扬子地块东南古生代上升流沉积相及其与烃源岩的关系

长江中下游苏、皖、赣、鄂一带属古生代扬子地块被动大陆边缘的东南缘,通过该区64条古生界剖面的实测、分析和对比,得出该区古生界寒武、奥陶、志留、石炭和二叠系等地层中的黑色碳质页岩、硅质页岩、硅质条带和结核以及磷矿层和磷结核等沉积是古特提斯海中上升流作用形成的。上升流水体中富营养盐和SiO2,在古生代低纬度的扬子地块东南缘生物大量繁殖,引发缺氧事件,形成上述硅质和磷质沉积以及有机质丰富的烃源岩、石煤和磷矿层等,由于上升流水体富营养盐和SiO2,生物化石属种丰富,个体大,多营底栖或固着浅海底生活,硅质生物放射虫等丰富。区内烃源岩有机质与上升流的强度呈正相关关系,可见它们之间存在着成因联系。上古生界油气发现于苏北及南黄海,因而,这一区域是与上升流沉积有关的、最有利的油气勘探目标区。     

Pore structure of Cambrian shales from the Sichuan Basin in China and implications to gas storage

The microstructure of black siliceous shale from the lower Cambrian Niutitang Formation, Sichuan Basin in China was investigated by the combination of field emission scanning electron microscope (FE-SEM) and argon ion beam milling. The nanometer-to micrometer-scale pore systems of shales are an important control on gas storage and fluid migration. In this paper, the organic porosity in shale samples within oil and gas window has been investigated, and the formation mechanism and diagenetic evolution of nanopores have been researched.FE-SEM reveals five pore types that are classified as follows: organic nanopores, pores in clay minerals, nanopores of framework minerals, intragranular pores in microfossils, and microfractures. Numerous organic nanopores are observed in shales in the gas window, whereas microfractures can be seen within the organic matter of shales in the oil window. Microfractures in oil window shales could be attributed to pressure buildup in the organic matter when incompressible liquid hydrocarbon are generated, and the orientation of microfractures is probably parallel to the bedding and strength anisotropy of the formation. Pores in clay minerals are always associated with the framework of clay flakes, and develop around rigid mineral grains because the pressure shadows of mineral grains protect pores from collapse, and the increasing of silt content would lead to an increase in pressure shadows and improve porosity. Nanopores of rock framework are probably related to dissolution by acidic fluids from hydrocarbon generation, and the dissolution-related pores promote permeability of shales. Porosity in the low-TOC, low-thermal-maturity shales contrast greatly with those of high-TOC, high-thermal-maturity shales. While the high-TOC shales contain abundant organic microporosity, the inorganic pores can contribute a lot to the porosity of the low-TOC shales.     

Modeling free gas content of the Lower Paleozoic shales in the Weiyuan area of the Sichuan Basin,China

Two sets of Lower Paleozoic organic-rich shales develop well in the Weiyuan area of the Sichuan Basin: the Lower Cambrian Jiulaodong shale and the Lower Silurian Longmaxi shale. The Weiyuan area underwent a strong subsidence during the Triassic to Early Cretaceous and followed by an extensive uplifting and erosion after the Late Cretaceous. This has brought about great changes to the temperature and pressure conditions of the shales, which is vitally important for the accumulation and preservation of shale gas. Based on the burial and thermal history, averaged TOC and porosity data, geological and geochemical models for the two sets of shales were established. Within each of the shale units, gas generation was modeled and the evolution of the free gas content was calculated using the PVTSim software. Results show that the free gas content in the Lower Cambrian and Lower Silurian shales in the studied area reached the maxima of 1.98–2.93 m³/t and 3.29–4.91 m³/t, respectively (under a pressure coefficient of 1.0–2.0) at their maximum burial. Subsequently, the free gas content continuously decreased as the shale was uplifted. At present, the free gas content in the two sets of shales is 1.52–2.43 m³/t and 1.94–3.42 m³/t, respectively (under a current pressure coefficient of 1.0–2.0). The results are roughly coincident with the gas content data obtained from in situ measurements in the Weiyuan area. We proposed that the Lower Cambrian and Lower Silurian shales have a shale gas potential, even though they have experienced a strong uplifting.     

Pore characterization of organic-rich Lower Cambrian shales in Qiannan Depression of Guizhou Province,Southwestern China

Nine organic-rich shale samples of Lower Cambrian black shales were collected from a recently drilled well in the Qiannan Depression, Guizhou Province where they are widely distributed with shallower burial depth than in Sichuan Basin, and their geochemistry and pore characterization were investigated. The results show that the Lower Cambrian shales in Qiannan Depression are organic rich with TOC content ranging from 2.81% to 12.9%, thermally overmature with equivalent vitrinite reflectance values in the range of 2.92–3.25%, and clay contents are high and range from 32.4% to 53.2%. The samples have a total helium porosity ranging from 2.46% to 4.13% and total surface area in the range of 9.08–37.19 m²/g. The estimated porosity in organic matters (defined as the ratio of organic pores to the volume of total organic matters) based on the plot of TOC vs helium porosity is about 10% for the Lower Cambrian shales in Qiannan Depression and is far lower than that of the Lower Silurian shales (36%) in and around Sichan Basin. This indicates that either the organic pores in the Lower Cambrian shale samples have been more severely compacted than or they did not develop organic pores as abundantly as the Lower Silurian shales. Our studies also reveal that the micropore volumes determined by Dubinin–Radushkevich (DR) equation is usually overestimated and this overestimation is closely related to the non-micropore surface area of shales (i.e. the surface area of meso- and macro-pores). However, the modified BET equation can remove this overestimation and be conveniently used to evaluate the micropore volumes/surface area and the non-micropore surface areas of micropore-rich shales.     

Mineral types and organic matters of the Ordovician-Silurian Wufeng and Longmaxi Shale in the Sichuan Basin,China: Implications for pore systems,diagenetic pathways,and reservoir quality in fine-grained sedimentary rocks

Mineral types (detrital and authigenic) and organic-matter components of the Ordovician-Silurian Wufeng and Longmaxi Shale (siliceous, silty, argillaceous, and calcareous/dolomitic shales) in the Sichuan Basin, China are used as a case study to understand the control of grain assemblages and organic matter on pores systems, diagenetic pathway, and reservoir quality in fine-grained sedimentary rocks. This study has been achieved using a combination of petrographic, geochemical, and mercury intrusion methods. The results reveal that siliceous shale comprises an abundant amount of diagenetic quartz (40–60% by volume), and authigenic microcrystalline quartz aggregates inhibit compaction and preserve internal primary pores as rigid framework for oil filling during oil window. Although silty shale contains a large number of detrital silt-size grains (30–50% by volume), which is beneficial to preserve interparticle pores, the volumetric contribution of interparticle pores (mainly macropores) is small. Argillaceous shale with abundant extrabasinal clay minerals (>50% by volume) undergoes mechanical and chemical compactions during burial, leading to a near-absence of primary interparticle pores, while pores preserved between clay platelets are dominant with more than 10 nm in pore size. Pore-filling calcite and dolomite precipitated during early diagenesis inhibit later compaction in calcareous/dolomitic shale, but the cementation significantly reduces the primary interparticle pores. Pore-throat size distributions of dolomitic shale show a similar trend with silty shale. Besides argillaceous shale, all of the other lithofacies are dominated by OM pores, which contribute more micropores and mesopores and is positively related to TOC and quartz contents. The relationship between pore-throat size and pore volume shows that most pore volumes are provided by pore throats with diameters <50 nm, with a proportion in the order of siliceous (80.3%) > calcareous/dolomitic (78.4%) > silty (74.9%) > argillaceous (61.3%) shales. In addition, development degree and pore size of OM pores in different diagenetic pathway with the same OM type and maturity show an obvious difference. Therefore, we suggest that the development of OM pores should take OM occurrence into account, which is related to physical interaction between OM and inorganic minerals during burial diagenesis. Migrated OM in siliceous shale with its large connected networks is beneficial for forming more and larger pores during gas window. The result of the present work implies that the study of mineral types (detrital and authigenic) and organic matter-pores are better understanding the reservoir quality in fine-grained sedimentary rocks.     

Comprehensive polynomial simulation and prediction for Langmuir volume and Langmuir pressure of shale gas adsorption using multiple factors

In this study, 32 experimental measurements on the isothermal adsorption of methane for 18 shale samples from China's three largest continental oil basins—Songliao, Bohai Bay, and Ordos basins—were used to construct comprehensive polynomial simulation and prediction models for Langmuir volume and Langmuir pressure. The models were based on shale properties (total organic carbon (TOC) content, amount of residual hydrocarbon S₁, and mineral composition of rocks) and adsorption condition (temperature) using a weighted sum of multiple variables. The influences of various factors were quantitatively characterized, and the prediction accuracy was verified. Langmuir volume is mainly affected by temperature, shale TOC content, amount of residual hydrocarbon, and clay mineral content; Langmuir pressure is mainly affected by clay, carbonate, feldspar and illite content (because shale pore size can be affected by shale mineral composition). Based on the resource potential and the producibility of shale gas, the area suitable for shale gas exploration and development should have high abundance of organic matter (TOC and residual hydrocarbon S₁), low clay mineral content and feldspar content, high conversion rate of montmorillonite to illite (strong diagenesis), and high carbonate content. The comprehensive polynomial prediction model can effectively simulate and predict Langmuir volume and Langmuir pressure, thereby reducing the amount of work necessary for evaluation of shale gas resource potential and economic feasibility.     

基于颜色显示快速估算页岩有机碳含量的新方法

有机碳含量(TOC)是页岩气储层评价的关键参数之一,它既是页岩生气的物质基础,也是页岩吸附气的重要载体。以鄂尔多斯盆地山西组页岩系统为例,根据不同的颜色显示划分出4种岩性:黑色煤、灰黑色页岩、灰色页岩、灰白色粉砂岩,赋予这4种岩性不同的颜色显示值,计算页岩系统的总颜色评价值(TCA),拟合页岩系统中TCA和实测TOC之间的关系,依据TCA估算页岩系统的TOC。研究发现,当页岩系统中4种岩性的颜色显示值为等比数列(1、2、4、8)时,TCA和实测TOC相关系数(R2)高,且以指数拟合和三次方拟合的相关系数(R2)最高;页岩系统中TCA的对数和实测TOC的对数呈现良好的正相关性,根据页岩中TCA估算的TOC和实测TOC十分接近。因此,在室外工作中可以利用该方法快速估算页岩系统的TOC,从而为页岩气目标层段的优选提供参考依据。     

Logging identification and characteristic analysis of marine–continental transitional organic-rich shale in the Carboniferous-Permian strata,Bohai Bay Basin

Currently, global shale gas exploration and exploitation are focused on marine shale. Recently, major shale gas-oil breakthroughs have been made within continental and marine–continental transitional shale in China. This study will show how transitional shale is of great importance. Based on geological field surveys, core observations, thin section analysis, organic geochemistry and X-ray diffraction, we systematically studied the basic geological characteristics (including lithology, mineral composition, and organic geochemistry) of this transitional shale. By comparative analysis of well logging data from 260 wells in the Taiyuan–Shanxi shale, we will show that these methods are effective for identifying organic-rich shale from conventional well logs and determining its thickness distribution in the Carboniferous–Permian strata of the Taiyuan–Shanxi transitional coal-bearing formation.The results indicate that the Taiyuan–Shanxi shale has a high TOC (most 2%–4%) and that the lithology is primarily carbonaceous shale with type Ⅱ₂-Ⅲ kerogens. The high thermal maturation (Ro ≥ 1.1%) favors the generation of gas. The mineral components primarily include clay minerals, quartz, and plagioclase with a moderate brittle mineral content (47 wt.%) and high clay mineral content (51 wt.%) dominated by kaolinite (43%) and mixed-layer illite-smectite (31%). The transitional organic-rich shale on conventional log curves is generally characterized by higher gamma ray (GR), neutron porosity (CNL), acoustic travel time (AC), resistivity (R_t), potassium (K), and uranium (U) readings and a lower density (DEN), photoelectric absorption index (PE) and thorium-uranium ratio (TH/U). After analyzing the log response characteristics of the organic-rich shale, the most sensitive logging curves (such as CNL, AC, DEN, PE and U) were optimized to conduct logging overlays and to construct cross-plots to qualitatively identify organic-rich shale. The identified organic-rich shale amalgamates in the middle-upper member of the Taiyuan Formation and the lower member of the Shanxi Formation consistent with the results of the TOC analysis and practical gas logging. Based on the qualitative evaluation methods of the modified △LogR and a multivariate linear regression model, we calculated the TOC of shale wells in the Taiyuan–Shanxi formation. From this we calculated the characteristic values of organic-rich shale thickness. The results indicate that organic-rich shale in the Taiyuan formation is thicker than that in the Shanxi formation. Additionally, the thickness of organic-rich shale within lagoons and deep reed swamp facies are much thicker (25–35 m and 40–80 m) than other structural profile types, whereas their lateral distribution is less than that of marine shale. The relatively small continuous thickness of the single shale layer and high clay content may have negative effects for developing the shale gas potential.     

Iron and manganese micro-precipitates within a cretaceous biosiliceous ooze from the Arctic Ocean: possible hydrothermal source

The oldest sediment most recently recovered from the Arctic Ocean is a biosiliceous ooze nearly devoid of nonbiogenic particles and exhibiting small-scale color changes. Color variations are due to changes in iron and manganese content. These elements are probably of local hydrothermal origin, and the Mn precipitation may be bacteria-mediated. An iron silicate phase seems to form at the expense of biogenic silica. The ooze deposited slowly until a sudden sediment input, probably a volcanigenic deposit now weathered to clay minerals, induced dissolution of siliceous microfossils. This clay layer contains calcium phosphate microspheres enriched in rare earth elements.     

Qualitative and quantitative characterization of a transitional shale reservoir: A case study from the Upper Carboniferous Taiyuan shale in the eastern uplift of Liaohe Depression,China

The paper takes the Upper Carboniferous Taiyuan shale in eastern uplift of Liaohe depression as an example to qualitatively and quantitatively characterize the transitional (coal-associated coastal swamp) shale reservoir. Focused Ion Beam Scanning Electron Microscope (FIB-SEM), nano-CT, helium pycnometry, high-pressure mercury intrusion and low-pressure gas (N₂ & CO₂) adsorption for eight shale samples were taken to investigate the pore structures. Four types of pores, i.e., organic matter (OM) pores, interparticle (InterP) pores, intraparticle (IntraP) pores and micro-fractures are identified in the shale reservoir. Among them, intraP pores and micro-fractures are the major pore types. Slit-shaped pores are the major shape in the pore system, and the connectivity of the pore-throat system is interpreted to be moderate, which is subordinate to marine shale. The porosity from three dimension (3D) reconstruction of SEM images is lower than the porosity of helium pycnometry, while the porosity trend of the above two methods is the same. Combination of mercury intrusion and gas absorption reveals that nanometer-scale pores provide the main storage space, accounting for 87.16% of the pore volume and 99.85% of the surface area. Micropores contribute 34.74% of the total pore volume and 74.92% of the total pore surface area; and mesopores account for 48.27% of the total pore volume and 24.93% of the total pore surface area; and macropores contribute 16.99% of the total pore volume and 0.15% of the total pore surface area. Pores with a diameter of less than 10 nm contribute the most to the pore volume and the surface area, accounting for 70.29% and 97.70%, respectively. Based on single factor analysis, clay minerals are positively related to the volume and surface area of micropores, mesopores and macropores, which finally control the free gas in pores and adsorbed gas content on surface area. Unlike marine shale, TOC contributes little to the development of micropores. Brittle minerals inhibit pore development of Taiyuan shale, which proves the influence of clay minerals in the pore system.     

华南寒武纪海洋中沉积矿床及其古环境

寒武纪早期是华南的一个重要的沉积矿床形成阶段。在华南扬子板块下寒武统黑色岩系中产有大量的金属及非金属矿床,其中倍受关注的矿床有Ni-Mo-PGE多金属硫化物矿床、磷矿床与重晶石矿床。Ni-Mo-PGE多金属硫化物矿床的形成可能与海底热液喷流作用有关,成矿元素除海水源外,有部分来自深部热液;磷矿床形成于特定的浅海环境,成矿物质的聚集可能与有机质和含铁胶体有关;重晶石矿床的形成也与海底热液和有机质有关。这些矿床保存了大量的古海洋信息,对其进行深入研究可以揭示华南寒武纪大爆发时期的古海洋环境变化特征。     

Sedimentary and residual gas geochemical characteristics of the Lower Cambrian organic-rich shales in Southeastern Chongqing,China

To study the sedimentary environment of the Lower Cambrian organic-rich shales and isotopic geochemical characteristics of the residual shale gas, 20 black shale samples from the Niutitang Formation were collected from the Youyang section, located in southeastern Chongqing, China. A combination of geochemical, mineralogical, and trace element studies has been performed on the shale samples from the Lower Cambrian Niutitang Formation, and the results were used to determine the paleoceanic sedimentary environment of this organic-rich shale. The relationships between total organic carbon (TOC) and total sulfur (TS) content, carbon isotope value (δ¹³C_org), trace element enrichment, and mineral composition suggest that the high-TOC Niutitang shale was deposited in an anoxic environment and that the organic matter was well preserved after burial. Stable carbon isotopes and biomarkers both indicate that the organic matter in the Niutitang black shales was mainly derived from both lower aquatic organisms and algaes and belong to type I kerogen. The oil-prone Niutitang black shales have limited residual hydrocarbons, with low values of S₂, I_H, and bitumen A. The carbon isotopic distribution of the residual gas indicate that the shale gas stored in the Niutitang black shale was mostly generated from the cracking of residual bitumen and wet gas during a stage of significantly high maturity. One of the more significant observations in this work involves the carbon isotope compositions of the residual gas (C₁, C₂, and C₃) released by rock crushing. A conventional δ¹³C₁–δ¹³C₂ trend was observed, and most δ¹³C₂ values of the residual gases are heavier than those of the organic matter (OM) in the corresponding samples, indicating the splitting of ethane bonds and the release of smaller molecules, leading to ¹³C enrichment in the residual ethane.     

中国南海北部珠江口-琼东南盆地钻井岩屑地球化学特征及深水区天然气聚集特征

The Qiongdongnan Basin and Zhujiang River(Pearl River) Mouth Basin, important petroliferous basins in the northern South China Sea, contain abundant oil and gas resource. In this study, on basis of discussing impact of oil-base mud on TOC content and Rock-Eval parameters of cutting shale samples, the authors did comprehensive analysis of source rock quality, thermal evolution and control effect of source rock in gas accumulation of the Qiongdongnan and the Zhujiang River Mouth Basins. The contrast analysis of TOC contents and Rock-Eval parameters before and after extraction for cutting shale samples indicates that except for a weaker impact on Rock-Eval parameter S_2, oil-base mud has certain impact on Rock-Eval S_1, Tmax and TOC contents. When concerning oil-base mud influence on source rock geochemistry parameters, the shales in the Yacheng/Enping,Lingshui/Zhuhai and Sanya/Zhuhai Formations have mainly Type Ⅱ and Ⅲ organic matter with better gas potential and oil potential. The thermal evolution analysis suggests that the depth interval of the oil window is between 3 000 m and 5 000 m. Source rocks in the deepwater area have generated abundant gas mainly due to the late stage of the oil window and the high-supper mature stage. Gas reservoir formation condition analysis made clear that the source rock is the primary factor and fault is a necessary condition for gas accumulation. Spatial coupling of source, fault and reservoir is essential for gas accumulation and the inside of hydrocarbon-generating sag is future potential gas exploration area.     

Smectite formation in metalliferous sediments near the East Pacific Rise at 13°N

A 43 cm long E271 sediment core collected near the East Pacific Rise(EPR) at 13°N were studied to investigate the origin of smectite for understanding better the geochemical behavior of hydrothermal material after deposition.E271 sediments are typical metalliferous sediments. After removal of organic matter, carbonate, biogenic opal,and Fe-Mn oxide by a series of chemical procedures, clay minerals(2 μm) were investigated by X-ray diffraction,chemical analysis and Si isotope analysis. Due to the influence of seafloor hydrothermal activity and close to continent, the sources of clay minerals are complex. Illite, chlorite and kaolinite are suggested to be transported from either North or Central America by rivers or winds, but smectite is authigenic. It is enriched in iron, and its contents are highest in clay minerals. Data show that smectite is most likely formed by the reaction of hydrothermal Fe-oxyhydroxide with silica and seawater in metalliferous sediments. The Si that participates in this reaction may be derived from siliceous microfossils(diatoms or radiolarians), hydrothermal fluids, or detrital mineral phases. And their δ30 Si values are higher than those of authigenic smectites, which implies that a Si isotope fractionation occurs during the formation because of the selective absorption of light Si isotopes onto Feoxyhydroxides. Sm/Fe mass ratios(a proxy for overall REE/Fe ratio) in E271 clay minerals are lower than those in metalliferous sediments, as well as distal hydrothermal plume particles and terrigenous clay minerals. This result suggests that some REE are lost during the smectite formation, perhaps because their large ionic radii of REE scavenged by Fe-oxyhydroxides preclude substitution in either tetrahedral or octahedral lattice sites of this mineral structure, which decreases the value of metalliferous sediments as a potential resource for REE.     

Multiple controls on the paleoenvironment of the Early Cambrian marine black shales in the Sichuan Basin,SW China: Geochemical and organic carbon isotopic evidence

In order to understand the paleoenvironment of the Early Cambrian black shale deposition in the western part of the Yangtze Block, geochemical and organic carbon isotopic studies have been performed on two wells that have drilled through the Qiongzhusi Formation in the central and southeastern parts of Sichuan Basin. It shows that the lowest part of the Qiongzhusi Formation has high TOC abundance, while the middle and upper parts display relative low TOC content. Redox-sensitive element (Mo) and trace elemental redox indices (e.g., Ni/Co, V/Cr, U/Th and V/(V + Ni)) suggest that the high-TOC layers were deposited under anoxic conditions, whereas the low-TOC layers under relatively dysoxic/oxic conditions. The relationship of the enrichment factors of Mo and U further shows a transition from suboxic low-TOC layers to euxinic high-TOC layers. On the basis of the Mo-TOC relationship, the Qiongzhusi Formation black shales were deposited in a basin under moderately restricted conditions. Organic carbon isotopes display temporal variations in the Qiongzhusi Formation, with a positive excursion of δ¹³C_org values in the lower part and a continuous positive shift in the middle and upper parts. All these geochemical and isotopic criteria indicate a paleoenvironmental change from bottom anoxic to middle and upper dysoxic/oxic conditions for the Qiongzhusi Formation black shales. The correlation of organic carbon isotopic data for the Lower Cambrian black shales in different regions of the Yangtze Block shows consistent positive excursion of δ¹³C_org values in the lower part for each section. This excursion can be ascribed to the widespread Early Cambrian transgression in the Yangtze Block, under which black shales were deposited.     

Effects of composition and pore structure on the reservoir gas capacity of Carboniferous shale from Qaidam Basin,China

Shale adsorption and breakthrough pressure are important indicators of shale gas development and key factors in evaluating the reservoir capacities of shales. In this study, geochemical tests, pore-structure tests, methane adsorption tests, and breakthrough-pressure tests were conducted on shales from the Carboniferous Hurleg Formation in eastern Qaidam Basin. The effects of the shale compositions and pore structures on the adsorption and breakthrough pressures were studied, and the reservoir capacities of the shales were evaluated by analyzing the shale adsorptions and sealing effects. The results indicate that the organic carbon content was only one of factors in affecting the adsorption capacity of the shale samples while the effect of the clay minerals was limited. Based on the positive correlation between the adsorption capacity and specific surface area of the shale, the specific surface area of the micropores can be used as an indicator to determine the adsorption capacity of shale. The micro-fracturing of brittle minerals, such as quartz, create a primary path for shale gas breakthrough, whereas the expansion of clay minerals with water greatly increases the breakthrough pressure in the shale samples. Methane adsorption tests showed that maximum methane adsorption for shale samples Z045 and S039 WAS 0.107 and 0.09655 mmol/g, respectively. The breakthrough pressure was 39.36 MPa for sample S039, maintained for 13 days throughout the experiment; however, no breakthrough was observed in sample Z045 when subjected to an injected pressure of 40 MPa for 26 days. This indicates that sample Z045, corresponding to a depth of 846.24 m, exhibited higher adsorption capacity and a better reservoir-sealing effect than sample S039 (498.4 m depth). This study provides useful information for future studies of Qaidam Basin shale gas exploration and development and for evaluation of shale quality.     

印度洋钙质软泥和硅质软泥稀土元素组成和富集机制

本文针对采自印度洋深海中最常见的两类生物成因沉积物——钙质软泥和硅质软泥,开展了全岩样和不同粒级组分中常微量元素、稀土元素和Y（REY）含量的系统分析,探讨了两类沉积物中REY的组成特征、物质来源和富集机制。研究表明,钙质软泥以富含CaO和Sr为主要特征,硅质软泥则富集SiO₂、Al₂O₃、Fe₂O₃等。钙质软泥中∑REY平均含量为40.56×10-6,轻稀土元素（LREE）略有富集,REY有向细粒沉积物中富集的特征,PAAS标准化后全岩样和不同粒级组分均表现为Ce负异常、Eu和Y正异常;REY以自生来源为主,继承了海水的组成特征,同时也受到了热液流体物质和洋底玄武岩风化产物的影响。硅质软泥中∑REY的含量为248.54×10-6,LREE相对富集,REY在4φ以细的沉积物中富集;研究站位沉积物中∑REY含量处于边界品位附近,但在细粒级沉积物中重稀土元素（HREY）含量则达到了工业品位;该类沉积物细粒组分中REY主要来自陆源或火山碎屑组分中黏土矿物和铁锰氧化物吸附作用,粗粒组分中REY来源则主要与生物作用相关;硅质软泥中REY的富集与沉积物中磷灰石等矿物相关,部分不同来源的REY可能是在沉积之后的成岩过程中再次分配向磷灰石、钙十字沸石等矿物中富集。     

Heterogeneous nanoporosity of the Silurian Longmaxi Formation shale gas reservoir in the Sichuan Basin using the QEMSCAN,FIB-SEM,and nano-CT methods

Nanoporosity of a shale gas reservoir provides essential information on the gas accumulation space and controls the gas reserves. The characteristics of heterogeneous nanoporosity of four shale samples are analyzed by combining quantitative evaluation of minerals by scanning electronic microscopy (QEMSCAN), focused ion beam-scanning electron microscopy (FIB-SEM), and nano-CT. The representative elementary area (REA) is proposed by QEMSCAN to detect the imaging area that can represent the overall contents of minerals and organic matter. Combined with the statistics of pores in minerals and organic matter by FIB-SEM, the quantitative nanoporosity is obtained. The nano-CT is used to compare the total nanoporosity that was obtained by FIB-SEM. The results show that shale has distinct characteristics in nanoporosities due to the variation in organic matter and mineral content. The major pore sizes of the organic matter and clay minerals are smaller than 400 nanometers (nm), and the pore sizes of feldspar and pyrite are mainly 200–600 nm. The pore sizes for pores developed in quartz and carbonate minerals range from a few nanometers to 1000 nm. Furthermore, pores smaller than 400 nm mainly provide the total nanoporosity. The nanoporosities in the organic matter are approximately 17%–21%. Since the organic matter content (0.54%–6.98%) is low, the organic matter contributes approximately 5%–33% of the total nanoporosity in shale. Conversely, the nanoporosities in quartz and clay are generally lower than 3%. Since the mineral content (93.02%–99.46%) is obviously higher than the organic matter content, the minerals contribute approximately 67%–95% of the total nanoporosity in shale.     

下扬子中二叠统上升流相与烃源岩的关系研究

下扬子区面积177020km^2,包括江苏、浙江、安徽、江西和上海绝大部分地区,这一区域的构造属性为被动大陆边缘,通过对该区古生界中二叠统的几十条剖面的实测、分析和对比,得出该区古生界中二叠统地层中的黑色碳质页岩、硅质页岩、硅质岩、硅质条带和结核以及磷矿层和磷结核等沉积是古特提斯海中上升流作用形成的。上升流水体中富营养盐和SiO2在古生代低纬度的下扬子地块生物大量繁殖,引发缺氧事件,形成上述硅质和磷质沉积以及有机质丰富的烃源岩、石煤和磷矿层等,由于上升流水体富营养盐和SiO2,生物化石属种丰富,个体大,多营底栖或固着浅海底生活,硅质生物放射虫等丰富。区内烃源岩有机质与上升流的强度呈正相关关系,可见它们之间存在着成因联系。     

Experimental investigation of thermal maturation on shale reservoir properties from hydrous pyrolysis of Chang 7 shale,Ordos Basin

Thermal maturity has a significant impact on hydrocarbon generation and the storage capacity within shales, but explicit and quantitative characterization of that impact on continental shales is scarce. To better understand how thermal maturation affects the organic and inorganic changes of the continental shale reservoirs, hydrous pyrolysis was performed to simulate the maturation process. TOC, Rock-Eval and adsorption isotherms tests were used to obtain various geochemical parameters of the shale solid residues. The results indicate that with pyrolysis temperature increasing from ambient temperature to 550 °C, the vitrinite reflectance increases from 0.5% to 2.5% Ro and the TOC (total organic carbon) loss weight reaches 25%. Regarding porosity, the fraction of micro-to meso-pores in the shale increases with an increase in the pyrolysis temperature, whereas the macro-pores do not change significantly. The total amount of gas adsorption does not necessarily increase as the TOC is consumed, but the gas adsorption capacity per unit of TOC increases with increasing thermal maturity. Our finding provides theoretical modelling for identifying shale gas development prospective zones according to thermal maturity mapping and for predicting quantitatively the geochemical and inorganic changes that occur with thermal evolution.