Dissolution rates of pure methane hydrate and carbon-dioxide hydrate in undersaturated seawater at 1000-m depth

To help constrain models involving the chemical stability and lifetime of gas clathrate hydrates exposed at the seafloor, dissolution rates of pure methane and carbon-dioxide hydrates were measured directly on the seafloor within the nominal pressure-temperature (P/T) range of the gas hydrate stability zone. Other natural boundary conditions included variable flow velocity and undersaturation of seawater with respect to the hydrate-forming species. Four cylindrical test specimens of pure, polycrystalline CH₄ and CO₂ hydrate were grown and fully compacted in the laboratory, then transferred by pressure vessel to the seafloor (1028 m depth), exposed to the deep ocean environment, and monitored for 27 hours using time-lapse and HDTV cameras. Video analysis showed diameter reductions at rates between 0.94 and 1.20 μm/s and between 9.0 and 10.6 · 10⁻² μm/s for the CO₂ and CH₄ hydrates, respectively, corresponding to dissolution rates of 4.15 ± 0.5 mmol CO₂/m²s and 0.37 ± 0.03 mmol CH₄/m²s. The ratio of the dissolution rates fits a diffusive boundary layer model that incorporates relative gas solubilities appropriate to the field site, which implies that the kinetics of the dissolution of both hydrates is diffusion-controlled. The observed dissolution of several mm (CH₄) or tens of mm (CO₂) of hydrate from the sample surfaces per day has major implications for estimating the longevity of natural gas hydrate outcrops as well as for the possible roles of CO₂ hydrates in marine carbon sequestration strategies.     

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.     

天然气水合物成因探讨

天然气水合物是未来的能源资源。其分布于极地地区、深海地区及深水湖泊中。在海洋里,天然气水合物主要分布于外大陆边缘和洋岛的周围,其分布与近代火山的分布范围具有一致性。同位素组成表明天然气水合物甲烷主要是由自养产甲烷菌还原CO₂形成的。典型的大陆边缘沉积物有机碳含量低（＜0．5％～1．0％）,不足以产生天然气水合物带高含量的甲烷。赋存天然气水合物的沉积物时代主要为晚中新世-晚上新世,具有一定的时限性,并且天然气水合物与火山灰或火山砂共存,表明其形成与火山-热液体系有一定联系。火山与天然气水合物空间上的一致性表明,天然气水合物甲烷的底物可能主要是由洋底火山喷发带来的CO2。由前人研究结果推断 HCO^－₃在脱去两个O原子的同时,可能发生了亲核重排,羟基 H原子迁移到 C原子上,形成了甲酰基（HCO^－）,使甲烷的第一个 H原子来源于水。探讨了甲烷及其水合物的形成机制,提出了天然气水合物成因模型。     

水合物生成过程中碳同位素组成变化的实验研究

天然气水合物是一种新型的洁净能源。甲烷天然气水合物是储量最丰富的一种类型,常出现在深海中或极地大陆上,其生成的过程中会发生同位素的分馏效应。通过实验室模拟水合物生成的过程,利用天然海水与甲烷或二氧化碳气体反应,以及更接近实际生成环境的甲烷-海水-沉积物动态聚散实验,对甲烷水合物和二氧化碳水合物生成前后δ13C值进行测定,研究水合物生成过程中δ13C的变化情况。实验证明,水合物反应中碳同位素分馏是存在的,其变化程度明显小于氧同位素和氢同位素。甲烷水合物碳同位素的分馏系数αC的值为1000 3~1000 9。二氧化碳水合物生成反应后气相的碳、氧同位素变轻,重同位素趋向于进入水合物中,二氧化碳水合物碳同位素的分馏系数αC的值为1000 7~1001 2。海水中溶解的CO2气体在甲烷水合物形成过程中会被水合物捕获,从而使得δ13CDIC值变小,重的碳同位素趋于进入水合物中,而较轻的碳同位素留在海水中。但由于海水中含有的溶解CO2气体有限,经过多轮水合物动态聚散后δ13CDIC值的变化幅度会越来越小。     

Gas Sources of Natural Gas Hydrates in the Shenhu Drilling Area, South China Sea: Geochemical Evidence and Geological Analysis

The Shenhu gas hydrate drilling area is located in the central Baiyun sag, Zhu Ⅱ depression, Pearl River Mouth basin, northern South China Sea. The gas compositions contained in the hydrate-bearing zones is dominated by methane with content up to 99.89% and 99.91%. The carbon isotope of the methane (δ13C1 ) are 56.7‰ and 60.9‰, and its hydrogen isotope (δD) are 199‰ and 180‰, respectively, indicating the methane from the microbial reduction of CO2 . Based on the data of measured seafloor temperature and geothermal gradient, the gas formed hydrate reservoirs are from depths 24-1699 m below the seafloor, and main gas-generation zone is present at the depth interval of 416-1165 m. Gas-bearing zones include the Hanjiang Formation, Yuehai Formation, Wanshan Formation and Quaternary sediments. We infer that the microbial gas migrated laterally or vertically along faults (especially interlayer faults), slump structures, small-scale diapiric structures, regional sand beds and sedimentary boundaries to the hydrate stability zone, and formed natural gas hydrates in the upper Yuehai Formation and lower Wanshan Formation, probably with contribution of a little thermogenic gas from the deep sedments during this process.     

The control of Phanerozoic atmosphere and seawater composition by basalt–seawater exchange reactions

We present results from a long term geochemical cycling model, with a focus on the sensitivity of atmospheric carbon dioxide, oxygen, and the major element composition of seawater to seafloor spreading rates. This model incorporates rock weathering, basalt–seawater exchange reactions, and the formation and destruction of chemical sediments and organic matter. Hydrothermal reactions between seafloor and seawater involving calcium, magnesium, sodium, potassium, sulfate and carbon are the high temperature counterparts to low temperature redox, weathering, precipitation and diagenetic reactions. A major source of uncertainty is the extent to which these exchange fluxes are controlled by seafloor spreading rate. In addition, the return fluxes of these components to the atmospheric and primary silicate reservoirs reflect not only the overall rates of subduction and metamorphism, but the distribution of the overlying sedimentary burden and authigenic minerals formed during basalt alteration as well. In particular, we show how the stoichiometry of exchange fluxes (Mg/Ca and SO₄/Ca) may buffer atmospheric CO₂ and O₂ concentrations.     

Prediction of CH4 and CO2 hydrate phase equilibrium and cage occupancy from ab initio intermolecular potentials

Presented is an improved model for the prediction of phase equilibria and cage occupancy of CH₄ and CO₂ hydrate in aqueous systems. Different from most hydrate models that employ Kihara potential or Lennard-Jones potential with parameters derived from experimental phase equilibrium data of hydrates, we use atomic site-site potentials to account for the angle-dependent molecular interactions with parameters directly from ab initio calculation results. Because of this treatment, our model can predict the phase equilibria of CH₄ hydrate and CO₂ hydrate in binary systems over a wide temperature-pressure range (from 243-318 K, and from 10-3000 bar for CH₄ hydrate; from 253-293 K, and from 5-2000 bar for CO₂ hydrate) with accuracy close to experiment. The average deviation of this model from experimental data is less than 3% in pressures for a given temperature. This accuracy is similar to previous models for pressures below 500 bar, but is more accurate than previous models at higher pressures. This model is also capable of predicting the cage occupancy and hydration number for CH₄ hydrate and CO₂ hydrate without fitting any experimental data. The success of this study validates the predictability of ab initio intermolecular potentials for thermodynamic properties.     

Dissolution of basalts and peridotite in seawater, in the presence of ligands, and CO2: Implications for mineral sequestration of carbon dioxide

Steady-state silica release rates (r_Si) from basaltic glass and crystalline basalt of similar chemical composition as well as dunitic peridotite have been determined in far-from-equilibrium dissolution experiments at 25 °C and pH 3.6 in (a) artificial seawater solutions under 4 bar pCO₂, (b) varying ionic strength solutions, including acidified natural seawater, (c) acidified natural seawater of varying fluoride concentrations, and (d) acidified natural seawater of varying dissolved organic carbon concentrations. Glassy and crystalline basalts exhibit similar r_Si in solutions of varying ionic strength and cation concentrations. Rates of all solids are found to increase by 0.3-0.5 log units in the presence of a pCO₂ of 4 bar compared to CO₂ pressure of the atmosphere. At atmospheric CO₂ pressure, basaltic glass dissolution rates were most increased by the addition of fluoride to solution whereas crystalline basalt rates were most enhanced by the addition of organic ligands. In contrast, peridotite does not display any significant ligand-promoting effect, either in the presence of fluoride or organic acids. Most significantly, Si release rates from the basalts are found to be not more than 0.6 log units slower than corresponding rates of the peridotite at all conditions considered in this study. This difference becomes negligible in seawater suggesting that for the purposes of in-situ mineral sequestration, CO₂-charged seawater injected into basalt might be nearly as efficient as injection into peridotite.     

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.     

A natural hydrate dissolution experiment on complex multi-component hydrates on the sea floor

Dissolution of natural hydrate cores was measured using time-lapse photography on the seafloor at Barkley Canyon (850 m depth and 4.17 °C). Two types of hydrate fabrics in close contact with one another were studied: a “yellow” hydrate stained with condensate oil and a “white” hydrate. From thermogenic origins, both fabrics contained methane as well as heavier hydrocarbons. These multi-component hydrates were calculated to be well within p-T stability conditions (<200 m water depth needed at 4.17 °C). While stable in pressure and temperature, the hydrates were bathed in under-saturated seawater, which promoted dissolution. The flux of gas from the shrinking yellow hydrate core was 0.15 ± 0.01 mmol gas/m² s, while the white hydrate dissolved faster at 0.25 ± 0.02 mmol gas/m² s. To determine the controlling mechanism for the observed changes in the hydrate cores, experimental results were compared with an engineering correlation for convective mass transfer. Using water velocity as a fitting parameter, the correlation agreed well with results from a previous dissolution experiment on well-characterized synthetic hydrates. Even with a number of other unknowns, when applied to the natural hydrate, the mass transfer correlation predicted the dissolution rate within 20%. This seafloor-based experiment, along with visual observations of seafloor hydrate dissolution over a 3-day period, were used to further understand the fate of natural seafloor hydrates exposed on the seafloor. By showing that mass transfer is the rate-controlling mechanism for dissolution of these natural hydrate outcrops, proper hydrodynamic calculations can be employed to give a refined estimate on hydrate dissolution rates.     

Carbon Sequestration and Release from Antarctic Lakes: Lake Vida and West Lake Bonney (McMurdo Dry Valleys)

Perennial ice covers on many Antarctic lakes have resulted in high lake inorganic carbon contents. The objective of this paper was to evaluate and compare the brine and CO₂ chemistries of Lake Vida (Victoria Valley) and West Lake Bonney (Taylor Valley), two lakes of the McMurdo Dry Valleys (East Antarctica), and their potential consequences during global warming. An existing geochemical model (FREZCHEM-15) was used to convert measured molarity into molality needed for the FREZCHEM model, and this model added a new algorithm that converts measured DIC into carbonate alkalinity needed for the FREZCHEM model. While quite extensive geochemical information exists for ice-covered Taylor Valley lakes, such as West Lake Bonney, only limited information exists for the recently sampled brine of >25 m ice-thick Lake Vida. Lake Vida brine had a model-calculated pCO₂ = 0.60 bars at the field pH (6.20); West Lake Bonney had a model-calculated pCO₂ = 5.23 bars at the field pH (5.46). Despite the high degree of atmospheric CO₂ supersaturation in West Lake Bonney, it remains significantly undersaturated with the gas hydrate, CO₂·6H₂O, unless these gas hydrates are deep in the sediment layer or are metastable having formed under colder temperatures or greater pressures. Because of lower temperatures, Lake Vida could start forming CO₂·6H₂O at lower pCO₂ values than West Lake Bonney; but both lakes are significantly undersaturated with the gas hydrate, CO₂·6H₂O. For both lakes, simulation of global warming from current subzero temperatures (?13.4 °C in Lake Vida and ?4.7 °C in West Lake Bonney) to 10 °C has shown that a major loss of solution-phase carbon as CO₂ gases and carbonate minerals occurred when the temperatures rose above 0 °C and perennial ice covers would disappear. How important these Antarctic CO₂ sources will be for future global warming remains to be seen. But a recent paper has shown that methane increased in atmospheric concentration due to deglaciation about 10,000 years ago. So, CO₂ release from ice lakes might contribute to atmospheric gases in the future.     

Chemistry of fluids from a natural analogue for a geological CO2 storage site (Montmiral, France): Lessons for CO2–water–rock interaction assessment and monitoring

Chemical and isotope studies of natural CO₂ accumulations aid in assessing the chemical effects of CO₂ on rock and thus provide a potential for understanding the long-term geochemical processes involved in CO₂ geological storage. Several natural CO₂ accumulations were discovered during gas and oil exploration in France’s carbogaseous peri-Alpine province (south-eastern France) in the 1960s. One of these, the Montmiral accumulation at a depth of more than 2400 m, is currently being exploited. The chemical composition of the water collected at the wellhead has changed in time and the final salinity exceeds 75 g/L. These changes in time can be explained by assuming that the fraction of the reservoir brine in the recovered brine–CO₂–H₂O mixture varies, resulting in variable proportions of H₂O and brine in the sampled water. The proportions can be estimated in selected samples due to the availability of gas and water flowrate data. These data enabled the reconstruction of the chemical and isotope composition of the brine. The proportions of H₂O and brine can also be estimated from isotope (δ²H, δ¹⁸O) composition of collected water and δ¹⁸O of the sulfates or CO₂. The reconstituted brine has a salinity of more than 85 g/L and, according to its Br⁻ content and isotope (δ²H, δ¹⁸O, δ³⁴S) composition, originates from an evaporated Triassic seawater that underwent dilution by meteoric water. The reconstitution of the brine’s chemical composition enabled an evaluation of the CO₂–water–rock interactions based on: (1) mineral saturation indices; and (2) comparison with initial evaporated Triassic seawater. Dissolution of K- and SO₄-containing minerals such as K-feldspar and anhydrite, and precipitation of Ca and Mg containing minerals that are able to trap CO₂ (carbonates) are highlighted. The changes in concentration of these elements in the brine, which are attributed to CO₂ interactions, illustrate the relevance of monitoring the water quality at future industrial CO₂ storage sites.     

Molecular and isotopic partitioning of low-molecular-weight hydrocarbons during migration and gas hydrate precipitation in deposits of a high-flux seepage site

Detailed knowledge of the extent of post-genetic modifications affecting shallow submarine hydrocarbons fueled from the deep subsurface is fundamental for evaluating source and reservoir properties. We investigated gases from a submarine high-flux seepage site in the anoxic Eastern Black Sea in order to elucidate molecular and isotopic alterations of low-molecular-weight hydrocarbons (LMWHC) associated with upward migration through the sediment and precipitation of shallow gas hydrates. For this, near-surface sediment pressure cores and free gas venting from the seafloor were collected using autoclave technology at the Batumi seep area at 845 m water depth within the gas hydrate stability zone.Vent gas, gas from pressure core degassing, and from hydrate dissociation were strongly dominated by methane (> 99.85 mol.% of ∑[C₁–C₄, CO₂]). Molecular ratios of LMWHC (C₁/[C₂ + C₃] > 1000) and stable isotopic compositions of methane (δ¹³C = ? 53.5‰ V-PDB; D/H around ? 175‰ SMOW) indicated predominant microbial methane formation. C₁/C₂₊ ratios and stable isotopic compositions of LMWHC distinguished three gas types prevailing in the seepage area. Vent gas discharged into bottom waters was depleted in methane by > 0.03 mol.% (∑[C₁–C₄, CO₂]) relative to the other gas types and the virtual lack of ¹⁴C–CH₄ indicated a negligible input of methane from degradation of fresh organic matter. Of all gas types analyzed, vent gas was least affected by molecular fractionation, thus, its origin from the deep subsurface rather than from decomposing hydrates in near-surface sediments is likely.As a result of the anaerobic oxidation of methane, LMWHC in pressure cores in top sediments included smaller methane fractions [0.03 mol.% ∑(C₁–C₄, CO₂)] than gas released from pressure cores of more deeply buried sediments, where the fraction of methane was maximal due to its preferential incorporation in hydrate lattices. No indications for stable carbon isotopic fractionations of methane during hydrate crystallization from vent gas were found. Enrichments of ¹⁴C–CH₄ (1.4 pMC) in short cores relative to lower abundances (max. 0.6 pMC) in gas from long cores and gas hydrates substantiates recent methanogenesis utilizing modern organic matter deposited in top sediments of this high-flux hydrocarbon seep area.     

Oxygen-18 enrichment in the water of a clathrate hydrate

The equilibrium constants for the fractionation of H₂¹⁸O and H₂¹⁶O between liquid and solid phases were determined by slow freezing of ice and by slow formation of the clathrate hydrate of tetrahydrofuran from liquid solution. Both systems gave α = 1.0026₈. It is likely that oxygen-18 enrichment of the water in clathrate hydrates generally is essentially the same as for ice and that the relatively high oxygen-18 content observed in pore waters from some deep-sea sediments arises from the recent presence of methane hydrate.     

Halogen systematics in the Mallik 5L-38 gas hydrate production research well,Northwest Territories,Canada: Implications for the origin of gas hydrates under terrestrial permafrost conditions

The authors report here halogen concentrations in pore waters and sediments collected from the Mallik 5L-38 gas hydrate production research well, a permafrost location in the Mackenzie Delta, Northwest Territories, Canada. Iodine and Br are commonly enriched in waters associated with CH₄, reflecting the close association between these halogens and source organic materials. Pore waters collected from the Mallik well show I enrichment, by one order of magnitude above that of seawater, particularly in sandy layers below the gas hydrate stability zone (GHSZ). Although Cl and Br concentrations increase with depth similar to the I profile, they remain below seawater values. The increase in I concentrations observed below the GHSZ suggests that I-rich fluids responsible for the accumulation of CH₄ in gas hydrates are preferentially transported through the sandy permeable layers below the GHSZ. The Br and I concentrations and I/Br ratios in Mallik are considerably lower than those in marine gas hydrate locations, demonstrating a terrestrial nature for the organic materials responsible for the CH₄ at the Mallik site. Halogen systematics in Mallik suggest that they are the result of mixing between seawater, freshwater and an I-rich source fluid. The comparison between I/Br ratios in pore waters and sediments speaks against the origin of the source fluids within the host formations of gas hydrates, a finding compatible with the results from a limited set of ¹²⁹I/I ratios determined in pore waters, which gives a minimum age of 29 Ma for the source material, i.e. at the lower end of the age range of the host formations. The likely scenario for the gas hydrate formation in Mallik is the derivation of CH₄ together with I from the terrestrial source materials in formations other than the host layers through sandy permeable layers into the present gas hydrate zones.     

Development of detection and monitoring techniques of CO2 leakage from seafloor in sub-seabed CO2 storage

Carbon dioxide capture and storage (CCS) in sub-seabed geological formations is currently being studied as a potential option to mitigate the accumulation of anthropogenic CO₂ in the atmosphere. To investigate the validity of CO₂ storage in the sub-seafloor, development of techniques to detect and monitor CO₂ leaked from the seafloor is vital. Seafloor-based acoustic tomography is a technique that can be used to observe emissions of liquid CO₂ or CO₂ gas bubbles from the seafloor. By deploying a number of acoustic tomography units in a seabed area used for CCS, CO₂ leakage from the seafloor can be monitored. In addition, an in situ pH/pCO₂ sensor can take rapid and high-precision measurements in seawater, and is, therefore, able to detect pH and pCO₂ changes due to the leaked CO₂. The pH sensor uses a solid-state pH electrode and reference electrode instead of a glass electrode, and is sealed within a gas permeable membrane filled with an inner solution. Thus, by installing a pH/pCO₂ sensor onto an autonomous underwater vehicle (AUV), an automated observation technology is realized that can detect and monitor CO₂ leakage from the seafloor. Furthermore, by towing a multi-layer monitoring system (a number of pH/pCO₂ sensors and transponders) behind the AUV, the dispersion of leaked CO₂ in a CCS area can also be observed. Finally, an automatic elevator can observe the time-series dispersion of leaked CO₂. The seafloor-mounted automatic elevator consists of a buoy equipped with pH/pCO₂ and depth sensors, and uses an Eulerian method to collect spatially continuous data as it ascends and descends.Hence, CO₂ leakage from the seafloor is detected and monitored as follows. Step 1: monitor CO₂ leakage by seafloor-based acoustic tomography. Step 2: conduct mapping survey of the leakage point by using the pH/pCO₂ sensor installed in the AUV. Step 3: observe the impacted area by using a remotely operated underwater vehicle or the automatic elevator, or by towing the multi-layer monitoring system.     

海底天然气渗漏系统演化特征及对形成水合物的影响

通过天然气沉淀水合物的动力学模拟计算,研究了墨西哥湾GC185区BushHill海底天然气渗漏系统的演化特征及对水合物沉淀的影响。渗漏早期,天然气渗漏速度大(q>18.4kg/m2-a),海底沉积以泥火山为主,渗漏天然气具有与气源天然气几乎一致的组成,形成的水合物具有最重的天然气成分。渗漏晚期,天然气渗漏速度很慢(q<0.55kg/m2-a),在海底附近没有水合物沉淀,主要以冷泉碳酸盐岩发育为主,水合物产于海底之下一定深度的沉积层中。介于二者间的渗漏中期(q:0.55～18.4kg/m2-a),海底发育水合物、自养生物群为特征,渗漏速度控制了水合物和渗漏天然气的组成及沉淀水合物的天然气比例。BushHill渗漏系统近10年的深潜重复采样显示,渗漏天然气和水合物天然气的化学组成在时空上是多变的,相对应的渗漏速度在时间上的变化约为3倍,在空间上的变化近2个数量级。     

水力输送法开采海底浅层天然气水合物技术研究

海洋天然气水合物占全球水合物总储量的99%,海洋天然气水合物大部分沉积在海底浅层没有良好的覆盖层,无法采用开采传统油气资源的方法进行开采.为了开采海底浅层天然气水合物,分析了海洋天然气水合物的存在类型及地质特征,探讨了目前开采海洋天然气水合物的理论方法及局限性.根据海底天然气水合物成矿的地质特点及水合物的物理特性,提出了以水力输送技术为主要理论的海洋浅层天然气水合物开采方法.该方法克服了其他方法开采海底天然气水合物面临的技术困难,为海洋天然气水合物的开采提供了技术基础及理论支撑.     

Velocity-porosity relationships in hydrate-bearing sediments measured from pressure cores,Shenhu Area,South China Sea

Evaluating velocity-porosity relationships of hydrate-bearing marine sediments is essential for characterizing natural gas hydrates below seafloor as either a potential energy resource or geohazards risks. Four sites had cored using pressure and non-pressure methods during the gas hydrates drilling project (GMGS4) expedition at Shenhu Area, north slope of the South China Sea. Sediments were cored above, below, and through the gas-hydrate-bearing zone guided with logging-while-drilling analysis results. Gamma density and P-wave velocity were measured in each pressure core before subsampling. Methane hydrates volumes in total 62 samples were calculated from the moles of excess methane collected during depressurization experiments. The concentration of methane hydrates ranged from 0.3% to 32.3%. The concentrations of pore fluid (25.44% to 68.82%) and sediments (23.63% to 54.28%) were calculated from the gamma density. The regression models of P-wave velocity were derived and compared with a global empirical equation derived from shallow, unconsolidated sediments data. The results were close to the global trend when the fluid concentration is larger than the critical porosity. It is concluded that the dominant factor of P-wave velocity in hydrate-bearing marine sediments is the presence of the hydrate. Methane hydrates can reduce the fluid concentration by discharging the pore fluid and occupying the original pore space of sediments after its formation.©2022 China Geology Editorial Office.     

Exhaustive brine production and complete CO2 storage in Jianghan Basin of China

Pressure buildup limits CO₂ injectivity and storage capacity and pressure loss limits the brine production capacity and security, particularly for closed and semi-closed formations. In this study, we conduct a multiwell model to examine the potential advantages of combined exhaustive brine production and complete CO₂ storage in deep saline formations in the Jiangling Depression, Jianghan Basin of China. Simulation results show that the simultaneous brine extraction and CO₂ storage in saline formation not only effectively regulate near-wellbore and regional pressure of storage formation, but also can significantly enhance brine production capacity and CO₂ injectivity as well as storage capacity, thereby achieving maximum utilization of underground space. In addition, the combination of brine production and CO₂ injection can effectively mitigate the leakage risk between the geological units. With regard to the scheme of brine production and CO₂ injection, constant pressure injection is much superior to constant rate injection thanks to the mutual enhancement effect. The simultaneous brine production of nine wells and CO₂ injection of four wells under the constant pressure injection scheme act best in all respects of pressure regulation, brine production efficiency, CO₂ injectivity and storage capacity as well as leakage risk mitigation. Several ways to further optimize the combined strategy are investigated and the results show that increasing the injection pressure and adopting fully penetrating production wells can further significantly enhance the combined efficiency; however, there is no obvious promoting effect by shortening the well spacing and changing the well placement.