皖南二叠纪海相暗色岩系成因及有机质富集模式

皖南二叠系已成为页岩气勘探的重要目标层位,暗色岩系的硅质来源长期存在争议,有机质富集堆积机理尚不清楚。本文通过皖南地区二叠纪海相栖霞组、孤峰组和大隆组暗色岩系的岩石学特征、古生物群落、沉积特征、有机质丰度和元素地球化学特征分析,探讨其沉积背景、硅质来源和有机质富集模式。研究表明：栖霞组硅质主要来源于热液;孤峰组硅质主要来源于生物和热液;大隆组硅质主要来源于生物和热液,少量来源于生物。二叠纪属热带—亚热带温暖潮湿气候,暗色岩系沉积于具缓慢沉积速率的厌氧—贫氧的100～300 m水体环境中,有机质含量高。栖霞组和孤峰组富有机质暗色岩系的形成除受控于局限滞留的缺氧环境外,还和海底热液活动提供生物繁盛的营养元素与矿物质和上升流的作用有较为密切的关系。大隆组富有机质暗色岩系的形成与长兴期多期火山喷发带入大量营养元素和微量元素,导致初级生产力提高,生物消亡—繁盛—再消亡—再繁盛—消亡,生烃母质快速堆积,且与缺氧环境密不可分。     

四川广元上寺剖面上二叠统大隆组有机质分布特征与富集因素

四川盆地上二叠统大隆组富有机质硅质泥岩是页岩气勘探的一套重要目的层系.利用扫描电子显微镜和元素地球化学等方法探究大隆组有机质类型、分布特征及富集因素,对该地区非常规油气勘探具有指导意义.根据扫描电镜图片,上寺剖面大隆组有机质按形态可分为形态有机质、弥散有机质和沥青.三者成因不同,形态有机质是选择性保存的结果,以离散状分布在所有岩性样品中;弥散有机质是大隆组有机碳总量(total organic carbon,TOC)的主体,主要分布在硅质泥岩样品中,硅质灰岩样品中极少,体现了粘土矿物的吸附作用;沥青是可溶有机质运移进入孔、缝系统,经高热演化后形成的块状有机质,主要分布于硅质灰岩和灰岩样品中.该剖面地球化学数据显示缺氧沉积环境有利于有机质保存,但海洋表层生产力才是控制TOC含量变化的主要因素.研究表明,晚二叠世海平面上升导致上寺剖面大隆组表层生产力增加及底层海水缺氧,该组富有机质黑色硅质泥岩段高TOC是沉积环境与矿物吸附共同作用的结果,同时也反映了原生有机质保存情况.更好的理解泥质烃源岩中有机质赋存类型有助于烃源岩评价及非常规油气勘探开发工作.      

Depositional and Ecological Features of Permian Oxygen Deficient Deposits at Shangsi Section, Northeast Sichuan, China

Because oxygen deficient conditions enhance the preservation of depositional organic matter, analysis on paleooxygenation conditions of depositional environments becomes a routine work in evaluations of potential hydrocarbon source rocks. The article focuses on depositional and ecological features relating to oxygen deficient shelfal environments at the Shangsi (上寺) Section, as a part of multidiscipline collaboration to reevaluate the hydrocarbon potential of the Middle and Upper Permian, Guangyuan (广元), Northeast Sichuan (四川) Province. Icbnofabric Zoophycos, sepioilte-bearing limestones (SBL) were interpreted as indicators of dysaerobic environments. Laminated calcareous and/or siliceous mudstones with pelagic ammonites and radiolarians were believed to be the deposits of anaerobic environments. When rhythmic succession was considered, average strategy was adopted for the oxygenation explanation of a given intervaL The anaerobic condition in this Permian section was observed in the upper part of the latest Permian Dalong (大隆) Formation, in which siliceous mudstones with ammonite, radiolarians develop in association with lower U/Mo ratio, lower biomarker ratio of Pr/Ph, and the highest TOC content. The topmost Maokou (茅口) Formation, featured by thin-bedded calcareous and siliceous mudstones with ammonite, thin-shelled bivalves, and laminations would be deposits of the quasianaerobic condition. The middle part of the Members and Ⅲ of the Chihsia Formation is proposed to be dysaerobic condition as indicated by occurrences of SBL and ichnofabric features, with the Member Ⅲ being the severe dysaerobic condition.     

Carbon and oxygen isotopes suggesting deep-water basin deposition associated with hydrothermal events （Shangsi Section,Northwest Sichuan Basin-South China）

Carbon and oxygen isotope records for Shangsi Section in Northwest Sichuan Basin, South China can help investigating depositional environments and processes, including the burial rate and possible contribution of hydrothermal events. Samples from the lower Chihsian Formation show δ13CPDB and δ18OPDB values close to those of typical marine limestone. However, the overlying Permian middle-upper Chihsian, Wujiaping, and Maokou Formation samples reveal negative δ18OSMOW values and strong positive δ13CPDB values. These indicate high biological productivity and rapid burial of organic carbon. Samples from the Dalong Formation present both negative δ13CPDB and negative δ18OPDB values, which are quite different from the underlying Permian strata. These abnormal carbon and oxygen isotope characteristics in the Dalong Formation may suggest that hydrothermal processes contributed to deposition.     

四川广元上寺剖面上二叠统大隆组优质烃源岩发育主控因素初探

对四川广元上寺上二叠统剖面进行岩石学和地球化学分析,并利用Al/Ti值评估古生产力,而利用Mo、u、V、Cr、V/Cr和V/(V+Ni)来评估沉积环境,进而探讨烃源岩中有机质的积累与海洋初级生产力、沉积环境(氧化还原条件)以及沉积速率之间的关系.研究发现,在大隆组中部,TOC、过剩铝、Cu、Ni和Cd出现高值(TOC平...     

下扬子地区上二叠统页岩气成藏条件分析

【研究目的】下扬子地区上二叠统广泛发育龙潭组-大隆组暗色页岩,是中国页岩气调查的重点层位。目前该区勘探程度低,导致对该区页岩气成藏条件认识不清。【研究方法】通过龙潭组和大隆组页岩地球化学特征、储集性能,以及保存条件等方面的研究,对该区页岩气资源潜力进行了评价,对有利区进行了优选。【研究结果】龙潭组和大隆组有机质丰度高,TOC含量普遍大于2.0%,热演化程度适中(介于1.3%～2.5%),储集空间以墨水瓶和狭缝状中孔为主,脆性矿物含量普遍高于50%,具有较好的生烃物质基础和可压裂性。龙潭组页岩累计厚度较大,具有良好的自封闭能力,保存条件总体优于大隆组。二者均发育多种类型的裂缝,是页岩气逸散的主要通道,此外,后期岩浆活动较为频繁,对于页岩气有很强的破坏作用,保存条件是页岩气富集的关键。【结论】下扬子地区上二叠统页岩气选区评价应以沉积环境、生烃能力、储集性能等为基础,以页岩气保存条件为关键,采取“强中找弱”的原则进行,最终在下扬子地区大隆组和龙潭组分别划分了5个有利区。     

Biogeochemical Records at Shangsi Section, Northeast Sichuan in China： The Permian Paleoproductivity Proxies

The marine primary producers assimilate the atmospheric CO2 to form the organic carbon in surface water. The organic carbon then settles down through the water column and is removed from the oceans by final preservation in sediments in the form of petroleum or nature gases. The reconstruction of paleoproductlvity will thus improve our understanding of the biological processes in the formation of fossil energy resource and help to locate new sites for future exploration. In this study, biorelated elements P, Cd, Al, Ba, as well as redox sensitive element Mo, were analyzed in the 448 rock samples collected from Permian strata at the Shangsi (上寺) Section, Guangyuan (广元), Northeast Sichuan (四川) in China. On the basis of the Ti content, the nondetrital contents of P, Ca, and Al, denoted as Pxs, Cdxs, and Alxs, were calculated and found to coincide with the TOC content throughout the whole section, with some enrichment intervals being found in the middle part of Chihsia Formation, topmost Maokou (茅口) Formation, and Dalong (大隆) Formation. This suggests that the biorelated elements could be used as proxies for the paleoproductivity here in this section. Baxs, a paleoproductivity indicator widely used in the paleoceanography, shows insignificant correlation with TOC, Pxs, Cdxs, and Alxs, probably arising from the loss of biological barium in anoxic conditions. Compiled with the data of TOC content and Pxs Cdxs, and Alxs, three episodes of enhanced paleoproductivity were identified in Permian strata including the middle part of Chihsla Formation, topmost Maokou Formation, and Dalong Formation.     

Carbon Isotope Records Indicative of Paleoceanographical Events at the Latest Permian Dalong Formation at Shangsi, Northeast Sichuan, China

Paired organic and carbonate carbon isotope compositions of Late Permian Wujiaping (吴家坪) and Dalong (大隆) formations at Shangsi (上寺), Northeast Sichuan (四川) were analyzed by MAT 251. An abrupt negative excursion in the two isotope records was observed in the middle part of Dalong Formation, in association with a drop in the carbon isotope difference of the two records and an increase of total organic carbon (TOC) content. The negative drop of the paired carbon isotope records issuggestive of the input of 12C-enriched CO2. The molecular ratios of pristane to phytane and dibenzothiophene to phenanthrene indicate the anoxic condition in this interval. The enhanced TOC content is indicative of the elevated preservation of organic matter due to the anoxic condition. These isotopic and organic geochemical data probably infer the occurrence of the upwelUng in this interval. The additional contribution of volcanism activity observed in South China cannot be excluded to the input of 12C-enriched CO2 and the negative shifts in carbon isotope composition of bulk organic matter and carbonate.     

扬子地区古生代主要烃源岩有机质富集的环境动力学机制与差异

在扬子地块古生界发育了3套区域性的优质烃源岩,即:下寒武统、上奥陶统一下志留统、二叠系(中、上二叠统).下寒武统烃源岩主要由硅质岩(留茶坡组)和上部的硅质泥岩、碳质泥岩(或石煤)(牛蹄塘组)组成.早寒武世在台一盆转换带(或台地边缘)广泛发育的海底热液活动,喷流出大量的富硅流体,使大量硅岩得以在台缘外侧-盆地区沉淀;同时...     

华南李家沱剖面寒武纪纽芬兰世海水氧化还原性质演化及其驱动因素

大气-海洋含氧量的演化对埃迪卡拉纪-寒武纪转折期的后生动物大爆发事件具有重要影响.为探讨寒武纪纽芬兰世中国南方海洋氧化还原性质的演化及其初级生产力、海水硫酸盐浓度等演化驱动因素, 分析了李家沱剖面纽芬兰世留茶坡组和小烟溪组微量元素、有机碳含量、有机碳同位素、总硫含量、黄铁矿硫同位素等.该剖面沉积于斜坡-盆地环境且出露齐全.该剖面上V/Sc、Th/U及Mo、U、V、Ni、Cu等元素的富集系数呈现出5个变化旋回, 其中留茶坡组中上部和小烟溪组中部各存在一氧化环境段, 其余层段处于缺氧环境, 而Re/Mo则显示仅在小烟溪组中部水体出现过短暂的氧化环境和含有游离H₂S的硫化环境, 其余层段处于没有游离H₂S的缺氧非硫化环境.Ba、Ni、Cu、Zn、Cd等微量元素的富集系数及TOC表明: 留茶坡组的有机质沉降量和埋藏量都明显小于上覆小烟溪组; 而在小烟溪组中, 其中部有机质的沉降量和埋藏量最低, 下部最高, 上部次之.TOC/TS、TS以及黄铁矿硫同位素的垂向演化趋势等都显示李家沱剖面纽芬兰世大都处于低海水硫酸盐浓度环境.低海水硫酸盐浓度是造成李家沱剖面纽芬兰世缺氧水体未富集游离H₂S的主要原因.大气含氧量的升高是导致李家沱剖面小烟溪组中部出现短暂氧化环境以及近硫化环境的主要原因.      

湘中南区晚二叠世大隆组牙形刺及其地层意义

通过对湘中南区部分剖面晚二叠世大隆组下部层位的系统采样和分析，获取了珍贵的牙形刺资料，其时限为晚二叠世。以大隆组下部所产Ａｌｔｕｄｏｃｅｒａｓ、Ｐａｒａｃｅｌｔｉｔｅｓ等菊石为依据将龙潭组时代全部划入中二叠世晚期（茅口期）的观点是不适宜的。     

四川盆地广元地区大隆组有机质富集规律

四川盆地西北广元地区上二叠统大隆组主要为碳酸盐岩、硅质岩和页岩互层沉积.对四川广元长江沟剖面进行精细解剖的结果表明,大隆组中有机碳质量分数为0.16%~14.6%,有机碳质量分数与岩性关系密切,高有机碳质量分数赋存于黑色页岩和纹层状灰岩中,其中碳酸盐岩的有机碳质量分数与纹层厚度呈反比,即纹层厚度越大有机碳质量分数越低.大隆组优质烃源岩位于大隆组中部岩段,岩性组合为黑色页岩和硅质岩互层,间夹薄层状灰岩或纹层状灰岩.微量元素分析结果显示有机质的富集明显受控于沉积阶段及早期成岩阶段的氧化还原条件.综合分析表明大隆组烃源岩有机质富集受晚二叠世沉积环境、氧化还原条件、生物生产力、深部热液流体的影响,其中厌氧、缺氧环境是大隆组烃源岩发育的主控因素,高生物产率是有机质富集的前提条件.     

Coincident negative shifts in sulfur and carbon isotope compositions prior to the end-Permian mass extinction at Shangsi Section of Guangyuan, South China

Sulfur isotope composition of carbonate-associated sulfate (δ³⁴S_CAS) and carbon isotope composition of carbonate (δ¹³C_carb) were jointly investigated on the Late Permian rocks at Shangsi Section, Guanyuan, Northeast Sichuan, South China. Both δ³⁴S_CAS and δ¹³C_carb show gradual decline trends in Late Permian strata, inferring the occurrence of the long-term variation of marine environmental conditions. Associated with the long-term variation are the two coincident negative shifts in δ³⁴S_CAS and δ¹³C_carb, with one occurring at the boundary between Middle Permian Maokou Formation and Late Permian Wujiaping Formation and another at Middle Dalong Formation. Of significance is the second shift which clearly predates the regression and the biotic crisis at the end of Permian at Shangsi Section, providing evidence that a catastrophic event occurred prior to the biotic crisis. The frequent volcanisms indicated by the volcanic rocks or fragments, and the upwelling are proposed to cause the second negative excursion. An abrupt extreme negative δ³⁴S_CAS (ca. −20‰) associated with a low relative concentration of CAS and total organic carbon without large change in δ¹³C_carb is found at the end of the second shift, which might arise from the short-term oxygenation of bottom waters and sediments that resulted from the abrupt sea level drop.     

Comparative geochemistry of cadmium, rhenium, uranium, and molybdenum in continental margin sediments

The concentrations of authigenic phases of Cd, Re, U, and Mo increase with depth in four 45-cm-long sediment box cores collected along the axis of the Laurentian Trough, Gulf of St. Lawrence. Average authigenic accumulation rates, estimated from element inventories, are similar to rates in other continental margin environments. Strong regional variations in sediment accumulation rate and sulfide concentration have little influence on the accumulation rates of Cd and Re. This suggests that slow precipitation kinetics controls the accumulation of Cd and Re in these sediments. The accumulation rate of authigenic U is more variable; it may be tied to the kinetics of microbially mediated U reduction and be controlled by the availability of reactive organic matter. Authigenic Mo is distinguished by a sharp subsurface concentration minimum, above which Mo cycles with manganese. Mo released to pore water upon reduction of Mn oxides diffuses downward and enriches the subsurface sediment. Mo accumulates most rapidly in the sediment with the highest sulfide content. Slow conversion of molybdate to thiomolybdate may explain the much slower Mo accumulation rate in the less sulfidic sediments. A component of authigenic Mo accumulates with pyrite in an approximately constant Mo:Fe ratio. The accumulation rate of pyrite and associated Mo is insensitive to AVS abundance. Pyrite formation may be limited by the reactivity of iron oxide minerals.     

Molybdenum isotope composition from Yangtze block continental margin and its indication to organic burial rate

The paper presents the molybdenum isotope data, along with the trace element content, to investigate the geochemical behavior of authigenic Mo during long-term burial in sediments in continental margin settings of the Yangtze block, as well as their indication to the burial of original organic carbon. The burial rate of original organic carbon was estimated on the basis of the amount of sedimentary sulfur (TS content), whilst the carbon loss by aerobic degradation was estimated according to calculated Mn contents. On these points, the original organic carbon flux was calculated, exhibiting a large range of variation (0.17–0.67 mmol/m²/day). The strong correlation between sedimentary Mo isotope values and organic carbon burial rates previously proposed on the basis of the investigations on modern ocean sediments, was also used here to estimate the organic carbon burial rate. The data gained through this model showed that organic carbon burial rates have large variations, ranging from 0.43–2.87 mmol/m²/day. Although the two sets of data gained through different geochemical records in the Yangtze block show a deviation of one order of magnitude, they do display a strong correlation. It is thus tempting to speculate that the Mo isotope signature of sediments may serve as a tracer for the accumulation rate of original organic carbon in the continental margin sediments. __________ Translated from Earth Science—Journal of China University of Geosciences, 2007, 32(6) [译自: 地球科学—中国地质大学学报]     

Remobilization of authigenic uranium in marine sediments by bioturbation

Uranium behaves as a nearly conservative element in oxygenated seawater, but it is precipitated under chemically reducing conditions that occur in sediments underlying low-oxygen bottom water or in sediments receiving high fluxes of particulate organic carbon. Sites characterized by a range of bottom-water oxygen (BWO) and organic carbon flux (OCF) were studied to better understand the conditions that determine formation and preservation of authigenic U in marine sediments. Our study areas are located in the mid latitudes of the northeast Pacific and the northwest Atlantic Oceans, and all sites receive moderate (0.5 g/cm² kyr) to high (2.8 g/cm² kyr) OCF to the sediments. BWO concentrations vary substantially among the sites, ranging from <3 to ∼270 μM. A mass balance approach was used to evaluate authigenic U remobilization at each site. Within each region studied, the supply of particulate nonlithogenic U associated with sinking particles was evaluated by means of sediment traps. The diffusive flux of U into sediments was calculated from pore-water U concentration profiles. These combined sources were compared with the burial rate of authigenic U to assess the efficiency of its preservation. A large fraction (one-third to two-thirds) of the authigenic U precipitated in these sediments via diffusion supply is later regenerated, even under very low BWO concentrations (∼15 μM). Bioturbating organisms periodically mix authigenic U-containing sediment upward toward the sediment-water interface, where more oxidizing conditions lead to the remobilization of authigenic U and its loss to bottom waters.     

Nitrogen isotope chemostratigraphy across the Permian–Triassic boundary at Chaotian,Sichuan, South China

Nitrogen isotopic compositions of upper Permian to lowermost Triassic rocks were analyzed at Chaotian in northern Sichuan, South China, in order to clarify changes in the oceanic nitrogen cycle around the Permian–Triassic boundary (P–TB) including the entire Changhsingian (Late Late Permian) prior to the extinction. The analyzed ca. 40 m thick interval across the P–TB at Chaotian consists of three stratigraphic units: the upper Wujiaping Formation, the Dalong Formation, and the lowermost Feixianguan Formation, in ascending order. The upper Wujiaping Formation, ca. 10 m thick, is mainly composed of dark gray limestone with diverse shallow-marine fossils such as calcareous algae and brachiopods, deposited on the shallow shelf. In contrast, the overlying Dalong Formation, ca. 25 m thick, is mainly composed of thinly bedded black mudstone and siliceous mudstone containing abundant radiolarians, deposited on the relatively deep slope/basin. Absence of bioturbation, substantially high total organic carbon contents (up to 15%), and abundant occurrence of pyrite framboids in the main part of the Dalong Formation indicate deposition under anoxic condition. The lowermost Feixianguan Formation, ca. 5 m thick, is composed of thinly bedded gray marl and micritic limestone with minor fossils such as ammonoids and conodonts, deposited on the relatively shallow slope. δ¹⁵N_TN values are in positive values around +1 to +2‰ in the upper Wujiaping Formation implying denitrification and/or anammox in the ocean. δ¹⁵N_TN values gradually decrease to −1‰ in the lower Dalong Formation and are consistently low (around 0‰) in the middle Dalong to lowermost Feixianguan Formation. No clear δ¹⁵N_TN shift is recognized across the extinction horizon. The consistently low δ¹⁵N_TN values suggest the enhanced nitrogen fixation in the ocean during the Changhsingian at Chaotian. Composite profiles based on previous and the present studies demonstrate the substantial δ¹⁵N variation on a global scale in the late Permian to earliest Triassic; a systematic δ¹⁵N difference by low and high latitudes is particularly clarified. Although the enhanced nitrogen fixation throughout the Changhsingian at Chaotian was likely a regional event in northwestern South China, the composite δ¹⁵N profiles imply that the sea area in which fixed nitrogen is depleted has gradually developed worldwide in the Changhsingian, possibly acting as a prolonged stress to shallow-marine biota.