Kerogen: chemical structure and formation conditions

The available data on the composition of the pyrolysis products of kerogen from the Mesozoic carbonaceous strata of the Russian Plate evidence that changes in the contents of total organic carbon (TOC) lead to a regular change of the mechanisms of organic-matter (OM) conservation in sediments. Each mechanism prevails for particular TOC contents. The initial increase in the TOC content of rocks is accounted for by the fact that the higher is the biologic productivity of the basin, the higher is the portion of nonmineralized organic matter. This is due mainly to the mechanism of selective accumulation of the most stable biochemical components such as algaenan. The appearance of H₂S first in the pore waters of sediment and then in the water column increases the degree of preservation of initial OM at the expense of its sulfurization. This process runs first in the lipid and then in the carbohydrate fractions of initial OM.     

Early Aptian oceanic anoxic event (OAE 1a) in Northeastern Arabian Plate setting: an example from Dariyan Formation in Zagros fold–trust belt,SE Iran

The Dariyan Formation (southwestern Iran) records the characteristic features of an oceanic anoxic event with organic- and radiolarian-rich hemipelagic intervals. A biostratigraphic study based on benthic and planktonic foraminifers provides an early Aptian age for the organic-rich succession and an Aptian age for the entire Dariyan Formation in this area. In this study, we report the first stable carbon isotope curve for the Dariyan Formation which is characterized by a pronounced negative spike (reaching ?2?‰) at the base of the section followed by a subsequent positive excursion (4?‰) and a plateau with values fluctuating around 3?‰. The integration of the δ¹³C record with the previously published litho- and biostratigraphy provides the characteristic features of the oceanic anoxic events (OAE) 1a interval. This detailed curve improved the stratigraphic resolution in this area and allowed the establishment of a temporal framework which showed good correlations with other OAE 1a sections worldwide. High production of organic matter and abundance of radiolarians and planktonic foraminifers suggest high-nutrient fluxes and meso- to eutrophic conditions at the time of deposition of the organic-rich interval of the Dariyan Formation. This is in agreement with enhanced greenhouse conditions. The facies distribution (from shallow to deep water environments) and the paleogeography of Arabian Plate during the early Aptian suggest that increasing continental runoff was a primary trigger of high trophic level conditions. Redox conditions, estimated from manganese (Mn) behavior, indicate dysoxic to anoxic conditions within the basin during OAE 1a.     

Benthic microbial mats: a possible major component of organic matter accumulation in the Lower Aptian oceanic anoxic event

Oceanic anoxic events (OAEs) throughout the Cretaceous were periods of high organic carbon burial leading to drawdown of atmospheric carbon dioxide and lowering of bottom-water oxygen concentration, thereby enhancing the preservation of organic matter (OM). Two dynamic depositional models have been proposed for these events in the Tethyan domain: one is based on strong thermohaline stratification and low surface productivity, the other on high surface productivity with intensified deep-water circulation. Here, we propose another explanation for the concentration of OM, derived essentially from microscopical observations (scanning electron microscope and transmission electron microscope) in the organic-richest interval of an Early Aptian OAE in central Italy (OAE1a or Selli level, 116 Ma). This high-resolution microscopical study of OM highlights benthic microbial mats as the possible source of organic-rich samples where amorphous OM is the major organic constituent. These mats could be more common in OAE black shales than previously thought.     

New age data on the deposits of the Kiselevka-Manoma accretionary complex based on radiolarian fossils

The Kiselevka-Manoma Complex, the youngest accretionary complex in the Russian Far East, is composed of Jurassic-Lower Cretaceous pelagic and hemipelagic oceanic deposits. The radiolarian biostratigraphic study made it possible to refine the stratigraphy of the upper portion of the siliceous sediments from the northeastern fragment of this accretionary complex in the vicinity of the Kiselevka settlement in the Lower Amur region. The transition from pelagic siliceous to hemipelagic siliceous-clayey sedimentation was established within the interval from the Late Barremian to the Middle Aptian in different parts of the complex. The age of the accretion of the oceanic rocks is defined as postmiddle Aptian.     

塔里木盆地下寒武统底部高熟海相烃源岩中有机质的赋存状态

近年来的研究证明,中新生代未熟—低熟海相富有机质泥质烃源岩中有机质是通过溶解在水中的分子规模的碳有机质以化学吸附的形式被吸附到矿物表面上和蒙脱石结构层内。然而,对于高熟海相泥质烃源岩中有机质的赋存状态却少有报道。通过对塔里木盆地下寒统底部高熟海相泥质烃源岩的有机碳含量、矿物表面积、扫描电镜和透射电镜的综合分析,得到了其有机质以细小的颗粒状保存于沉积物颗粒之间的结论。同时,通过高熟海相烃源岩与现代未熟海相烃源岩有机质赋存状态的对比,提出了值得进一步研究的有关科学问题。     

缺氧沉积物及其衍生物的Re-Os同位素定年与示踪

Os属铂族元素,其不同于亲石元素的地球化学性质使得Re-Os同位素体系在金属矿床和超基性-基性岩浆岩的定年与地球化学示踪研究中得到了广泛应用。Re、Os元素具有亲铁和一定程度的亲铜性质,能在还原环境中与硫化物和/或有机物结合而发生相对富集,因此可应用Re-Os同位素体系对缺氧环境中形成的富有机质沉积物及其衍生物进行定年与示踪研究。本文综述了近年来Re-Os地球化学在这一领域的研究新进展,包括黑色页岩中Re-Os富集机制的探讨,沉积岩的等时线法定年,风化作用、烃类成熟度和变质作用等对黑色页岩等富有机质沉积岩Re-Os同位素体系的影响,沉积环境的Os同位素示踪以及黑色页岩Os模式年龄的意义等,并对这些研究成果在石油、沥青等有机矿产的成因研究及其勘查工作中的应用前景进行了评述。     

Occurrence of Highly Mature Organic Matter in Marine Black Shale Petroleum Source Rocks of Basal Cambrian from Northern Tarim Basin, China

More and more evidence indicates that organic matter (OM) in immature organicrich sediments and sedimentary rocks is chemically adsorbed onto the outer surfaces of minerals and into interlayer (inner) surfaces of smectitic clay minerals in the form of amorphous molecular-scale carbon. But there have been few reports about the occurrence of highly mature OM in marine black shales ( petroleum source rocks ). The occurrence of highly mature OM in the black shales of basal Cambrian from northern Tarim Basin is studied in this paper. Based on the comprehensive analyses of total organic carbon contents (TOC) , maximum thermolysis tempera tures ( Tmax ) of OM, mineral surface areas (MSA) ,and scanning electronic microscopic (SEM) and transmission electronic microscopic (TEM) observations of the black shales, it is concluded that the highly mature OM in the marine black shales of the basal Cambrian from northern Tarim Basin occurs in particulates ranging in size from 1 to 5 μm in diameter. Through the contrast of the occurrence of the highly mature OM in the black shales with that of the immature ones in modern marine continental margin sediments, some scientific problems are proposed, which are worth to study further in detail.     

Biogeochemical processes of carbon and sulfur cycles in sediments of the outer shelf of the Black Sea (Russian Sector)

Within the mass of recent (unit-I) and ancient Black Sea (unit-II) sediments on the outer shelf of the Russian sector of the Black Sea, the rates of anoxic processes participating in diagenetic transformations of carbon and sulfur compounds were first measured using ³⁵S and ¹⁴C radioactive tracers. The main energy source for biogeochemical processes in (unit-I) sediments is the organic matter (OM) supplied to the bottom from the water mass. In (unit-II) sediments, this is methane in a migratory form proved by the excess of its oxidation rate over that of its generation. In recent silt, the primary microbial process is sulfate reduction; in unit-II, this is methane anoxic oxidation by the consortium of archeides and sulfate reductants. The organic matter produced in methane oxidation, in turn, acts as an energy source for the community of anaerobic heterotrophic microorganisms in the bottom sediments, which are remote from the water-sediment interface.     

Organic matter in Oligocene Maikop Sequence of the North Caucasus

The results of the thorough study of organic matter (OM) in the Oligocene-Miocene Maikop sequence of the North Caucasus are considered. It is shown that its distribution within the Maikop sequence is characterized by irregular patterns. Despite that these rocks show the elevated TOC content, their hydrocarbon-generating potential is, as a rule, low. The low quality of OM is partly related to its intense anaerobic decomposition in anoxic environments with terrigenous sedimentation. The elevation of OM concentrations and hydrocarbon-generating potential could be connected with the reinforced phytoplankton influx into sediments. Sediments deposited in the second half of the Early Oligocene were synchronously enriched in OM. This enrichment chronologically corresponded to the restoration of connection with the World Ocean of the formerly partly isolated and freshened basin. Most probably, this event resulted from the sharp increase in biological productivity.     

Early Cretaceous anoxic basin of the Russian Plate: Organic geochemistry

Compositions of organic matter in the bituminous shale accumulated under anoxic conditions and in the underlying clay deposited in aerated basin are noticeably different. Organic matter (OM) of the clay is depleted in hydrogen and kerogen of the clay during pyrolysis produces 2.5 times less aliphatic hydrocarbons than kerogen, which is separated from the bituminous shale, and dozens of times less sulfurous compounds, such as thiophenes and benzothiophenes. Accumulation of OM in the clay was primarily related to the direct inheritance of polymeric lipid biochemical components of the initial OM and lignin included in the higher plants. Changes of gas regime in the basin and sediments, expressed in the origin of anoxic conditions during the accumulation of bituminous shales, intensified the early diagenetic sulfuration and the consequent formation of sulfur- and hydrogen-rich kerogen in the shales. At the same time, less stable lipids and, possibly, carbohydrates were also conserved.Translated from Litologiya i Poleznye Iskopaemye, No. 1, 2005, pp. 25–34.Original Russian Text Copyright 2005 by Bushnev.     

Carbonate microfacies and chemostratigraphy of a late Aptian–early Albian marine distal section from the primitive South Atlantic (SE Brazilian continental margin): Record of global ocean-climate changes?

Late Aptian–early Albian limestones from the eastern Brazilian continental margin record the early evolution of the South Atlantic Ocean. In Tethyan and North Atlantic domains, a planktic foraminiferal turnover and organic-rich deposits related to Oceanic Anoxic Event 1b (OAE 1b) point to major ocean-climate changes through this interval. Coeval organic-rich deposits of the South Atlantic Ocean have been interpreted as the product of restricted circulation rather than attributed to a global event. However, previous investigations of the early marine phase of South Atlantic lack data from more distal facies, making correlations to global events difficult. Here, we present C, O, and Sr isotopes, elemental geochemistry, TOC and pyrolysis data, as well as a microfacies analysis of an upper Aptian–lower Albian distal section from the Campos Basin (southeastern Brazil). Our focus is on the paleoenvironmental characterization of and the possible association between organic-rich deposits and major perturbations related to Aptian–Albian transition. Five microfacies associations (MA) were identified in the informal units I and III, which were deposited in the neritic region on a carbonate ramp. Organic-rich deposits were described in unit III, composed of planktic-dominated wackestones interbedded with black shales, in a distal dysoxic to anoxic environment. The carbonates ⁸⁷Sr/⁸⁶Sr ratios showed a drastic increase (0.7072–0.7074), interpreted as enhanced chemical weathering, supported by the increase of continental input to the top of section. This trend was accompanied by a long-term δ¹³C_carb negative excursion, which were assigned to the latest late Aptian–early Albian interval of the isotope reference curves, in accordance with the described occurrence of Colomiella recta. This scenario matches those proposed for the late Aptian–early Albian transition and OAE 1b set, as an enhanced greenhouse stage, pointing to the influence of the referred ocean-climate changes on the deposition of organic-rich deposits of the early South Atlantic Ocean. This investigation gives more evidences that these perturbations were a widespread event, as a product of broad-scale disturbances in the global carbon cycle which also controlled organic deposition and preservation on restricted settings.     

Comparative geochemistry of quaternary carbonaceous sediments from the continental slope of the Baja California and the miocene monterey formation

The geochemistry of Upper Quaternary organic-rich (C_org 3.7–10.0%) sediments recovered by the 40-m-long Core MD02-2508 from the upper continental slope of Baja California is compared to the chemical composition of sedimentary rocks from the Miocene Monterey Formation, California. It is ascertained that concentrations of most macroelements (Al, Ti, Mg, K, Fe, M, S, C_org) and many microelements, including chalcophiles Ag, As, Mo, Sb, Se, Zn, along with some others (U, Co, Ni, Y, and REE) are nearly equal in both types of sediments. In addition, concentrations of most microelements in both types of sediments are close, to the average values common for the worldwide carbonaceous black shales irrespective of their lithology and age, indicating a stable influence of organic matter on their concentration during sedimentation and early digenesis.     

Organic Matter Accumulation in the Upper Permian Dalong Formation from the Lower Yangtze Region, South China

The Late Permian was marked by a series of important geological events and widespread organic-rich black shale depositions, acting as important unconventional hydrocarbon source rocks. However, the mechanism of organic matter (OM) enrichment throughout this period is still controversial. Based on geochemical data, the marine redox conditions, paleogeographic and hydrographic environment, primary productivity, volcanism, and terrigenous input during the Late Permian in the Lower Yangtze region have been studied from the Putaoling section, Chaohu, to provide new insights into OM accumulation. Five Phases are distinguished based on the TOC and environmental variations. In Phase I, anoxic conditions driven by water restriction enhanced OM preservation. In Phase II, euxinic and cycling hydrological environments were the two most substantial controlling factors for the massive OM deposition. During Phase III, intensified terrestrial input potentially diluted the OM in sediment and the presence of oxygen in bottom water weakened the preservation condition. Phase IV was characterized by a relatively higher abundance of mercury (Hg) and TOC (peak at 16.98 wt%), indicating that enhanced volcanism potentially stimulated higher productivity and a euxinic environment. In Phase V, extremely lean OM was preserved as a result of terrestrial dilutions and decreasing primary productivity. Phases I, II and IV are characterized as the most prominent OM-rich zones due to the effective interactions of the controlling factors, namely paleogeographic, hydrographic environment, volcanism, and redox conditions.     

Re-Os同位素在沉积地层精确定年及古环境反演中的应用进展

Re-Os同位素亲有机质的性质,使得富有机质沉积岩在沉积的过程中能够吸附富集海水中的Re、Os,沉积岩的沉积压实过程也是其中Re-Os同位素体系封闭计时的过程,沉积岩Re-Os同位素等时线年龄代表地层沉积时代,Os同位素初始比值187Os/188Os反映沉积时海水的Os同位素比值。Re-Os同位素体系在富有机质沉积岩中的成功应用,能够直接确定地层沉积时代,从而对地层界线进行直接厘定,并且能够对一些沉积矿床形成时代、冰川事件发生时代进行厘定和限制。通过沉积岩Re-Os同位素特征,可以对古环境进行反演,有助于了解全球大气海洋的演化,气候的变化,对研究生物灭绝等重大地质事件发生的时限和机制以及金属矿床的成矿物质来源具有重要意义。文章阐述了Re-Os同位素在富有机质沉积岩中应用的原理,并列举了Re-Os同位素在沉积地层精确定年及古环境反演中应用实例,说明了富有机质沉积岩Re-Os同位素分析精度及其影响因素,以使Re-Os同位素体系作为一种强有力的工具,解决更多的沉积地层时代问题以及更好地对古环境进行反演。     

鄂西地区上二叠乐平统大隆组硅质岩成因及有机质富集机理

晚二叠世是古生代环境、生物演化的关键时期,发育广泛的富有机质沉积,并成为南方重要的烃源岩层位。为了解该时期的富有机质堆积机理,我们选择了鄂西台内盆地晚二叠世大隆组富有机质硅质岩(TOC平均值为5.8%,峰值为18%)作为研究对象。硅质岩中常量元素Al/Fe均值为0.79,Mn/Ti均值为0.21,显示为大陆边缘环境下的生物成因,即非热水成因。∑REE值与Al2O3含量有着良好的正相关关系,表明当时陆源物质的输入对硅质岩的形成有很大影响。微量元素U/Th、V/(V+Ni)均说明硅质岩沉积环境为缺氧水体环境。通过对草莓状黄铁矿粒径的统计表明,大多数(64%～89%)的草莓状黄铁矿粒径小于5μm,反映缺氧甚至硫化的环境。而且,U、V、Mo的富集以及Ni、Cu元素的亏损说明水体的缺氧主要是由于海水分层,水体循环受阻造成的。TOC与氧化还原参数的变化步调基本一致,两者有着较好的正相关关系,而与生产力指标Ba/Al相关性很差,说明有机质富集主要是由水体的缺氧而不是初级生产力控制的。     

The Features of the Transformation of Organic Matter of Precambrian Carboniferous Rocks of the Ukrainian Crystalline Shield

The main features of the transformation of organic matter (OM) in the greenschist, amphibolite, and granulite facies of metamorphism are considered based on the example of the Ukrainian crystal shield. The occurrence area and OM content in highly carbonaceous ancient rocks are characterized. The composition of primary sedimentary rocks and the processes of accumulation of biophile elements under the OM transformation are reconstructed.     

Lower Aptian Subbetic organic-rich facies, radiolarites, and associated deposits: the local expression of Oceanic Anoxic Event 1a (Carbonero Formation, southern Spain)

The Carbonero Formation represents a scarce, well documented example of Aptian anoxic facies in the Betic Cordillera. Generally, the Aptian record in the pelagic Subbetic basin is both very discontinuous and affected by frequent hiatuses, but in some subsident areas controlled by extensional faults (as in the Carbonero trough) an interesting record is preserved. The Carbonero Formation is characterised by a thick pelagic succession composed of marls with intercalations of calcareous turbidites and a thick interval of anoxic facies. This interval, dated as early Aptian, most likely represents the local expression of Ocean Anoxic Event 1a in the Subbetic basin. A multidisciplinary study including lithostratigraphy, biostratigraphy, and sedimentology has been carried out in the Carbonero Formation, with special attention to the anoxic interval. A collection of facies and sedimentary features has been characterised and interpreted, including barite concretions, calcareous concretions, black shales, siliceous marls and radiolarites, and calcareous turbidites. All these facies seem to have been deposited under oxygen-depleted conditions on a fault-bounded depression with a high subsidence rate. The accumulation and burial of sediments and the preservation of organic matter were controlled by both local and regional factors, such as the physiography of the basin and tectonic setting, as well as by global factors, such as palaeoceanographic and climatic changes.     

The late Cenomanian paleoecological event (OAE 2) in the eastern Caucasus basin of Northern Peri-Tethys

The Cretaceous sections of the eastern Caucasus contain rich in organic matter (OM) sediments corresponding to the late Cenomanian Oceanic Anoxic Event 2. They are marked by positive δ¹³C and negative δ¹⁸O isotopic anomalies, which are characteristic for this level in many areas of the world. The sediments exhibit distinct cyclic patterns reflected in an alternation of black OM-rich and gray more calcareous layers. The rocks are enriched with many chemical elements, although concentrations of some of them (Mo, Se) are lower than in typical sediments of anoxic basins. It is inferred that anoxic environments in the paleobasin were unstable and locally developed. Nannofossil assemblages from OAE 2 sediments are dominated by the highly resistant eurytropic taxon Watznaueria accompanied by common cool-water Eprolithus and rare warm-water Rhagodiscus representatives, which implies the development of environments unfavorable for the normal marine nannoflora and short-term cooling in the basin during OAE 2. The OM-rich sediments were deposited against the background of the rapid eustatic transgression due to a significant increase in productivity of phytoplankton in the paleobasin. The OAE 2 duration is estimated to be approximately 400 ka.     

Geochemistry of trace element in carbonaceous sediments from recent seas and oceans

Published and original data on the contents of 50 elements in carbonaceous sediments from seas (Black, Baltic, and Caspian) and fertile oceanic shelves (shelves of Namibia, Peru, Chile, and California) are generalized. The comparison of these results with the average composition of ancient carbonaceous shales reveals both similarities and differences in the distribution of indicator trace elements (Re, Hg, Se, Ag, Cd, Tl, U, Mo, As, Ni, and Zn). Correlation coefficients were analyzed to determine the characteristic element associations. It is established that oceanic carbonaceous sediments are closer in composition to carbonaceous shales than their marine analogues, which is related to the differences in sedimentation conditions, including hydrological, hydrochemical, and biogeochemical factors. The role of anoxic environment in the accumulation of chalcophile elements in sediments is estimated. The comparison of the contents of some mobile trace elements in oceanic water and carbonaceous sediments of modern oceans demonstrates that the water composition affects the composition of carbonaceous sediments and can be used for deciphering the composition of ancient ocean water.     

Paleoenvironmental Characteristics of Paleogene Lacustrine Source Rocks in the Western Bozhong Sag, Bohai Bay Basin, China: Evidence from Biomarkers, Major and Trace Elements

The organic matter (OM) enrichment mechanisms and depositional environment characteristics of lacustrine source rocks in the western Bozhong Sag, Bohai Bay Basin in Northeast China remain controversial. To address these issues, based on Rock-Eval pyrolysis, kerogen macerals, H/C and O/C ratios, GC-MS, major and trace elements, the Dongying Formation Member (Mbr) 3 (E3d3), the Shahejie Formation mbrs 1 and 2 (E2s1+2), and the Shahejie Mbr 3 (E2s3) source rocks in the western Bozhong Sag were studied. The above methods were used to reveal their geochemical properties, OM origins and depositional environments, all of which indicate that E2s1+2 and E2s3 are excellent source rocks, and that E3d3 is of the second good quality. E3d3 source rocks were formed under a warm and humid climate, mainly belong to fluvial/delta facies, the E3d3 sediments formed under weakly oxidizing and freshwater conditions. Comparatively, the depositional environments of E2s1+2 source rocks were arid and cold climate, representing saline or freshwater lacustrine facies, and the sediments of E2s1+2 belong to anoxic or suboxic settings with large evaporation and salinity. During the period of E2s3, the climate became warm and humid, indicating the freshwater lacustrine facies, and E2s3 was characterized by freshwater and abundant algae. Moreover, compared with other intervals, the OM origin of E3d3 source rocks has noticeable terrestrial input. The OM origin of the E2s1+2 and E2s3 are mainly plankton and bacteria. Tectonic subsidence and climate change have affected the changes of the depositional environment in the western Bozhong Sag, thus controlling the distribution of the source rocks, the geochemical characteristics in the three intervals of lacustrine source rocks have distinct differences. Overall, these factors are effective to evaluate the paleoenvironmental characteristics of source rocks by biomarkers, major and trace elements. The established models may have positive implications for research of lacustrine source rocks in offshore areas with few drillings.