First data on methylhopanes in Lower Cambrian organic matter of the Siberian platform

Hopane hydrocarbons of bitumoids from the organic matter of the Lower Cambrian Sinyaya and Kutorgina formations on the northern slope of the Aldan anteclise were studied using chromatography?mass spectrometry. Methylhopanes were found for the first time in autochthonous bitumoids of scattered organic matter from Cambrian sedimentary basins in Siberia. The biological sources of these molecules, along with the features of geochemistry, sedimentation conditions, diagenesis, and degree of maturity of methylhopanecontaining organic matter are considered. Methylhopanes were recommended to be used jointly with other biomarkers of the Sinyaya formation rocks enriched in organic matter to determine the possible source of naphthides in the southeastern part of the Siberian platform.     

Hopanes and hopenes of the Lower Cambrian Sinyaya Formation (northern slope of the Aldan Anteclise)

Hopane hydrocarbons contained in organic matter from the Lower Cambrian Sinyaya Formation, southeast of the Siberian platform, were analyzed by gas chromatography/mass spectrometry. This study first identified C₂₈ 28, 30-bisnorhopane and its homologues present in high concentrations in autochthonous organic matter from East Siberian sedimentary basins. These biomarkers can be used in distinguishing between the sources of naphthides on the northern slope of the Aldan anteclise. Two saturated naphthenic hydrocarbons, C₃₁ homohopene and C₃₁ 28-norhomohopene, were also detected. This study provides some details on hopane distribution, organic matter accumulation conditions, and the degree of OM catagenesis.     

New Geochemical Data on the Organic Matter in Rocks of the Lower and Middle Cambrian Kuonamka Complex,the Lena–Amga Interfluve Area,Southeastern Siberian Platform

Saturated hydrocarbon biomarkers were studied in bitumens from organic matter (OM) in the Lower and Middle Cambrian Kuonamka Complex in the Lena–Amga interfluve of East Siberia. Their contents and distribution were analyzed. It was established that OM of siliceous and carbonate rocks from the lower part of the sequence differs from OM of overlying mainly mixed siliceous–carbonate rocks in terms of distribution of alkanes, steranes, tricyclanes, hopanes, and ratios of their homologs. It was concluded that the peculiarities of molecular composition of OM in the rocks are related to the biochemistry of microorganism communities, the remains of which were accumulated in sediments of Cambrian sea. It is possible that the microbiota changed its composition in response to a sharp change of sedimentation settings, which follows from biomarker proxies. It is suggested that sediments in the lower part of the sequence were formed under conditions of H₂S contamination. Catagenesis of OM and contribution of the Lower and Middle Cambrian potentially oil-generating rocks in naphthide generation on the northern slope of the Aldan anteclise are discussed.     

Phenanthrene biomarkers in the organic matter of Precambrian and Phanerozoic deposits and in the oils of the Siberian Platform

The composition and distribution of phenanthrenes (polyaromatic compounds) have been studied in chloroform extracts from dispersed organic matter (OM) of clayey, siliceous, carbonate, and terrigenous rocks of different ages and facies and from some oils of the Siberian Platform. Phenanthrenes have been analyzed by gas chromatography-mass spectrometry. High contents of 1,7,8-trimethylphenanthrene and 1,1,7,8-tetramethyl-1,2,3,4-tetrahydrophenanthrene are present in the OM of Vendian and Cambrian carbonate-shale deposits and in ancient oils of the Nepa-Botuobiya and Anabar anteclises. The OM of Permian continental deposits and oils of the Vilyui syneclise is dominated by 1-methyl-7-isopropylphenanthrene (retene). A triangular diagram for identification of the types of original OM of rocks and classification of genetically related oils has been constructed based on the assessment of phenanthrene biomarker distribution. Putative pathways of the formation of phenanthrene biomarkers are discussed.     

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。     

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.     

Petroleum geochemistry of the Potwar Basin,Pakistan: II – Oil classification based on heterocyclic and polycyclic aromatic hydrocarbons

In a previous study, oils in the Potwar Basin (Upper Indus) of Pakistan were correlated based on the dissimilarity of source and depositional environment of organic matter (OM) using biomarkers and bulk stable isotopes. This study is aimed at supporting the classification of Potwar Basin oils into three groups (A, B and C) using the distribution of alkylnaphthalenes, alkylphenanthrenes, alkyldibenzothiophenes, alkyldibenzofurans, alkylfluorenes, alkylbiphenyls, triaromatic steroids, methyl triaromatic steroids, retene, methyl retenes and cadalene. The higher relative abundance of specific methyl isomers of naphthalene and phenanthrene and the presence of diagnostic aromatic biomarkers clearly indicate the terrigenous and oxic depositional environment of OM for group A oil. Group B and C oils are of marine origin and the aforementioned heterocyclic and polycyclic aromatic hydrocarbons (HCs) differentiate them clearly into two different groups. The relative percentages of heterocyclic aromatic HCs reveal that the distribution of these compounds is controlled by the depositional environment of the OM. Sulfur-containing heterocyclic aromatic HCs are higher in crude oils generated from source rocks deposited in suboxic depositional environments, while oxygen-containing heterocyclic aromatic HCs in combination with alkylfluorenes are higher in marine oxic and deltaic oils. Biomarker and aromatic HC parameters do not indicate significant differences in the thermal maturity of Potwar Basin oils. Triaromatic and methyl triaromatic steroids support the division of Potwar Basin oils into the three groups and their relative abundances are related to source OM rather than thermal maturity. Significantly higher amounts of C₂₀ and C₂₁ triaromtic steroids and the presence or absence of long chain triaromatic steroids (C₂₅, C₂₆, C₂₇, and C₂₈) indicates that these compounds are probably formed from different biological precursors in each group. Different isomers of methyl substituted triaromatic steroids are present only for short chain compounds (C₂₀–C₂₂) and the origin of these compounds may be short chain methyl steranes from unknown biological precursors.     

Loss on ignition and kjeldahl digestion for estimating organic carbon and total nitrogen in estuarine marsh soils: Calibration with dry combustion

Soils (n=250) were collected from ten salt and brackish-water marshes of North Carolina and analyzed for organic matter content by loss on ignition (LOI) and Kjeldahl nitrogen (KN). Total organic carbon and total nitrogen were determined on the same samples using an elemental CHN analyzer. Regression analyses indicated that LOI and KN were excellent estimators of organic C (R²=0.990) and total N(R²=0.986), respectively, in low clay content (0–11%) marsh soils containing a wide range of soil organic C (0.1–28%) and total N (0–1.6%). A quadratic equation best described the relationship between organic C and organic matter (Organic C=0.40 [LOI] +0.0025 [LOI]²) while a linear model accurately described the relationship between total N and Kjeldahl N (Total N=1.048 [KN]?0.010). The proportion of organic C in organic matter (C/OM) increased with increasing soil organic matter content, probably as a result of aging. Young marshes, which are characterized by low soil organic content contain C/OM ratios similar to emergent vegetation (40–45%). In old organic soils (70–80% organic matter), C/OM increased to 57–60% due to accumulation of reduced organic materials.     

应用TIMA分析技术研究Alum页岩有机质和黄铁矿粒度分布及沉积环境特征

Alum页岩(中寒武—早奥陶世)是北欧一套重要的海相烃源岩,其成熟度跨度从为成熟-过成熟度阶段。由于我国下古生界海相烃源岩均已过成熟,未成熟-低成熟度的Alum页岩是研究下古海相的烃源岩生烃潜力特征的重要参照样品。因此,对这套成熟度较低的Alum页岩的生物组成特征、矿物组成及其沉积环境的分析,可为后续国内外下古生界海相烃源岩的对比研究奠定基础。本文以欧洲上寒武统富含有机质Alum页岩为主要研究对象,在有机碳含量(TOC)和有机岩石学观察的基础上,应用综合矿物分析技术(TIMA)进行扫描,通过细化样品扫描参数,获得了页岩矿物组成、含量及粒度分布。Alum页岩有机质成熟度较低(固体沥青反射率为0.30),TOC含量在11.16%~12.24%之间。有机质主要为浮游藻类降解形成的层状藻类体、底栖藻类来源的海相镜状体和裂缝中充填的固体沥青。TIMA扫描获得的有机质相对质量百分含量为9.79%~10.64%,略低于碳硫分析仪测定的TOC含量;黄铁矿含量为4.17%~4.49%。TIMA扫描获得的有机质与黄铁矿比值与化学法的C/S比值相近,均分布在2.18~2.55范围。粒径分布特征上,有机质粒径主要分布在0.9~27.0μm之间(80%以上颗粒分布在1.2~5.5μm);草莓状黄铁矿粒径分布在0.9~17.0μm之间(小于0.5μm的颗粒占78%以上),反映了缺氧甚至硫化的环境。综合C/S比、有机岩石学与TIMA黄铁矿粒度分布特征,认为该页岩形成于闭塞封闭甚至硫化的沉积水体体系。该研究为油气地质领域的烃源岩(包括页岩)的研究提供了一种新的技术支持。     

Geochemical Characteristics of Organic Matter from Maikop Rocks of Eastern Azerbaijan

Based on investigation of more than 170 samples taken from natural outcrops of the Maikop Formation (Oligocene–Lower Miocene) in eastern Azerbaijan, the genetic hydrocarbon potential and the organic matter (OM) maturity of these rocks were estimated. In the study region, sedimentary rocks of this formation were deposited under reductive or weakly oxidative conditions. Possessing a relatively high (1.9%, on the average) content of organic matter of a mixed (continental–marine) OM, these rocks are able to generate both liquid and gaseous hydrocarbons under favorable conditions. Contributions of both the continental and marine components to the total organic carbon (TOC) varied in time and space. The upper and lower subformations of the Maikop Formation differ in the qualitative and quantitative compositions of OM. Oligocene rocks have a relatively lower OM content and are characterized by better oil-generating properties, as compared to lower Miocene rocks.     

Oil-and gas-bearing prerequisites in the Anadyr basin based on geochemical indicators

The Anadyr oil-and gas-bearing region is one of the promising areas for the development of oil and gas prospecting exploration research. The goal of this paper is estimation of the oil source potential in the deposits of the section, distinguishing the degree of potential realization and the character of the distribution of the main potential columns over the section in the basin, and revealing the genetic nature of hydrocarbons (HCs) with an attempt to find the genetic relations of the oil deposits with generating columns. Oils and organic matter (OM) from different parts of the sections were investigated. The oil source potentials of individual complexes were estimated, and an attempt was made to estimate the potential of the basin as a whole.     

Effect of N content and soil texture on the decomposition of organic matter in forest soils as revealed by solid-state CPMAS NMR spectroscopy

N has a controlling effect on litter biodegradation in the forest floor, while stabilization of organic matter in the mineral soil may be influenced by physical parameters related to soil texture. In this study, in order to understand the processes involved in soil organic matter (SOM) formation, the chemical composition of SOM was followed and evaluated with regards to N contents and soil texture. Samples were taken on sites covered with Norway spruce and displaying contrasting values of C/N ratios in the forest floor. The chemical structure of OM was characterized using solid-state CPMAS ¹³C and ¹⁵N nuclear magnetic resonance (NMR) spectroscopy, along with Proton Spin Relaxation Editing (PSRE) sequences. Four groups of sampling sites were defined based on the NMR spectra of Oh and A horizons. In each group displaying similar NMR characteristics, N content and soil texture could be highly different among sites. Some Oh horizons with similar NMR spectra had very different N contents. Highly humified OM in Oh horizons were observed mainly on sites with low N contents. Some A horizons with different soil texture displayed similar OM chemical structure. High contents of O-alkyl C in some A horizons could originate from higher fresh root material input.     

Organic matter preservation in the carbonate matrix of a recent microbial mat – Is there a ‘mat seal effect’?

Phototrophic mats (microbial mats with a phototrophic top layer) are complex systems in terms of microbial diversity, biogeochemical cycles and organic matter (OM) turnover. It has been proposed that these mats were a predominant life form in Proterozoic shallow water settings, prior to the emergence of bioturbating organisms in the Ediacaran–Cambrian transition. For most of the Precambrian, microbial mats were not only quantitative important carbon fixing systems, but also influenced the transfer and transformation of OM before it entered the geosphere. The profound alteration of compound inventories during transit through microbial mats, implying substantial consequences for OM preservation in the Proterozoic, was recently proposed as a “mat-seal effect” [Pawlowska et al. (2012) Geology 41, 103–106]. To obtain a better understanding of the early diagenetic fate of primary produced OM in microbial mats, we studied a recent calcifying mat from a hypersaline lake in Kiritimati, which showed in the deeper mat layers a maximum ¹⁴C_carbonate age of ∼1500 years. We particularly focused on OM entrapped in the carbonate matrix, because of the better potential of such biomineral-encapsulated OM to reach the geosphere before degradation (and remineralization). Our data indicate that selective preservation is important in phototrophic mats. While a diagenetic transformation of lipid fatty acids (FAs) was evident, their fatty acyl-derived hydrocarbon moieties were not introduced into protokerogen, which was instead mainly comprised of cyanobacterial and/or algal biomacromolecules. Our data support the proposed major impact of the “mat-seal effect” on OM turnover and preservation; i.e. the suppression of biosignatures derived from the upper mat layers, while signals of heterotrophic microbes thriving in deeper mat layers become preferentially preserved (e.g. high hopane/sterane ratios). This mechanism may have broad consequences for the interpretation of biomarkers from Proterozoic shelf environments, because biosignatures of phototrophic mat dwellers as well as planktonic signals may have become heavily biased by the production and turnover of OM in microbial mat systems.     

Sources and composition of organic matter for bacterial growth in a large European river floodplain system (Danube, Austria)

Dissolved and particulate organic matter (DOM and POM) distribution, lignin phenol signatures, bulk elemental compositions, fluorescence indices and microbial plankton (algae, bacteria, viruses) in a temperate river floodplain system were monitored from January to November 2003. We aimed to elucidate the sources and compositions of allochthonous and autochthonous organic matter (OM) in the main channel and a representative backwater in relation to the hydrological regime. Additionally, bacterial secondary production was measured to evaluate the impact of organic carbon source on heterotrophic prokaryotic productivity. OM properties in the backwater tended to diverge from those in the main channel during phases without surface water connectivity; this was likely enhanced due to the exceptionally low river discharge in 2003. The terrestrial OM in this river floodplain system was largely derived from angiosperm leaves and grasses, as indicated by the lignin phenol composition. The lignin signatures exhibited significant seasonal changes, comparable to the seasonality of plankton-derived material. Microbially-derived material contributed significantly to POM and DOM, especially during periods of low discharge. High rates of bacterial secondary production (up to 135 μg C L(-1) d(-1)) followed algal blooms and suggested that autochthonous OM significantly supported heterotrophic microbial productivity.     

Oil source rocks at mesozoic and cenozoic continental margins: Communication 2. Oil source rocks at continental margins in the second half of the cretaceous and in the Cenozoic

Oil source rocks represent sequences with the C_org content ranging from 3–5 to 15–20%. Sedimentary sections of large petroliferous basins usually include one or two such sequences, which generated liquid and gaseous hydrocarbons (HCs) during their long-term subsidence to the elevated temperature zone. The middle episode of the Late Cretaceous was marked by the accumulation of sediments with a high C_org content in different areas of the World Ocean. However, truly unique settings favorable for accumulation of the sapropelic organic matter (OM) appeared at continental margins that primarily faced the Tethys Ocean. The La Luna Formation is one of the best known source rock sequences responsible for the generation of liquid HCs in basins of the Caribbean region. In the Persian Gulf, the Kazhdumi Formation composed of marls and clayey limestones is considered the main oil-generating sequence. In the Paleogene after closure of the Tethys, the Pacific continental margins became the main domains that accumulated source rocks. The maximal deposition of sapropelic OM in this region corresponded to the early-middle Eocene. In the Neogene, the accumulation of source sediments was associated with deltas and submarine fans of large rivers and with upwelling zones. In basins of the Californian borderland, the main oil-generating sequences are represented by siliceous rocks of the Monterey Formation. They were deposited in a regional upwelling zone related to the cold California Current.     

黔北下寒武统牛蹄塘组烃源岩的生物标志物 特征和沉积环境

为研究黔北地区下寒武统牛蹄塘组烃源岩母质来源和沉积环境,开展了生物标志化合物分析,结果表明：①正构烷烃OEP接近1.0,无明显奇偶优势,受轻微生物降解影响,正构烷烃多表现为双峰型(C18/C25),(nC21+nC22)/(nC28+nC29)值为0.54~1.01,显示重烃组分占绝对优势;Pr/Ph值范围在0.51~0.82之间,具有植烷优势。②烃源岩样品组成相对丰度五环三萜烷>三环萜烷>四环萜烷,三环萜烷中C21、C23、C24呈倒V字形分布,Ts/(Tm+Ts)为0.45~0.50。③C27规则甾烷/C29规则甾烷略小于1或者接近1,芳烃化合物DBT/P为0.05~0.09。根据这些特征并结合干酪根同位素及正构烷烃同位素组成和变化规律,认为该区域下寒武统牛蹄塘组烃源岩形成于浅海还原环境,且有机质主要来源于细菌、藻类等低等水生生物,有机质热演化程度较高。根据常量、微量元素指标并结合有机地化指标刻划出从灯影组到牛蹄塘组和明心寺组沉积时期的水体环境,将牛蹄塘组烃源岩的形成分为3个阶段,第一阶段为早寒武世初始快速海侵阶段,第二阶段为深水还原高有机质产力阶段,第三阶段为海水缓慢变浅高有机质产力阶段,而到了明心寺组沉积时期为浅水氧化非烃源岩阶段。     

Organic matter and nutrients in an altered subtropical marsh system,Chiricahueto, NW Mexico

Seven sediment push-cores were extracted from Chiricahueto, a marsh affected by urban, industrial and agricultural wastes. Concentrations of total phosphorus (300-1,620 µg g^-1), organic carbon (4-39 mg g^-1) and total nitrogen (0.5-4.5 mg g^-1) in the sediments showed an exponential decrease with depth, related to the decomposition of organic matter (OM). Between 20 and 40% of OM initially deposited is degraded at the sediment-water interface under oxic conditions. Another fraction (40-60%) of non-refractory OM is decomposed within the sediments by oxidants other than oxygen. Likewise, the preservation of OM (<20%) was estimated as burial concentrations of C, N and P linked to organic compounds. The C/N ratios, '¹³C and '¹⁵N suggested that the major source of OM to the sediments derives from marine phytoplankton. The allochthonous sources of OM were overprinted by the high flux of marine autochthonous OM. However, an indirect terrestrial influence is recognised, in which high nutrient load derived from agricultural, domestic and industrial activities promoted high productivity.     

Bulk organic matter characteristics in the Pichavaram mangrove – estuarine complex,south-eastern India

The Pichavaram mangrove ecosystem is located between the Vellar and Coleroon Estuaries in south-eastern India. To document the spatial-depth-based variabilities in organic matter (OM) input and cycling, five sediment cores were collected. A comparative study was carried out of grain-size composition, pore water salinity, dissolved organic C (DOC), loss-on-ignition (LOI), elemental ratios (C/N and H/C), pigments (Chl a, Chl b, and total carotenoids), and humification indices. Sand is the major fraction in these cores ranging from 60% to 99% followed by silt and clay; cores from the estuarine margin have high sand content. In mangrove forests, pore-water DOC concentrations are high (32 ± 14 mg L⁻¹), whereas salinity levels are low (50 ± 5.5‰). Likewise, LOI, organic C and N, and pigment concentrations are high in mangroves. OM is mainly derived from upstream terrestrial matter and/or mangrove litter, and marine OM. The humification indices do not vary significantly with depth because of rapid OM turnover. The bulk parameters indicate that the Vellar and Coleroon Estuaries are more affected by anthropogenic processes than mangrove forests. Finally, greater variability and sometimes lack of specific trends in bulk parameters implies that the 2004 tsunami caused extensive mixing in sediments.     

Geochemical Characteristics of the Upper Permian Longtan Formation from Northeastern Sichuan Basin: Implications for the Depositional Environment and Organic Matter Enrichment

A set of organic-rich shales of the upper Permian Longtan Formation, which is widely developed in the northeastern part of the Sichuan Basin, is a key formation for the next step of exploration and development. At present, most studies on this set of formations have focused on the reservoir characteristics and reservoir formation mechanism of the shales, and basic studies on the palaeoenvironment and organic matter(OM) enrichment mechanism have not been fully carried out. In this paper, we recov...     

Composition and genesis of the organic matter in the bottom sediments of the East Siberian Sea

The chemical composition of organic matter (C_org, N_org, δ¹³C, δ¹⁵N, and n-alkanes) was studied in the top layer of bottom sediments of the East Siberian Sea. Possible ways were proposed to estimate the amount of the terrigenous component in their organic matter (OM). The fraction of terrigenous OM estimated by the combined use of genetic indicators varied from 15% in the eastern part of the sea, near the Long Strait, to 95% in the estuaries of the Indigirka and Kolyma rivers, averaging 62% over the sea area.