Weathering characteristics of the Lower Paleozoic black shale in northwestern Guizhou Province,south China

The northwestern Guizhou in the Yangtze Craton of south China has a tremendous potential of shale gas resource. In this paper, we present results from major and trace elements, total organic carbon, mineralogical composition analysis and petrophysical parameters to characterise shale weathering features. Further, the differences of black shale between underground and outcrops have also been presented to examine the changes of black shale after weathering. Our results show that the trace elements of shale have varying degrees of loss in the weathering leaching process, both in Niutitang shale and Longmaxi shale, the loss of B, V, Ni, Cu, Zn and Ba is obvious, but the element migration quantity in the former is greater than in the latter. Decomposition of minerals such as pyrite, feldspar and calcite result in the leaching of Na, Ca, Mg and Fe. The loss rate of total organic carbon (TOC) in black shales ranges from 18% to 70% with an average of 43%; moreover, the loss of organic carbon in samples with high TOC content is larger than in those samples with low TOC content. Results following the testing of porosity and permeability show that porosity increases significantly after weathering but permeability changes little. Furthermore, the increment of porosity is greater in the Niutitang shale (with more sulphide minerals) than in the Longmaxi shale, suggesting that the oxidation of sulphide minerals may have led to the formation of an acidic environment, causing the other minerals in the black shale to weather more quickly, thus resulting in increased porosity. The content of clay minerals in the core samples is slightly lesser than the outcrop samples, but the TOC content in the core samples is greater and has a larger specific surface area. This suggest that the TOC content played a decisive role on the specific surface area of shale. In addition, changes in the black shale caused by the weathering process mainly depend on the mineral composition and the TOC content in shale. In this study, we try to establish relations between outcrop samples and core samples, in order to better understand the underground characteristics of shale reservoir.     

黔西北地区龙马溪组页岩气储层孔隙特征及其储气意义

中国南方下志留统龙马溪组海相页岩有机质含量高且热成熟度高,是重要的页岩气储集层位。本文以黔西北地区习页1井与桐页1井的岩心样品为研究对象,研究龙马溪组页岩的孔隙特征及孔隙发育的影响因素,并对其储气性能进行综合的分析与评价。通过扫描电镜的大量观察可知,该区龙马溪组页岩内发育的孔隙多为纳米(nm)量级,包含矿物基质孔(可分为粒间孔和粒内孔)、有机质孔以及微裂缝等多种类型的孔隙,其中有机质孔最为发育。通过测试可知,该区页岩的总有机碳(TOC)含量平均为3.80%,热成熟度(Ro)平均为2.73%,有效孔隙度平均为1.56%;主要组成矿物为黏土矿物与碎屑矿物(石英、长石等),黏土矿物含量平均为32.42%,碎屑矿物含量平均为43.97%;BET比表面积平均为16.98m2/g,BJH总孔体积平均为0.013 7mL/g,孔隙的平均孔径为33.75nm。通过分析可知,TOC含量为孔隙发育的主要影响因素,样品的有效孔隙度与TOC、碎屑矿物含量呈线性正相关关系,与黏土矿物含量呈线性负相关关系。另测得样品对甲烷气体的饱和吸附量平均为2.42m3/t,饱和吸附量与TOC含量呈强烈的正相关性,TOC含量为吸附性能的主控因素;饱和吸附量与有效孔隙度、碎屑矿物含量、BET比表面积以及BJH总孔体积均呈明显的正相关性,而与黏土矿物含量的相关性不显著。     

页岩气储层孔隙类型及特征研究:以渝东南下古生界为例

通过薄片分析、扫描电镜及氩离子抛光技术,对渝东南下古生界含气页岩中的孔隙类型及特征进行了分类观察、描述,结合有机碳含量、X衍射、岩石物性、氮气吸附及甲烷等温吸附实验测试,分析了页岩气储层中各类孔隙的储气贡献,探讨这些孔隙对页岩中烃类运移的影响。研究认为,有机质孔隙、颗粒内孔、粒间孔隙及微裂隙是页岩气储层孔隙的4种类型,有机质表面的分散状孔隙多为nm级,石英碎屑可形成粒内或粒间孔隙,黄铁矿颗粒内部小晶体排列分布产生孔隙空间,黏土絮状沉淀形成片粒状结构孔隙,微裂隙普遍发育在页岩基质中,可达mm级。不同类型的孔隙能够为页岩气的赋存提供不同尺度的储集空间,页岩吸附含气量与表征孔隙特征的参数(TOC、BET比表面积、BJH总孔体积)具有显著的正相关关系。微裂隙与粒间孔隙对页岩中烃类的运移最有利。     

Organic matter maturity and oil/gas prospects in Middle-Upper Proterozoic and Lower Paleozoic carbonate rocks in northern China

Middle-Upper Proterozoic and Lower Paleozoic carbonate formations in northern China are well developed with an accumulative thickness of 6000–1400 m. Both seepages and oils have been found in the outcrops and drilling wells. The maturity of organic matter in these carbonate formations in obviously lower than that in southern China, as viewed from reflectance (R°), H/C (atomic ratio), the amount and distribution of hydrocarbons,T _max°C and so on.T _max°C may be used as a principal index for determining the maturity of organic matter in carbonate rock-covered areas. According to the results of themeasurement ofT _max°C andR° for natural samples and simulating experiments on bitumens from carbonate rocks, the limitation values for oil and gas have been estimated at 455°C (R°=1.35) and 476°C(R°=2.25), respectively. On this basis, the map of organic matter maturity for the Middle-Upper Proterozoic, Ordovician, Cambrian and Carboniferous of northern China has been compiled. It has been proposed that prospects of both oil and gas are expected, with oil and condensate dominant in the Ordovician, and condensate and dry gas in the Middle-Upper Proterozoic. The Cambrian is intermediate between them.     

Geochemistry of organic matter and elements of black shale during weathering in Northern Guizhou,Southwestern China: Their mobilization and inter-connection

Different from previous studies on effect of weathering upon geochemical variation along a single weathered profile, this paper provides a new methodology validated by comparing a weathered outcrop samples and their stratigraphic counterpart un-weathered core samples in a nearby shallow borehole. This outcrop and borehole penetrated the Ordovician-Silurian Wufeng–Longmaxi shales, located in the same anticline structure in the northern part of Guizhou Province, Southern China. The mineral composition, major, trace and rare earth elements (REEs) composition and Rock-Eval parameters of outcrop and core samples were analyzed and compared. Organic matter (OM) was observed in the microscope and extracted for elements analysis. The results show that short-term weathering still has significant influence on OM, mineral and elemental composition of black shales. The elements composition shows the outcrop profile was moderately weathered. The REEs compositions do not alter much during weathering process and the REEs composition and their relative ratios still are valid for rock origin determination. The OM, mainly composed by graptolite and bitumen, even entering the highly-over thermal maturity, is still sensitive to the weathering with a systematic loss 30–50% of TOC along the outcrop profile, which suggests that the OM consumption is predominantly controlled by weathering duration and the distance from the weathering surface. In turn, OM has significant influence on the trace elements transportation behavior during weathering. Some trace elements associated with the OM such as V, Cr, Th, U, Ni and Co, change significantly in their absolute concentration during weathering, but their relative ratios do not necessarily change too much and might be still reliable proxies for paleo-environmental determination. The mobility of shale minerals during weathering is in the following order: plagioclase?>?potassium feldspar and dolomite >pyrite and OM. Short-term weathering can also result in considerable transportation of elements and significant variation of minerals content in black shale, which may pose potentially high environmental and engineering risk in the regions rich in black shale.     

四川盆地龙马溪组页岩气储层石英类型与特征

为了解页岩气储层石英类型和特征,以四川盆地龙马溪组页岩为研究对象,对样品进行了薄片观察、氩离子抛光-场发射环境扫描电镜观察、能谱分析、X-射线衍射分析、有机碳含量测试。结果表明,龙马溪组页岩石英含量在23%～83%之间,平均值为52%。根据成因,可分为5类:陆源碎屑石英、生物骨骼相关石英、沉积期-成岩早期混合石英、成岩期自生石英和裂缝中石英脉。石英含量与有机碳含量成正相关,其中有机石英在还原环境下能更好地指示有机质的发育情况。有机石英是指保留有软体并演化成干酪根的生物骨骼石英、交代生物骨架石英和与沥青伴生石英。与沥青伴生石英堆积在页岩原生孔隙中,降低了储层的孔隙度,但在一定程度上抑制了后期成岩作用,为沥青的充注保留了空间,且石英与沥青之间发育的缝隙与有机孔一起形成连通的孔隙网络。     

Enzymatic and Microbial Degradation of Organic Matter in Lake Hongfeng, Guizhou Province, China

1IntroductionEnzymaticandmicrobialdegradationoforganicmatterhasabearingnotonlyonearlydiagene sis,butalsoonelementcyclingandmicrobedistributioninlakesediments.Somereportsshowedtheabundancevariationsoforganicmatterinsediments (BurdigeandGardner,1998;ArthurandDean ,1998;WanGuojiangetal.,2 0 0 0 ) .However,duetothecomplexchemicalcompositionoforganicmatter,mechanismsofenzymaticandmicrobialdegradationandvariationsofeachchemicalcomponentneedtobestudiedfurther.Underanoxiccondition ,SO2 -4 isanimpo…     

The association of organic molecules with clay minerals in aqueous solutions

The uptake of dissolved organic molecules by kaolinite and montomorillonite clay minerals was measured in distilled water and saltwater solutions. Glucose and valine exhibited low affinities for both clay minerals over a wide range of concentrations in distilled water and seawater solutions. Stearic acid was efficiently removed by both clay minerals from all solutions over the concentration range 10–1000 ppb. These experiments suggest that some dissolved organic molecules may be preferentially removed by clay minerals in natural waters. It is unlikely, however, that the partitioning of simple organic molecules between natural waters and suspended clay minerals could produce the high concentrations of organic matter that occur in most fine-grained sediments.     

Effect of organic matter and selected heavy metals on sorption of acenaphthene,fluorene and fluoranthene onto various clays and clay minerals

The effects of organic matter (80% humic and 15% fulvic acid) and coexistence of heavy metals (Ni, Pb and Zn) on sorption of three polycyclic aromatic hydrocarbons (PAHs)—acenaphthene, fluorene and fluoranthene—were examined for kaolinite, 60% kaolinite?+?40% sand, and 43% kaolinite?+?42% sand?+?15% bentonite. In total 108 batch sorption tests of PAHs were conducted for three types of clay mineral mixtures in six possible combinations of soil organic matter and heavy metal contents from no heavy metals and organic matter added to maximum organic matter added with spiked heavy metals. Results showed that the existence of metals increased the sorption of PAHs onto kaolinite from 4.7% for acenaphthene to 17.9% for fluoranthene. Organic matter in a kaolinite-sand-bentonite matrix could increase PAH sorption by up to 140% for fluoranthene. In all cases, increases were greater for fluoranthene, a larger PAH molecule. Heavy metals coexisting with organic matter led to enhanced sorption of PAHs compared to clay minerals without organic matter. Synergistic effects of organic matter and heavy metals on PAH sorption increments in the mixtures studied were such that the overall sorption could be 10–41% higher than that based on summation of the separate effects of metals and organics.     

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.     

川东南-鄂西渝东地区下古生界页岩气勘探前景

中上扬子地台发育2套重要的海相深灰色-黑色页岩,分别为下寒武统牛蹄塘组和上奥陶统五峰组-下志留统龙马溪组,主要由富含黄铁矿、有机质或生物化石的黑色炭质页岩组成,厚度大、分布广.牛蹄塘组页岩有机质演化程度高、埋藏相对较深、钻井无天然气显示;龙马溪组页岩有机质演化程度相对中等、埋藏深度适度、钻井天然气显示丰度高,特别是志留系其它粉砂岩层段可产工业性气流.因此,下志留统页岩更有利于研究区页岩气的勘探和开发,更加适合作为中国南方页岩气战略先导区的重点目标勘探层位.总体上,两套页岩在川东南-鄂西渝东地区出露范围广,有利于针对页岩展开相关研究,特别是背斜和向斜的翼部区是页岩气勘探最为有利的地区.     

页岩气储层浅表样品垂向风化特征——以贵州习水龙马溪组页岩为例

页岩风化作用较为复杂,风化页岩由于有机质和矿物组成等发生改变,在页岩气资源评估过程中不能直接利用地表样品。前人主要利用露头样品关注其对环境的影响,少有从影响页岩气资源评估的角度进行研究。本文以页岩气重要储层下志留龙马溪组黑色页岩为研究对象,采集了贵州省习水骑龙村龙马溪组竖直钻孔样品共5 m,运用主微量元素分析、X射线衍射、总有机碳含量测试、热分析以及扫描电镜等方法,系统研究了该储层浅表样品的垂向风化特征。结果表明,研究区地表0 m处页岩严重风化,0.5~1.5 m范围内中等风化,2~5 m范围内可视为未风化的母岩。因此在页岩气资源初期评估时需要尽可能采集2 m以下新鲜样品。本研究查明了贵州习水龙马溪组页岩垂向风化作用规律,为页岩气早期资源评估野外采样提供了科研依据。     

四川盆地及周缘下古生界页岩气深埋藏-强改造独特地质作用

四川盆地位于特提斯-喜马拉雅构造域和滨太平洋构造域的交接转换部位,盆地及其周缘海相、海陆过渡相富有机质页岩经历了多旋回构造体系下的深埋藏(高演化)、强隆升、强剥蚀和强变形,强改造作用过程。这是我国南方中上扬子地区页岩与北美页岩气产层在地质特征和演化上的最大不同。晚白垩世以来四川盆地多阶段性隆升过程致使地表普遍具有1 000~4 000m剥蚀厚度。地表差异性剥蚀幅度与陆相地层沉积厚度共同控制着其下伏地层的古埋深。四川盆地及其周缘下志留统龙马溪组底界和下寒武统牛蹄塘组底界古埋深分别大于6 500m和9 000m,等深线总体呈NE-SW展布,且二者底界埋深均具有由北东向南西逐渐减小的趋势。龙马溪组底界古埋深最浅处位于盆地南缘宜宾南绥江地区(约6 000m),最大埋深处为川北地区(约9 000m),古埋深分别向盆地东南缘和北缘明显加深,且盆地中央具有明显的NE-SW向展布低值或浅埋深带,即绥江—宜宾—泸州地区和达州—巴中地区。牛蹄塘组底界古埋深特征与现今埋深特征总体相似,最大埋深处位于川西-川北前陆盆地(古埋深大于11 000m);最小古埋深处位于川中—川西南宜宾—自贡—遂宁一带(古埋深小于8 000m)。四川盆地及其周缘下古生界页岩深埋藏与其高演化具有密切相关性。下志留统龙马溪组和下寒武统牛蹄塘组黑色页岩热成熟度Ro值普遍大于2.4%和2.8%,与其古埋深相似均具有由盆地北东向南西逐渐减小的趋势。强隆升、强剥蚀和强变形作用致使下古生界页岩经历强改造作用,具有动态的应力-应变、温度和压力变化特征,及其保存条件有效性的动态调整。四川盆地及其周缘现今钻探成果揭示差异性埋藏-隆升剥蚀-构造变形作用对下古生界页岩气富集与分布具有较大的控制作用。因此,我国南方中上扬子地区下古生界页岩气地质研究,不仅与北美一样,研究常规油气的优质烃源岩如何转化为非常规页岩气的优质储层,而且还须探讨在强改造作用下页岩气优质储层如何才能成为具商业价值的页岩气产层。     

Apparent permeability and representative size of shale: a numerical study on the effects of organic matter

The impact of organic matter on the flow capacity of shale oil rocks is presumably significant, and the knowledge about the representative size is fundamental for the upscaling studies. The error of the experimentally determined permeability values is comparable with the contribution of kerogen to shale permeability, instead a 2D numerical model is employed to explore the normalised equivalent permeability and the representative elementary area (REA) of shale oil rocks in detail incorporating the effects of kerogen. The discussions on the normalised equivalent permeability and the REA are based on the statistical average and standard deviation from 1000 different runs, respectively. The inorganic permeability heterogeneity is introduced based on the assumption of a lognormal pore size distribution and the Monte Carlo sampling method. The effects of kerogen geometric characteristics are incorporated by putting forward several representative cases for comparison. The effects of the organic permeability contrast (ratio of permeability to the inorganic permeability with no heterogeneity), total organic carbon (TOC, volume fraction), inorganic permeability heterogeneity and kerogen geometric characteristics on the normalised equivalent permeability (ratio of the intrinsic equivalent permeability to inorganic permeability with no heterogeneity) and the REA are discussed comprehensively. This work can provide a better understanding of shale oil rocks at the micrometer scale.     

页岩气藏超低含水饱和度形成模拟及其意义

页岩气属于非常规天然气,资源丰富,开发潜力巨大。含水饱和度是控制致密气藏持续生产最关键的储层参数,然而现阶段对页岩气成藏中超低含水饱和度是否存在尚存在疑问。选取川渝地区页岩露头岩样,采用气驱法模拟了成藏过程中含水饱和度变化,结合川南页岩气储层地质特征,建立了生烃排驱的地质模型,提出了气携液的概念模型。结果表明,页岩气藏存在超低含水饱和度现象;页岩气成藏过程中大量生烃产生排驱效应与气携液作用,有利于页岩气储层超低含水饱和度的形成,气携液作用、裂缝和高温环境加速了含水饱和度降低;超低含水饱和度增加页岩气储层吸附能力,增大储层可流动孔喉范围,提高气相传输能力,但在工程作业过程中加大水相渗吸速率,强化水相滞留效应,使页岩气藏水相圈闭损害潜力更大。在页岩气有利区评价、气藏钻完井、开发过程中,须倍加重视超低含水饱和度这一客观事实和其衍生的工程作业问题。     

Pore structure and heterogeneity of shale gas reservoirs and its effect on gas storage capacity in the Qiongzhusi Formation

Fine characterization of pore systems and heterogeneity of shale reservoirs are significant contents of shale gas reservoir physical property research.The research on micro-control factors of low productivity in the Qiongzhusi Formation(Fm.)is still controversial.The lower Cambrian Qiongzhusi Fm.in the Qujing,Yunnan was taken as the object to investigate the influence of mineral compositions on the phys-ical properties of the reservoir and the heterogeneity of shale,using the algorithm to improve the char-acterization ability of Atomic Force Microscopy(AFM).The results showed that:(1)The pores are mainly wedge-shaped pores and V-shaped pores.The pore diameter of the main pore segment ranges from 5 to 10 nm.Mesopores are mainly developed in the Qiongzhusi Fm.shale in Well QD1,with the average pore diameter of 6.08 nm.(2)Microscopic pore structure and shale surface properties show strong hetero-geneity,which complicates the micro-migration of shale gas and increases the difficulty of identifying high-quality reservoirs.(3)The increase of clay mineral content intensifies the compaction and then destroys the pores.Conversely,brittle minerals can protect pores.The support and protection of brittle minerals to pores space depend on their content,mechanical properties and diagenesis.(4)Compression damage to pores,large microscopic roughness and surface fluctuations and strong pore structure heterogeneity are the reasons for the poor gas storage capacity of the Qiongzhusi Fm.,which will lead to poor productivity in the Qiongzhusi Fm.     

Effects of mechanical layering on hydraulic fracturing in shale gas reservoirs based on numerical models

Generally, induced hydraulic fractures are generated by fluid overpressure and are used to increase reservoir permeability through forming interconnected fracture systems. However, in heterogeneous and anisotropic rocks, many hydraulic fractures may become arrested or offset at layer contacts under certain conditions and do not form vertically connected fracture networks. Mechanical layering is an important factor causing anisotropy in sedimentary layers. Hence, in this study, with a shale gas reservoir case study in the Longmaxi Formation in the southeastern Chongqing region, Sichuan Basin, we present results from several numerical models to gain quantitative insights into the effects of mechanical layering on hydraulic fracturing. Results showed that the fractured area caused by hydraulic fracturing indicated a linear relationship with the neighboring layer’s Young’s modulus. An increase of the neighboring layer’s Young’s modulus resulted in better hydraulic fracturing effects. In addition, the contact between two neighboring layers is regarded as a zone with thickness and mechanical properties, which also influences the effects of hydraulic fracturing in reservoirs. The initial hydraulic fracture was unable to propagate into neighboring layers under a relatively low contact’s Young’s modulus. When associated local tensile stresses exceeded the rock strength, hydraulic fractures propagated into neighboring layers. Moreover, with the contact’s Young’s modulus becoming higher, the fractured area increased rapidly first, then slowly and finally became stable.     

我国下古生界碳酸盐岩烃源岩评价研究现状

碳酸盐岩烃源岩评价对我国油气资源评价与勘探至关重要。本文从有机质成熟度、有机质丰度下限、有机质丰度及生烃潜力的恢复、碳酸盐岩生烃机制与生烃模式等几个方面,介绍了我国碳酸盐岩烃源岩的研究现状,提出了运用生烃动力学对碳酸盐岩烃源岩进行研究的新方法,展望了需要继续关注的问题。     

Interactions between organic matter and minerals in two bituminous coals of different rank

The association between specific mineral and organic constituents in two Asturian bituminous coals of different rank was studied. For this, raw coals were fractionated by density and the variation of a number of parameters was followed in parallel. Results of coal chemical analyses, including analyses for 22 elements, were used to establish the elemental association with coal organic matter. Petrographic analyses determined the distribution of macerals among densimetric fractions, vitrinite reflectance being at a minimum in the intermediate density fractions. Mineral species were identified by X-ray diffraction, FT-IR spectroscopy and Mössbauer spectroscopy. Comparison of trends for different parameters determined using this set of techniques allowed classification of the various minerals according to their association with organic matter. Carbonates seem to be specifically associated with the organic matter of the low-volatile bituminous coal whereas sulfides concentrate in the organic matter of the high-volatile bituminous coal. Vitrinite is the maceral exhibiting the most probable association with inorganic matter. The possibility of a merely physical association of fine-grained detrital minerals with organic matter cannot be excluded; nevertheless, one must bear in mind that even this type of interaction is important due to its effect on various coal preparation and utilization processes.