天然气水合物体系动态演化研究（I）：地质历史演变

1995年Dickens对55．5Ma前古新世末增温事件进行了研究，提出天然气水合物作为全球环境变化重要因子的假说．认为古新世末增温事件溶解无机碳-2～-3‰的^13δC位移可以用水合物所含甲烷的释放与随后氧化成二氧化碳来解释．此后，地质历史演变中的天然气水合物演化研究蓬勃发展，本文总结古新世末增温事件、新元古代末期雪球事件、第四纪千年尺度事件等最新进展，为天然气水合物动态演化研究提供基础．开展天然气水合物-天然气体系动态演化过程数值模拟与特征分析，可望促进天然气水合物在全球变化与碳循环中作用的深入认识．     

非活动大陆边缘的天然气水合物及其成藏过程述评

非活动陆缘是板块活动相对较弱的地区，也是水合物发育的有利地区。通过对世界各地非活动陆缘地区水合物富集情况的系统分析，发现断褶组合构造、底辟构造以及“麻坑”地貌（Pockmark)与水合物的关系密切。尽管模拟海底反射层（Bottom Simulating Reflector,简称BSR，下同）是最重要的水合物识别标志，但水合物与BSR之间并不存在严格的一一对应关系。非活动陆缘具有丰富的烃类物质来源和适宜的温压条件，而断裂－褶皱组合构造、垒堑式构造和底辟构造等则为烃类气体的运移、富集和成藏提供了有利的构造环境，便于最终形成水合物。非活动陆缘的深水区往往发育有多期叠合盆地，因其物源、温压、构造和沉积条件的内在关联性，常常形成深部石油、中部天然气、浅部水合物的“三位一体”烃类能源结构模式。     

A methane fuse for the Cambrian explosion: carbon cycles and true polar wander

The dramatic diversification of animal groups known as the Cambrian Explosion (evolution's ‘Big Bang’) remains an unsolved puzzle in Earth Science. The Vendian–Cambrian interval is characterized by anomalously high rates of apparent plate motion, interpreted as True Polar Wander (TPW), and by more than a dozen large, high-frequency perturbations in carbon isotopes that dwarf all others observed through the past 65 million years. We suggest that these biological, tectonic, and geochemical events are intimately related in the following fashion. First, tropical continental margins and shelf-slopes which formed during fragmentation of the supercontinent Rodinia accumulated massive quantities of isotopically-light organic carbon during Late Neoproterozoic time, as indicated by strikingly heavy isotope ratios in inorganic carbon during interglacial intervals. Second, an initial phase of Vendian TPW moved these organic-rich deposits to high latitude, where conditions favored trapping biogenic methane in layers of gas hydrate and perhaps permafrost. Continued sedimentation during Late Vendian time added additional hydrate/gas storage volume and stabilized underlying units until the geothermal gradient moved them out of the clathrate stability field, building up deep reservoirs of highly pressurized methane. Finally, a burst of TPW brought these deposits back to the Tropics, where they gradually warmed and were subjected to regional-scale thermohaline eddy variation and related sedimentation regime changes. Responding to the stochastic character of such changes, each reservoir reached a critical failure point independently at times throughout the Cambrian. By analogy with the Late Paleocene Thermal Maximum event, these methane deposits yield transient, greenhouse-induced pulses of global warming when they erupt. Temperature correlates powerfully with biodiversity; the biochemical kinetics of metabolism at higher temperature decrease generation time and maintain relatively rich and dense invertebrate populations. Repeated thermal pulses along with progressive disruption and alteration of global ocean circulation patterns by TPW could cause the increase in diversity that accompanied the radiation of metazoans. We suggest that a methane ‘fuse’ ignited the Cambrian Evolutionary Explosion.     

天然气水合物体系动态演化研究(Ⅲ):水合物的产生、聚集和分解

从天然气水合物的产生、聚集和分解，分析天然气水合物的动态演化过程，沉积压实、地温梯度、构造运动以及深部流体对水合物产生的效率起决定作用，根据流体的运移和天然气水合物在水合物稳定带中的分布状况，天然气水合物的聚集可以分为构造聚集、地层聚集和混合聚集三种模式，当由于各种原因引起海底温压条件变化时，天然气水合物会发生分解，水合物也会在水体中上浮，在这个过程中，水合物的分解速率能高出其溶解速率二至三个数量级，海底泥火山、甲烷气柱、甲烷气裂缝、双似海底反射等大量的证据，都有助于揭示天然气水合物体系的动态演化的特征，弄清楚天然气水合物的动态演化过程对于我们未来对这种潜在能源的开发利用，并分析其在全球变化、碳循环以及海底滑坡中所起的作用有着相当重要的意义。     

利用不纯净十水芒硝与纯净氯化钾制取硫酸钾的研究

本文通过相图分析，对利用不纯净十水芒硝与纯净氯化钾通过二步转化制取硫酸钾进行了物料配比计算．给出了最佳物料配比及十水芒硝中氯离子的最大含量，对实际生产有指导意义。     

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.     

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.     

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.     

DEM simulations of methane hydrate exploitation by thermal recovery and depressurization methods

Methane hydrate (MH, also called fiery ice) exists in forms of pore filling, cementing and load-bearing skeleton in the methane hydrate bearing sediment (MHBS) and affects its mechanical behavior greatly. To study the changes of macro-scale and micro-scale mechanical behaviors of MHBS during exploitation by thermal recovery and depressurization methods, a novel 2D thermo-hydro-mechanical bonded contact model was proposed and implemented into a platform of distinct element method (DEM), PFC2D. MHBS samples were first biaxially compressed to different deviator stress levels to model different in-situ stress conditions. With the deviator stress maintained at constant, the temperature was then raised to simulate the thermal recovery process or the pore water pressure (i.e. confining pressure for MH bond) was decreased to simulate the depressurization process. DEM simulation results showed that: during exploitation, the axial strain increased with the increase of temperature (in the thermal recovery method) or decrease of pore water pressure (in the depressurization method); sample collapsed during MH dissociation if the deviator stress applied was larger than the compression strength of a pure host sand sample; sample experienced volume contraction but its void ratio was slightly larger than the pure host sand sample at the same axial strain throughout the test. By comparison with the laboratory test results, the new model was validated to be capable of reproducing the exploitation process by thermal recovery and depressurization methods. In addition, some micro-scale parameters, such as contact distribution, bond distribution, and averaged pure rotation rate, were also analyzed to investigate their relationships with the macroscopic responses.