 and early 2000. The highlights were successful retrievals of abundant gas hydrate-bearing cores in a variety of sediments from the main hole and the post survey well-2, keeping the cored gas hydrate stable, and the obtaining of continuous well log data in the gas hydrate-dominant intervals from the main hole, the post survey well-1 and the post survey well-3. Gas-hydrate dominant layers were identified at the depth interval from 205 to 268 mbsf. Pore-space hydrate, very small in size, was recognized mostly filling intergranular pores of sandy sediments. Anomalous chloride contents in extracted pore water, core temperature depression, core observations as well as visible gas hydrates confirmed the presence of pore-space hydrates within moderate to thick sand layers. Gas hydrate-bearing sandy strata typically were 10 cm to a meter thick with porosities of about 40 %. Gas hydrate saturations in most hydrate-dominant layers were quite high, up to 90 % pore saturation.
All the gas hydrate-bearing cores were subjected to X-ray CT imagery measurements for observation of undisturbed sedimentary textures and gas-hydrate occurrences before being subjected to other analyses, such as (1) petrophysical properties, (2) biostratigraphy, (3) geochemistry, (4) microbiology and (5) gas hydrate characteristics.     

Application of AVO Analysis to Seismic Data for Detection of Gas below Methane Hydrate Stability Zone in Nankai Trough Area

Abstract. For the purpose of development of methane hydrate, occurring in the deep marine subsurface, as a resource, the most important issue is to understand the methane hydrate system (generation, migration and accumulation) as well as to delineate the methane hydrate reservoir properties. We have applied the Amplitude Versus Offset (AVO) analysis to the seismic data acquired in the Nankai Trough, offshore Japan, in order to confirm the occurrence of gas just below the methane hydrate-bearing zone, assuming that gas will show a so-called Class-3 AVO response. Knowledge of the amount and occurrence of gas in the sediment below methane hydrate-bearing zone is one of the keys to understand the methane hydrate system.
We have utilized the qualitative analysis of AVO methodology to delineate how gas is located below the BSR, which is thought to be the reflection event from the interface between the methane hydrate-bearing zone and the underlying gas-bearing zone. In the region of MITI Nankai Trough Well PSW-3, we observe two BSRs separated by 25 ms. After AVO modeling using well data, we applied AVO attribute analysis and attribute crossplot analysis to the seismic data. Finally we applied an offset-amplitude analysis to CMP gather data at specific locations to confirm the results of AVO attribute analysis. The AVO analysis shows that there is very little gas located in the underlying sediment below methane hydrate-bearing zone. This result supports the fact that we could not obtain any clear evidence of gas occurrence just below the methane hydrate-bearing zone in the Nankai Trough well drilling.     

Geochemical Process of Gas Hydrate Formation in the Nankai Trough Based on Chloride and Isotopic Anomalies in Interstitial Water

Abstract: Interstitial water expelled from gas hydrate-bearing and -free sediments in the Nankai Trough are analyzed in terms of Cl-, SO₄²-, δ¹⁸O and δD. The baselines for the Cl- concentration and δ¹⁸O value are close to seawater values (530 mM and 0%), indicating that the interstitial water is of seawater origin. The δD values decrease with depth, implying isotopic exchange of hydrogen between upwelling biogenic methane depleted in D and interstitial water. The Cl- concentrations in gas hydrate-bearing sediments are anomalously low, while the δ¹⁸O and δD values are both high, suggesting that the water forming these gas hydrates was poor in Cl- and enriched in ¹⁸O and D during gas hydrate formation. Calculation of the gas hydrate saturations using Cl "and δ¹⁸O anomalies gives results of up to 80 % in sand, and shows that the δ¹⁸O baseline is not consistent with the Cl" baseline. The δ¹⁸O baseline increases by +1% in gas hydrate-free clay and silt. This is considered to be caused by clustering of water molecules after gas hydrate dissociation in response to the upward migration of the base of gas hydrate stability, as indicated by the presence of a double bottom-simulating reflector at this site. The water clusters enriched in ¹⁸O are responsible for the increase in the δ¹⁸O baseline with normal Cl". The abrupt shallowing of the base of gas hydrate stability may induce the dissociation of gas hydrates and the accumulation of gases in the new stability zone, representing a geological process that increases gas hydrate saturation.     

Detection of Methane Hydrate-Bearing Zones from Seismic Data

Abstract. The MITI Nankai Trough wells were drilled offshore Japan in the Tokai area in 1999 and 2000. The occurrence of methane hydrate was confirmed by various indicators in the borehole logs and from core data. These findings have a large impact on potential future Japanese energy resources and other related-scientific interests.
We first tried to find the methane hydrate-bearing zones using interval velocities derived from NMO velocity analysis. However, this analysis produced poor resolution. To achieve a more detailed delineation of the gas hydrate- and gas-bearing zones, we executed a seismic impedance inversion calibrated by the logs from two of the MITI Nankai Trough wells. Although these two wells are only about 90 m apart, we were able to produce an impedance section with fine detail by adopting a simple initial model and incorporating physical properties of the methane hydrate-bearing zones. The locations of the methane hydrate-bearing zones are readily apparent in the final section.     

Lithology, Biostratigraphy, and Magneto stratigraphy of Gas Hydrate-Bearing Sediments in the Eastern Nankai Trough

Abstract: Stratigraphic controls on the formation and distribution of gas hydrates were examined for sediments from a BH-1 well drilled in the landward slope of the Nankai Trough, approximately 60 km off Omaezaki, Japan. Three lithologic units were recognized in the 250 m-thick sequence of sediments: Unit 1 (0–70 mbsf) consists of calcareous silt and clay with thin volcanic ash layers, Unit 2 (70–150 mbsf) consists of calcareous silt and clay with volcanic ash and thin sand layers, and Unit 3 (150–250 mbsf) consists of weakly consolidated calcareous silt and clay with thick and frequent sand layers. Soupy structures and gas bubbles in the sediments indicate the presence of two hydrate zones between 40 and 130 mbsf and below 195 mbsf. Nannofossil biostratigraphy and magnetostratigraphy indicate that the sequence recovered at the BH-1 well is mostly continuous and represents sediments deposited from 0 to 1.5 Ma. Calculation of the sedimentation rate reveals a condensed section between 65 and 90 mbsf. The inferred distribution of gas hydrates in the BH-1 well appears to be strongly controlled by the stratigraphy and lithology of the sediments. Thick, gently inclined sand layers in Unit 3 provide a conduit for the migration of gases from deeper regions, and are considered responsible for the formation of the hydrate zone below 195 mbsf. At shallower levels, thin, gently inclined sand layers are also considered to allow for the migration of gases, leading to the formation of the upper hydrate zone between 40 and 130 mbsf. The overlying sub-horizontal silt and clay of the condensed section, truncating the underlying gently inclined sand and silt/clay layers, may provide an effective trap for gases supplied through the sand layers, further contributing to hydrate formation in the upper hydrate zone.     

Geochemical insights into contribution of petroleum hydrocarbons to the formation of hydrates in the Taixinan Basin,the South China Sea

Methane hydrate in the South China Sea(SCS)has extensively been considered to be biogenic on the basis of itsδ13C and δD values.Although previous efforts have greatly been made,the contribution of thermogenic oil/gas has still been underestimated.In this study,biomarkers and porewater geochemical parameters in hydrate-free and hydrate-bearing sediments in the Taixinan Basin,the SCS have been measured for evaluating the contribu-tion of petroleum hydrocarbons to the formation of hydrate deposits via a comparative study of their source inputs of organic matters,environmental conditions,and microbial activities.The results reveal the occurrence of C14-C16 branched saturated fatty acids(bSFAs)with relatively high concentrations from sulfate-reducing bacteria(SRBs)in hydrate-bearing sediments in comparison with hydrate-free sediments,which is in accord with the positive δ13C values of dissolved inorganic carbon(DIC),increasing methane concentrations,decreasing alka-linity,and concentration fluctuation of ions(Cl-,Br,SO2-,Ca2+,and Mg2+).These data indicate the relatively active microbial activities in hydrate-bearing sediments and coincident variations of environmental conditions.Carbon isotope compositions of bSFAs(-34.0％o to-21.2％o),n-alkanes(-34.5％o to-29.3％o),and methane(-70.7％o to-69.9％o)jointly demonstrate that SRBs might thrive on a different type of organic carbon rather than methane.Combining with numerous gas/oil reservoirs and hydrocarbon migration channels in the SCS,the occurrence of unresolved complex mixtures(UCMs),odd-even predominance(OEP)values(about 1.0),and biomarker patterns suggest that petroleum hydrocarbons from deep oil/gas reservoirs are the most probable carbon source.Our new results provide significant evidence that the deep oil/gas reservoirs may make a contribution to the formation of methane hydrate deposits in the SCS.     

Detection and Evaluation of Gas Hydrates in the Eastern Nankai Trough by Geochemical and Geophysical Methods

Abstract: Interstitial waters extracted from the sediment cores from the exploration wells, “BH‐1” and “MITI Nankai Trough”, drilled ～60 km off Omaezaki Peninsula in the eastern Nankai Trough, were analyzed for the chloride and sulfate concentrations to examine the depth profiles and occurrence of subsurface gas hydrates. Cored intervals from the seafloor to 310 mbsf were divided into Unit 1 (～70 mbsf, predominated by mud), Unit 2 (70–150 mbsf, mud with thin ash beds), Unit 3 (150–250+ mbsf, mud with thin ash and sand), and Unit 4 (275–310 mbsf, predominated by mud). The baseline level for Cl “concentrations was 540 mM, whereas low chloride anomalies (103 to 223 mM) were identified at around 207 mbsf (zone A), 234–240 mbsf (zone B), and 258–265 mbsf (zone C) in Unit 3. Gas hydrate saturation (Sh %) of sediment pores was calculated to be 60 % (zone A) to 80 % (zones B and C) in sands whereas only a few percent in clay and silt. The total amount of gas hydrates in hydrate‐bearing sands was estimated to be 8 to 10 m³ of solid gas hydrate per m², or 1.48 km³ CH₄ per 1 km². High saturation zones (A, B and C) were consistent with anomaly zones recognized in sonic and resistivity logs. 2D and high‐resolution seismic studies revealed two BSRs in the study area. Strong BSRs (BSR‐1) at ～263 mbsf were correlated to the boundary between gas hydrate‐bearing sands (zone C) and the shallower low velocity zone, while the lower BSRs (BSR‐2) at～289 mbsf corresponded to the top of the deeper low velocity zone of the sonic log. Tectonic uplift of the study area is thought to have caused the upward migration of BGHS. That is, BSR‐1 corresponds to the new BGHS and BSR‐2 to the old BGHS. Relic gas hydrates and free gas may survive in the interval between BSR‐1 and BSR‐2, and below BSR‐2, respectively. Direct measurements of the formation temperature for the top 170 m interval yield a geothermal gradient of ～4.3d?C/ 100 m. Extrapolation of this gradient down to the base of gas hydrate stability yields a theoretical BGHS at～230 mbsf, surprisingly ～35 m shallower than the base of gas hydrate‐bearing sands (zone C) and BSR‐1. As with the double BSRs, another tectonic uplift may explain the BGHS at unreasonably shallow depths. Alternatively, linear extrapolation of the geothermal gradient down to the hydrate‐bearing zones may not be appropriate if the gradient changes below the depths that were measured. Recognition of double BSRs (263 and 289 mbsf) and probable new BGHS (～230 mbsf) in the exploration wells implies that the BGHS has gradually migrated upward. Tectonically induced processes are thought to have enhanced dense and massive accumulation of gas hydrate deposits through effective methane recycling and condensation. To test the hypothetical models for the accumulation of gas hydrates in Nankai accretionary prism, we strongly propose to measure the equilibrium temperatures for the entire depth range down to the free gas zone below predicted BGHS and to reconstruct the water depths and uplift history of hydrate‐bearing area.     

Significance of earthquake-related anomalies in fluids of Val D'Agri (southern Italy)

Geochemical investigations carried out at the Campano–Lucano Apennine (Southern Italy) revealed the presence of fluids composed of a mixing between components of shallow and deep origin, where mantle-derived helium is also detectable. For the gas phase, the deep component is represented by both CH₄ and CO₂-rich gases, while the shallow one is N₂-dominated. Coinciding with the 3 April 1996  M _L=4.9 earthquake, the CH₄-rich component mixed with the shallow, N₂-dominated one at the Tramutola well (Val d'Agri), displaying wide variations in mixing proportions. In contrast, no significant modifications occurred in relation to the 1998 M _L=5.5 event. According to the collected data, an earthquake-related transient modification of local crustal permeability is suggested for the 1996 event. The different crustal response to the two events may be related to different stress distributions around the epicentres or may suggest a different tectonic connection between the Val d'Agri and the two earthquake locations.     

羌塘北缘开心岭—乌丽冻土区水溶烃组分及甲烷碳、氢同位素特征研究

羌塘北缘开心岭—乌丽冻土区沿隐伏断层发育多处冷泉含水溶解烷烃,采用水溶烃组分和甲烷的稳定碳、氢同位素特征对其成因开展了分析研究。结果表明,开心岭—乌丽冻土区水溶烃组分中甲烷含量比例高达99.83%~99.96%,同时伴随有少量乙烷、丙烷,另含微量的乙烯和丙烯。开心岭一带水溶烃甲烷δ¹³C_PDB值介于-46.5‰~-55.1‰,δD_VSMOW值为-281.0‰~-342.0‰;乌丽一带水溶烃甲烷δ¹³C_PDB值介于-47.8‰~-58.9‰,δD_VSMOW值为-339.0‰~-346.0‰,指示水溶烃甲烷为有机成因,但气源较复杂,利用δ¹³C_CH4-δD_CH4、δ¹³C₁-C₁/(C₂+C₃)等成因图解判别,得出甲烷主要属微生物气,次之为热解成因气,混有少量原油伴生气。推断甲烷主要为有机质在微生物作用下分解的烃类气体或次生生物气,与晚二叠世那益雄组含煤烃源岩有关,气源条件暗示该地区冻土带200~500 m深度内有利于微生物成因气为主的甲烷天然气水合物形成。     

青海聚乎更钻探区含水合物岩心气体组成及其指示意义

对青海聚乎更钻探区含天然 气水合物岩心气体组成特征进行研究,有助于弄清钻探区天然气水合物的气体成因及来源,对于区内天然气水合物的勘探开发具有重要的指导意义。对DK8-19、DK10-17、DK11-14、DK12- 13和DK13-11等5个钻孔获得的18个含水合物岩心样品,开展了气体组成和同位素特征及C_l/(C₂+C₃)-δ¹³C_C1、δD_C1-δ¹³C_C1和δ¹³C_C2-δ¹³C_C1等关系图解的综合研究。结果显示：青海聚乎 更钻探区含水合物岩心气体以轻烃为主,具湿气特征,其同位素表现为正碳同位素系列特征。除DK8-19孔浅层岩心烃类气体可能含有少量生物成因气外,钻探区其余各孔所有样品的气源组成均以热解成因气为主,为典型的有机成因烃类气体,且来源于淡水环境下形成的天然气。     

A review of the geochemistry of methane in natural gas hydrate

The largest accumulations on Earth of natural gas are in the form of gas hydrate, found mainly offshore in outer continental margin sediment and, to a lesser extent, in polar regions commonly associated with permafrost. Measurements of hydrocarbon gas compositions and of carbon-isotopic compositions of methane from natural gas hydrate samples, collected in subaquatic settings from around the world, suggest that methane guest molecules in the water clathrate structures are mainly derived by the microbial reduction of CO₂ from sedimentary organic matter. Typically, these hydrocarbon gases are composed of > 99% methane, with carbon-isotopic compositions (δ¹³C_PDB) ranging from − 57 to − 73‰. In only two regions, the Gulf of Mexico and the Caspian Sea, has mainly thermogenic methane been found in gas hydrate. There, hydrocarbon gases have methane contents ranging from 21 to 97%, with δ¹³C values ranging from − 29 to − 57‰. At a few locations, where the gas hydrate contains a mixture of microbial and thermal methane, microbial methane is always dominant. Continental gas hydrate, identified in Alaska and Russia, also has hydrocarbon gases composed of > 99% methane, with carbon-isotopic compositions ranging from − 41 to − 49‰. These gas hydrate deposits also contain a mixture of microbial and thermal methane, with thermal methane likely to be dominant. Published by Elsevier Science Ltd     

南海沉积物中烃类气体(酸解烃)特征及其成因与来源

烃类气体是形成天然气和天然气水合物的物质基础,可通过顶空气、吸附烃和酸解烃等方法来探测。南海473个站位767件沉积物样品的酸解烃分析结果表明,甲烷含量为0.8~22153.6μl/kg,平均为335.8μl/kg,并可分成台西南—东沙、笔架南、琼东南—西沙海槽、中建南—中业北、万安—南薇西和南沙海槽等6大异常区,其中南沙海槽是异常最强烈的地区,台西南盆地次之。154件甲烷样品的碳同位素分析结果表明,其δ13C1值为-101.7‰~-24.4‰(PDB标准,下同),平均为-44.5‰,其中南沙海槽的δ13C1值明显偏低,为-101.7‰~-71.4‰,应是微生物气或是以微生物气为主的混合气,而南海其他地区的δ13C1值相对较高,为-51.0‰~-24.4‰,明显属于热解气。     

Halogen concentrations in pore waters and sediments of the Nankai Trough,Japan: Implications for the origin of gas hydrates

Presented here are halogen concentrations (Cl, Br and I) in pore waters and sediments from three deep cores in gas hydrate fields of the Nankai Trough area. The three cores were drilled between 1999 and 2004 in different geologic regions of the northeastern Nankai Trough hydrate zone. Iodine concentrations in all three cores increase rapidly with depth from seawater concentrations (0.00043 mmol/L) to values of up to 0.45 mmol/L. The chemical form of I was identified as I⁻, in accordance with the anaerobic conditions in marine sediments below the SO₄ reduction depth. The increase in I is accompanied by a parallel, although lesser increase in Br concentrations, while Cl concentrations are close to seawater values throughout most of the profiles. Large concentration fluctuations of the three halogens in pore waters were found close to the lower boundary of the hydrate stability zone, related to processes of formation and dissociation of hydrates in this zone. Generally low concentrations of I and Br in sediments and the lack of correlation between sediment and pore water profiles speak against derivation of I and Br from local sediments and suggest transport of halogen rich fluids into the gas hydrate fields. Differences in the concentration profiles between the three cores indicate that modes of transportation shifted from an essentially vertical pattern in a sedimentary basin location to more horizontal patterns in accretionary ridge settings. Because of the close association between organic material and I and the similarity of transport behavior for I⁻ and CH₄, the results suggest that the CH₄ in the gas hydrates also was transported by aqueous fluids from older sediments into the present layers.     

Overview of the MITI Nankai Trough Wells: A Milestone in the Evaluation of Methane Hydrate Resources

Abstract. Bottom-simulating reflectors suggestive of the presence of methane hydrates are widely distributed below the ocean floor around Japan. In late 1999, drilling of the MITI Nankai Trough wells was conducted to explore this potential methane hydrate resource and a Tertiary conventional structure. The wells are located in the Northwest Pacific Ocean off Central Japan at a water depth of 945 m. A total of six wells were drilled, including the main well, two pilot wells, and three post survey wells at intervals of 10–100 m. All wells except the first confirmed the occurrence of hydrates based on logging-while-drilling, wire-line logging and/or coring using a pressure and temperature coring system in addition to conventional methods. Based on the various well profiles, four methane hydrate-bearing sand-rich intervals in turbidite fan deposits were recognized. Methane hydrates fill the pore spaces in these deposits, reaching saturation of up to 80 % in some layers. The methane hydrate-bearing turbiditic sand layers are less than 1 m thick, with a total thickness of 12–14 m. The bottom depth of high hydrate concentration correlates well with the depth of the bottom-simulating reflector. Based on these exploration results, the Japanese government inaugurated a 16-year methane hydrate exploitation program in 2001.     

Archaeal polar lipids in subseafloor sediments from the Nankai Trough: Implications for the distribution of methanogens in the deep marine subsurface

Although the methane in marine methane hydrates is mainly of microbial origin, information about the distribution of methanogens in subseafloor sediments is limited. To address this issue, we analyzed sediment core samples from two sites in the Nankai Trough, off the Pacific coast of central Japan, including those bearing methane hydrates from depths > 100 m below the seafloor (mbsf), for isopranyl ether-linked polar lipids (i.e. with polar head groups of phosphate, sugar, or both) as biomarkers of archaea, including methanogens. In most samples, including the deepest (381 mbsf), archaeol, and sn-2- and sn-3-hydroxyarchaeols were detected as their hydrolyzed derivatives. Concentrations of these three archaeal lipids correlated strongly with each other, suggesting a common biological source. The δ¹³C values of phytane derived from the phytanyl groups in the archaeal lipids were distinctly higher than those of methane, indicating that methanogens rather than anaerobic methanotrophic archaea were the major biological source. Depth profiles of polar sn-2-hydroxyarchaeol concentration were consistent with those of the potential methane production activity previously estimated from incubation of core sediments from the same sites. This observation, together with results of previous studies showing the presence of sn-2-hydroxyarchaeol mainly in shallow young sediments, strongly suggests that this polar lipid is a valid biomarker for in situ methanogens in sediments. There was a strong correlation between the concentration of polar sn-2-hydroxyarchaeol and that of total organic carbon, suggesting that bulk organic matter concentration is a primary control on the distribution of methanogens in sediments.     

Application of a Simulation Model for the Formation of Methane Hydrate to the Nankai Trough and the Blake Ridge: Natural Examples of Two End-member Cases

Abstract. Simulation experiments with a one-dimensional static model for formation of methane hydrate are used to demonstrate models of hydrate occurrence and its generation mechanism for two end-member cases. The simulation results compare well with experimental data for two natural examples (the Nankai Trough and the Blake Ridge).
At the MITI Nankai Trough wells, the hydrate occurrence is characterized by strongly hydrated sediments developing just above the BGHS. Such occurrence can be reproduced well by simulation in which the end-member case of upward advective fluid flow from below the BGHS is set. The strongly hydrated sediments is formed by oversaturated solution with free gas which directly enters the BGHS by the upward advective fluid flow. The recycling of dissociated methane of preexisting hydrate also contributes to the increase of hydrate saturation.
At the Site 997 in the Blake Ridge area, the hydrate occurrence is characterized by thick zone with poorly hydrated sediments and no hydrate zone developing above the hydrate zone. Such occurrence can be reproduced well by simulation in which the end-member case of in-situ biogenic production of methane in the sediment of methane hydrate zone is set. The distribution pattern of hydrate saturation is basically controlled by that of TOC. However, the hydrate concentration near the bottom of the hydrate zone is increased by the effect of recycling of dissociated methane of pre-existing hydrate. No hydrate zone expresses the geologic time needed until the local concentration of methane exceeds the solubility by gradual accumulation of in-situ biogenic methane with burial.     

论河北丰宁牛圈银（金）矿床的成矿时限问题

南沙海槽的构造和沉积受控于南海的构造运动和加里曼丹西北大陆边缘的演化,具有适于天然气水合物形成的物源基础、温压条件、输导系统和储藏场所。似海底反射层(BSR)出现在水深650~2 800 m、海底下65~350 m深的晚中新世沉积物中,与褶皱、逆冲推覆构造及穹窿构造有关;沉积物中的甲烷含量和孔隙水的SO24-含量表现出异常变化特征,硫酸盐-甲烷界面(SMI)深度仅为8~11 m;表层沉积的自生石膏和黄铁矿的成岩环境与甲烷流体排溢引起的厌氧甲烷氧化(AOM)有关,这些地球物理和地球化学指标均指示南沙海槽发育天然气水合物。研究表明,南沙海槽沉积物的甲烷以二氧化碳还原型微生物成因为主,少量为混合气,海槽东南部可能是最有潜力的天然气水合物远景区。     

中国近海天然气水合物找矿前景

天然气水合物是一种新型能源，在海底沉积物和陆上永远冻土带中均有广泛分布。西太平洋是全球三大天然气水合物成矿带之一，在其中已发现许多水合物矿床或矿点。中国近海，包括南海、东海和台湾东部海域，具备良好的天然气水合物成矿条件和找矿前景，并已在这些海域中发现了一系列的找矿标志。南海的西沙海槽、台湾西南陆坡和台西南盆地、笔架南盆地及其东缘增生楔、东沙群岛东南坡、南部陆坡区，东海的冲绳海槽和台湾东北部海域是中国近海最有利的天然气水合物找矿远景区。     

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

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.