Investigation of gas content of organic-rich shale:A case study from Lower Permian shale in southern North China Basin,central China

Measuring gas content is an essential step in estimating the commerciality of gas reserves. In this study,eight shale core samples from the Mouye-1 well were measured using a homemade patented gas desorption apparatus to determine their gas contents. Due to the air contamination that is introduced into the desorption canister, a mathematical method was devised to correct the gas quantity and quality.Compared to the chemical compositions of desorbed gas, the chemical compositions of residual gas are somewhat different. In residual gas, carbon dioxide and nitrogen record a slight increase, and propane is first observed. This phenomenon may be related to the exposure time during the transportation of shale samples from the drilling site to the laboratory, as well as the differences in the mass, size and adsorptivity of different gas molecules. In addition to a series of conventional methods, including the USBM direct method and the Amoco Curve Fit(ACF) method, which were used here for lost gas content estimation, a Modified Curve Fit(MCF) method, based on the 'bidisperse' diffusion model, was established to estimate lost gas content. By fitting the ACF and MCF models to gas desorption data, we determined that the MCF method could reasonably describe the gas desorption data over the entire time period, whereas the ACF method failed. The failure of the ACF method to describe the gas desorption process may be related to its restrictive assumption of a single pore size within shale samples. In comparison to the indirect method, this study demonstrates that none of the three methods studied in this investigation(USBM, ACF and MCF) could individually estimate the lost gas contents of all shale samples and that the proportion of free gas relative to total gas has a significant effect on the estimation accuracy of the selected method. When the ratio of free gas to total gas is lower than 45%, the USBM method is the best for estimating the lost gas content, whereas when the ratio ranges from 45% to 75% or is more than 75%, the ACF and MCF methods, are the best options respectively.     

Multi-factor sensitivity analysis on the stability of submarine hydrate-bearing slope

There are many factors affecting the instability of the submarine hydrate-bearing slope (SHBS), and the interaction with hydrate is very complicated. In this paper, the mechanical mechanism of the static liquefaction and instability of submarine slope caused by the dissociation of natural gas hydrate (NGH) resulting in the rapid increase of pore pressure of gas hydrate-bearing sediments (GHBS) and the decrease of effective stress are analyzed based on the time series and type of SHBS. Then, taking the typical submarine slope in the northern South China Sea as an example, four important factors affecting the stability of SHBS are selected, such as the degree of hydrate dissociation, the depth of hydrate burial, the thickness of hydrate, and the depth of seawater. According to the principle of orthogonal method, 25 orthogonal test schemes with 4 factors and 5 levels are designed and the safety factors of submarine slope stability of each scheme are calculated by using the strength reduction finite element method. By means of the orthogonal design range analysis and the variance analysis, sensitivity of influential factors on stability of SHBS are obtained. The results show that the degree of hydrate dissociation is the most sensitive, followed by hydrate burial depth, the thickness of hydrate and the depth of seawater. Finally, the concept of gas hydrate critical burial depth is put forward according to the influence law of gas hydrate burial depth, and the numerical simulation for specific submarine slope is carried out, which indicates the existence of critical burial depth.     

川东南丁山地区龙马溪组页岩裂缝特征及对含气性的影响

川东南丁山地区是近年来四川盆地页岩气勘探开发的热点区域,裂缝的发育对页岩含气性及保存条件有重要的影响。综合运用野外露头、岩心、测井资料,结合岩石脆性矿物含量、岩石力学参数等数据,深入分析龙马溪组页岩裂缝发育特征和控制因素,并探讨了裂缝发育对含气性的影响。结果表明,丁山地区龙马溪组页岩裂缝主要以构造成因的剪切缝为主,裂缝优势方位共6组,主要包括4组平面剪切缝和2组剖面剪切缝,其发育主要受2个方向、3个阶段的构造应力场影响而成;裂缝延伸稳定,平均密度小,宽度小,充填程度高,主要被方解石和黄铁矿等充填。裂缝受控因素主要包括古构造应力场、构造部位、脆性矿物组分、岩石力学性质等;断层对裂缝发育具有明显的控制作用,其中断层两盘均存在裂缝发育程度急剧下降的临界范围,临界范围内裂缝发育程度高,超过此临界范围,裂缝发育程度变差且变化趋于平缓;不同期次的裂缝中,形成时间晚、规模过大、充填程度不高、与现今地应力方向一致或呈低角度相交的裂缝易造成页岩气的散失,对提高页岩含气性不利;龙马溪组岩石脆性矿物含量高,脆性指数属中等偏上程度,有利于构造缝发育且可压性较好。随着距齐岳山断裂距离的适当增加,龙马溪组页岩埋藏深度适中,地层压力增大,抗压强度增强高,脆性指数适中,构造保存条件变好,有利于不同方位的裂缝发育和页岩含气量的增加,位于该区域的DY2井与DY4井均位于该有利区域,含气性良好。研究结果对下一步深化页岩气勘探开发具有重要指导作用。     

番红砗磲外套膜色素提取条件优化及成分分析

以番红砗磲(Tridacna crocea)为实验对象,通过单因素对比实验对其外套膜色素的提取条件进行了优化,并利用薄层层析色谱法对色素组成进行了初步分析。结果表明:丙酮和乙醇为适宜的番红砗磲外套膜色素提取剂;使用丙酮为提取剂时,浸提时间为4 h,提取温度为25℃,料液比为1︰40。使用乙醇为提取剂时,浸提时间为4 h,提取温度为30℃,料液比为1︰200;利用薄层色谱法分离外套膜颜色为蓝色和红棕色的番红砗磲外套膜色素后发现,蓝色番红砗磲外套膜色素由9种色素组分构成,红棕色个体番红砗磲外套膜色素由10种色素组分构成。     

柴达木盆地烃蚀变矿物高光谱遥感识别研究

高光谱遥感识别烃蚀变矿物可用于探测油气烃类微渗漏和定位地下油气藏.以有天然气分布的柴达木盆地东部三湖地区为研究区,对Hyperion高光谱数据进行重采样处理,克服了目标识别矿物不明显和传感器低信噪比的影响.通过确定烃蚀变矿物高光谱遥感探测的指示标志,采用线性光谱(SAM)拟合与光谱匹配(SAM)相结合的方法确定了影像端元对应的矿物组分.识别结果表明,合理缩减影像波段数和确定影像端元的方法,能有效提高烃蚀变矿物的高光谱遥感识别精度.     

Effective medium modeling to assess gas hydrate and free-gas evident from the velocity structure in the Makran accretionary prism, offshore Pakistan

Seismic properties of sediments are strongly influenced by pore fluids. Stiffness of unconsolidated marine sediment increases with the presence of gas hydrate and decreases with the presence of gas. A strong bottom-simulating reflector (BSR) observed on a seismic profile in the Makran accretionary prism, offshore Pakistan, indicates the presence of gas hydrate and free-gas across the BSR. Elastic properties of gas depend largely on pressure and temperature. We, therefore, first determine the elastic modulus of gas at pressure and temperature calculated at the BSR depth in the study region. The interval velocities derived from the seismic data are interpreted by the effective medium theory, which is a combination of self-consistent approximation and differential effective medium theories, together with a smoothing approximation, for assessment of gas hydrate and free-gas. The results show the saturations of gas hydrate and free-gas as 22 and 2.4% of pore space, respectively, across the BSR.     

Geochemistry of pore waters from the Xisha Trough, northern South China Sea and their implications for gas hydrates

This paper reports all available geochemical data on sediments and pore waters from the Xisha Trough on the northern continental margin of the South China Sea. The methane concentrations in marine sediments display a downhole increasing trend and their carbon isotopic compositions (δ ¹³C = −25 to −51‰) indicate a thermogenic origin. Pore water Cl⁻ concentrations show a range from 537 to 730 mM, and the high Cl⁻ samples also have higher concentrations of Br⁻, Na⁺, K⁺, and Mg²⁺, implying mixing between normal seawater and brine in the basin. The SO₄ ²⁻ concentrations of pore waters vary from 19.9 to 36.8 mM, and show a downhole decreasing trend. Calculated SMI (sulfate-methane interfaces) depths and sulfate gradients are between 21 and 47 mbsf, and between −0.7 and −1.7 mM/m, respectively, which are similar to values in gas hydrate locations worldwide and suggest a high methane flux in the basin. Overall, the geochemical data, together with geological and geophysical evidence, such as the high sedimentation rates, high organic carbon contents, thick sediment piles, salt and mud diapirs, active faulting, abundant thermogenic gases, and occurrence of huge bottom simulating reflector (BSR), are suggestive of a favorable condition for occurrence of gas hydrates in this region.     

6种鱼类肌肉组织肌苷酸的检测分析

采用高效液相色谱技术,在国内首次测定了条纹斑竹鲨(Chilocsyllium plagiosum)、大黄鱼(Pseudosci-aena crocea)、鳜(Siniperca chuatsi)、青石斑鱼(Epinephelus awoara)、牙鲆(Paralichthys olivaceus)和乌塘鳢(Bostrichthys sinensis)等6种鱼类新鲜和冻存肌肉组织中肌苷酸含量。结果表明:(1)不同鱼类肌肉组织中肌苷酸质量比不同,牙鲆新鲜肌肉组织中肌苷酸质量比最高,为4.214 mg/g,其余5种鱼类为2.365~3.634 mg/g。(2)10 d冻存试验中,经-70℃超低温冻存,6种鱼类冻存肌肉组织中肌苷酸质量比均高于新鲜肌肉组织,大黄鱼肌肉组织冻存1 d肌苷酸质量比达最大值,鳜肌肉组织冻存10 d肌苷酸质量比呈上升态势未出现最大值,其余5种鱼类肌肉组织肌苷酸质量比均在冻存第5天达到最大值。长时间的冻存将会降低食用鱼肉中肌苷酸质量比,导致鲜味下降,但经1周左右短时间的冻存后可明显提高鱼肉中肌苷酸质量比,增加鲜味,提高食用价值。     

Winkler's method overestimates dissolved oxygen in seawater: Iodate interference and its oceanographic implications

Dissolved oxygen in seawater has been determined by using the Winkler's reaction scheme for decades. An interference in this reaction scheme that has been heretofore overlooked is the presence of naturally occurring iodate in seawater. Each mole of iodate can result in an apparent presence of 1.5 mol of dissolved oxygen. At the concentrations of iodate in the surface and deep open ocean, it can lead to an overestimation of 0.52 ± 0.15 and 0.63 ± 0.05 μmol kg^− 1 of oxygen in these waters respectively. In coastal and inshore waters, the effect is less predictable as the concentration of iodate is more variable. The solubility of oxygen in seawater was likely overestimated in data sources that were based on the Winkler's reaction scheme for the determination of oxygen. The solubility equation of García and Gordon [Garcia H.E., Gordon, L.I., 1992. Oxygen solubility in seawater: Better fitting equations. Limnol. Oceanogr. 37, 1307–1312] derived from the results of Benson and Krause [Benson, F.B., Krause, D. Jr., 1984. The concentration and isotopic fractionation of oxygen dissolved in freshwater and seawater in equilibrium with the atmosphere. Limnol. Oceanogr. 29, 620–632] is free from this source of error and is recommended for general use. By neglecting the presence of iodate, the average global super-saturation of oxygen in the surface oceans and the corresponding efflux of oxygen to the atmosphere both have been overestimated by about 8%. Regionally, in areas where the degree of super-saturation or under-saturation of oxygen in the surface water is small, such as in the tropical oceans, the net air–sea exchange flux can be grossly under- or overestimated. Even the estimated direction of the exchange can be reversed. Furthermore, the presence of iodate can lead to an overestimation of the saturation anomaly of oxygen in the upper ocean attributed to biological production by 0.23 ± 0.07%. AOU may have been underestimated by 0.52 ± 0.15 and 0.63 ± 0.05 μmol kg^− 1 in the surface mixed layer and deep water, while preformed phosphate and preformed nitrate may have been overestimated by 0.004 ± 0.001 and 0.06 ± 0.02 μmol kg^− 1 in the surface mixed layer, and 0.005 ± 0.0004 and 0.073 ± 0.006 μmol kg^− 1 in the deep water. These are small but not negligible corrections, especially in areas where the values of these parameters are small. At the increasing level of sophistication in the interpretation of oxygen data, this source of error should now be taken into account. Nevertheless, in order to avoid confusion, an internationally accepted standard needs to be adopted before these corrections can be applied.     

A predictive numerical model for potential mapping of the gas hydrate stability zone in the Gulf of Cadiz

This paper presents a computational model for mapping the regional 3D distribution in which seafloor gas hydrates would be stable, that is carried out in a Geographical Information System (GIS) environment. The construction of the model is comprised of three primary steps, namely: (1) the construction of surfaces for the various variables based on available 3D data (seafloor temperature, geothermal gradient and depth-pressure); (2) the calculation of the gas function equilibrium functions for the various hydrocarbon compositions reported from hydrate and sediment samples; and (3) the calculation of the thickness of the hydrate stability zone. The solution is based on a transcendental function, which is solved iteratively in a GIS environment.The model has been applied in the northernmost continental slope of the Gulf of Cadiz, an area where an abundant supply for hydrate formation, such as extensive hydrocarbon seeps, diapirs and fault structures, is combined with deep undercurrents and a complex seafloor morphology. In the Gulf of Cadiz, the model depicts the distribution of the base of the gas hydrate stability zone for both biogenic and thermogenic gas compositions, and explains the geometry and distribution of geological structures derived from gas venting in the Tasyo Field (Gulf of Cadiz) and the generation of BSR levels on the upper continental slope.