Molecular Structure of Kerogen in the Longmaxi Shale: Insights from Solid State NMR,FT‐IR,XRD and HRTEM

Kerogen plays an important role in shale gas adsorption, desorption and diffusion. Therefore, it is necessary to characterize the molecular structure of kerogen. In this study, four kerogen samples were isolated from the organic-rich shale of the Longmaxi Formation. Raman spectroscopy was used to determine the maturity of these kerogen samples. High-resolution transmission electron microscopy (HRTEM), 13C nuclear magnetic resonance (13C NMR) , X-ray diffraction (XRD) and Fourier transform infrared (FT-IR) spectroscopy were conducted to characterize the molecular structure of the shale samples. The results demonstrate that VReqv of these kerogen samples vary from 2.3% to 2.8%, suggesting that all the kerogen samples are in the dry gas window. The macromolecular carbon skeleton of the Longmaxi Formation kerogen is mainly aromatic (fa’=0.56). In addition, the aromatic structural units are mainly composed of naphthalene (23%), anthracene (23%) and phenanthrene (29%). However, the aliphatic structure of the kerogen macromolecules is relatively low (fal*+falH=0.08), which is presumed to be distributed in the form of methyl and short aliphatic chains at the edge of the aromatic units. The oxygen-containing functional groups in the macromolecules are mainly present in the form of carbonyl groups (fac=0.23) and hydroxyl groups or ether groups (falO=0.13). The crystallite structural parameters of kerogen, including the stacking height (Lc=22.84 ?), average lateral size (La=29.29 ?) and interlayer spacing (d002=3.43 ?), are close to the aromatic structural parameters of anthracite or overmature kerogen. High-resolution transmission electron microscopy reveals that the aromatic structure is well oriented, and more than 65% of the diffractive aromatic layers are concentrated in the main direction. Due to the continuous deep burial, the longer aliphatic chains and oxygen-containing functional groups in the kerogen are substantially depleted. However, the ductility and stacking degree of the aromatic structure increases during thermal evolution. This study provides quantitative information on the molecular structure of kerogen samples based on multiple research methods, which may contribute to an improved understanding of the organic pores in black shale.     

Prognostication of hydrocarbon generative potential in the onshore and offshore Niger Delta,Nigeria using TOC content and rock-eval pyrolysis techniques

This article prognosticates the hydrocarbon generation potential of core samples from fields A, B, C and D in Niger delta, Nigeria. The objectives of this study are to characterize the quality of these core samples by organic geochemical analyses. A total of ten core samples collected from fields A, B, C and D in Niger delta were analyzed using total organic carbon （TOC） content analysis, rock-eval pyrolysis technique. The analytical results of the stud- ied core samples reveal that they have generally high total organic carbon contents （TOC）, suggesting that conditions in the Niger delta favour organic matter production and preservation. There is a variation in the kerogen types and this may be attributed to the relative stratigraphic positions of the core samples within the Niger delta. The rock-eval results indicate that the samples from fields C and D contain predominantly Type II kerogen with a capacity to gen- erate oil and gas and hence have good generative potential. The samples from fields A and B contain mainly Type III kerogen and are gas-prone with moderate generative potential.     

Determining the Main Gas-generation Phase of Marine Organic Matters in Different Occurrence States using the Kinetic Method

This paper probes the determination of the main gas-generation phase of marine organic mattes using the kinetic method. The main gas-generation phase of marine organic matters was determined by coupling the gas generation yields and rates in geological history computed by the acquired kinetic parameters of typical marine organic matters （reservoir oil, residual bitumen, lowmaturity kerogen and residual kerogen） in both China and abroad and maturity by the EasyRo（%） method. Here, the main gas-generation phase was determined as Ro%=1.4%-2.4% for type Ⅰ kerogen, Ro%=1.5-3.0% for low-maturity type Ⅱ kerogen, Ro%=1.4-2.8% for residual kerogen, Ro%=1.5-3.2% for residual bitumen and Ro%=1.6-3.2% for reservoir oil cracking. The influences on the main gas-generation phase from the openness of the simulated system and the ＂dead line＂ of natural gas generation are also discussed. The results indicate that the openness of simulation system has a definite influence on computing the main gas-generation phase. The main gas-generation phase of type Ⅱ kerogen is Ro%=1.4-3.1% in an open system, which is earlier than that in a closed system. According to our results, the ＂dead line＂ of natural gas generation is determined as Ro=3.5 % for type Ⅰ kerogen, Ro=4.4-4.5% for type Ⅱ kerogen and Ro=4.6% for marine oil. Preliminary applications are presented taking the southwestern Tarim Basin as an example.     

Composition of Kerogen in Kupferschiefer from Southwest Poland

Thirty-seven Kupferschiefer samples from southwestern Poland were analyzed by microscopy, Rock-Eval approach and instrumental neutron activation analysis to understand the geochemical and morphological characteristics of kerogen present in the samples. The analytical results indicate that there are two different types of kerogens. One type was only subjected to thermal alteration processes, and the other was further oxidized after deposition of the sediment.In the oxidized samples migrabitumen was transformed into pyrobitumen. Rock-Eval analyses show a significant decrease in HI values in the oxidized samples and an increase in OI values in relation to the samples that were not influenced by oxidation. Variations in S2 versus Corg contents indicate a change in kerogen from Type II to Type III with progressing oxidation. The presence of pyrobitumen and the depletion of hydrogen in the altered kerogen allow one to conclude that the kerogen was used as hydrogen donor for thermochemical sulfate reduction(TSR).     

Hydrocarbon Generating Potential of Mineral—Bituminous Matrix in Source Rocks

Mineral-bituminous matrix(MBM) makes up a major part of source rocks,but its potential in hydrocarbon generation is uncertain,Mineral and organic (Maceral and kerogen) compositions,organic maturity and fluorescence of MBM are studied based on source rock samples from eastern Jiuquan(Jiudong)Basin.The results show that MBM is dominated by inorganic minerals and among the small percentage of organic components those of secondary origins are predominant over the primary species.This strongly indicates that the significance of MBM in hydrocarbon generation is limited.     

Geochemistry, Petrology and Mineralogy of Coal Measure Shales in the Middle Jurassic Yanan Formation from Northeastern Ordos Basin, China: Implications for Shale Gas Accumulation

The Jurassic Yanan Formation is one of the most important coal-producing formations and hydrocarbon source rocks in the Ordos Basin, North China. To evaluate the shale gas potential of the Yanan shale, a total of 48 samples from north Ordos Basin were sampled, and their geochemical, petrological, mineralogical and pore characteristics were investigated. It was found that the shale samples are a suite of early mature source rock. The total organic carbon (TOC) content ranges from 0.33% to 24.12% and the hydrogen index (HI) ranges from 43.31mg/g to 330.58 mg/g. The relationship between Tmax and HI indicates the organic matter is type Ⅱ-Ⅲ. This conclusion is also supported by the organic petrological examination results, which shows that the kerogen is mainly liptinite and vitrinite. Minerals in the samples are composed mainly of quartz, clay and feldspar, and the clay minerals are composed of prevailing kaolinite, illite/smectite, chlorite and a small amount of illite. Under scanning electron microscope, OM pores in the Yanan shale are scarce except pores come from the kerogen intrinsic texture or clay aggregates within the organic particles. As the weak compaction caused by shallow burial depth, interparticle pores and intraparticle pores are common, the hydrocarbon storage capacity of the Yanan shale was improved. According to evaluation, the Yanan shale is considered as a good shale gas reservoir, but its hydrocarbon potential is more dependent on biogenic and coal-derived gas as the thermogenic gas is limited by the lower thermal maturity.     

Discovery of Early Tertiary Hydrothermal Activity and Its Significance in Oil／Gas Geology,Dougpu Depression,Henan Province,China

Data from the super-deep wells(PS10,PS14 and YS1)led to the discovery of widespread met-al-bearing hydrothermal fluids (or hot brines) related to basic magmas in the Lower Tertiary clastic sequence in the Dongpu Depression .In terms of SEM and EDAX analyses, pore-casting thin section examination of sandstone ,the composition and forming temperature of fluid inclusions ,the trace ele-ment composition of mustone and kerogen and organic geochemical analyses, it is demonstrated that the hydrothermal fluids existing in the area studied are ejecting fluids, which have a close bearing on diagenesis and sedimentation, rather than intrusive veins along the tectonic fractures.The main indicators of hydrothermal activity are:(1)abnormal alteration of kerogen;(2) high-temperature altered mineral assemblage;(30abnormal distribution of hydrocarbons;(4) specific assemblages and abnormal contents of heavy metals in mudstone and kerogen;(5) specific composi-tion of complex compounds and assemblages of fluid inclusions in sandstone;(6) periodic basaltic magma activity.Results of geological observations and laboratory simulating experiments demonstrated that the hydrothermal fluids have a close bearing on hydrocarbon generation in the Dongpu Depression. Two aspects of the effect of hydrothermal fluids are noticed:hydrothermal hydrocarbon production and strong metal catalysis in oil and gas generation.     

Methane adsorption comparison of different thermal maturity kerogens in shale gas system

To determine the effect of thermal maturity on the methane sorption in shale gas system, two different thermal maturity kerogens of type II isolated from Barnett shale of Fort Worth Basin were used to measure the methane adsorption amount under the pressure ranging from 0 to 14 MPa at constant temperatures. One kerogen was called Lee C-5-1 with 0.58% of vitrinite reflectance; the other was called Blakely#1 kerogen with 2.01% of vitrinite reflectance. The results suggested that the methane sorption capacity of kerogen Blakely#1 was higher than the immature kerogen Lee C-5-1, and its Langmuir constant and Langmuir maximum sorption amount, which were reached by fitting the measured data for at least square method, greater than the immature kerogen Lee C-5-1. This may be associated with that nanopores opened up during the degradation of organic matter, and which increased the specific surface area of kerogen. Therefore, the over mature kerogen has greater methane adsorption capacity.     

Geochemical Evaluation of the Permian Ecca Shale in Eastern Cape Province,South Africa: Implications for Shale Gas Potential

Shale gas has been the exploration focus for future energy supply in South Africa in recent time. Specifically, the Permian black shales of the Prince Albert, Whitehill, Collingham, Ripon and Fort Brown Formations are considered to be most prospective rocks for shale gas exploration. In this study,outcrop and core samples from the Ecca Group were analyzed to assess their total organic carbon(TOC), organic matter type, thermal maturity and hydrocarbon generation potential. These rocks have TOC ranging from 0.11 to 7.35 wt%. The genetic potential values vary from 0.09 to 0.53 mg HC/g,suggesting poor hydrocarbon generative potential. Most of the samples have Hydrogen Index(HI) values of less than 50 mg HC/g TOC, thus suggesting Type-Ⅳ kerogen. Tmax values range from 318℃ to601℃, perhaps indicating immature to over-maturity of the samples. The vitrinite reflectance values range from 2.22% to 3.93%, indicating over-maturity of samples. Binary plots of HI against Oxygen Index(OI), and HI versus Tmax show that the shales are of Type II and mixed Type Ⅱ-Ⅲ kerogen.Based on the geochemical data, the potential source rocks are inferred as immature to over-matured and having present-day potential to produce gas.     

Origin of natural gases and their differences between the eastern and western parts of central Tarim Basin

The origin of natural gases in central Tarim Basin is very complicated and there has been no definite conclusion in this aspect. Based on the results of systematic research on their composition and carbon isotopic characteristics, natural gases in central Tarim Basin are composed mainly of hydrocarbon gas, Ordovician natural gas with the characteristics of crude oil-cracking gas, and Carboniferous natural gas not only originating from kerogen cracking, but also from oil cracking. There are significant differences in composition and carbon isotope of natural gases between the eastern and western areas. The causes for the differences in geochemical characteristics of natural gases are presented as follows: different thermal evolution degrees of organic matter. Natural gases in the western region may have generated from the Middle- Upper Ordovician source rocks, and natural gases in the eatern region may be derived from the Cambrian source rocks, which entered into high to over mature stages; the gases migrated from west to east and caused the different compositional and carbon isotopic characteristics of natural gases; difference in the strength of thermal sulfate reduction between the eastern and western parts, with the reduction in the eastern part being stronger than that in the western part.     

Assessing Possibilities and Limitations for Biomarker Analyses on Outcrop Samples: A Case Study on Carbonates of the Shibantan Member (Ediacaran Period,Dengying Formation,South China)

Abstract: The Shibantan Member (Dengying Formation, South China) represents one of only two carbonate settings with Ediacara-type organisms and offers a rare opportunity to study the biogeochemistry of these ecosystems. To evaluate possibilities and limitations for future biomarker studies on fossil-bearing outcrop samples of the Shibantan Member, we analysed the spatial distribution of hydrocarbons in extractable organic matter (i.e. bitumen) on a millimetre scale. Our study demonstrates that the sample and most likely also other rocks from the same setting are contaminated with petroleum-derived compounds that bear the potential for erroneous interpretations in palaeo-reconstructions. The contamination was revealed by distribution patterns and amounts of extractable n-alkanes and acyclic isoprenoids. The contamination is linked to the external weathering surfaces but also to cracks within the rock, and the extent most likely depends on concentration gradients between these contamination sources. Here we show that contamination can successfully be distinguished from syngenetic signals obtained from non-extractable organic matter (i.e. kerogen) using catalytic hydropyrolysis (HyPy). However, we observed that decalcification is necessary to achieve sufficient yields of kerogen-bound hydrocarbons and to avoid artificial alteration of the biomarker signals due to matrix effects.     

石油演化理论与实践（Ⅰ）——石油演化的机理与石油演化的阶段

Mechanism and stagcs are discussed and a schematic diagram suggested for petroleum evolution based on a preliminsry review of the characteristics of some oil and gas bearing areas in China and a comparison of tbe content and nature of paraffins between shallower sediments .(ineluding recent sediments and organisms)and deed rocks (especially source rocks). During the early stage of petroleum evolution, when biochemical agency in shallower sediments plays the dominant role, most of the primary organic material changes into kerogen, with a certain amount of “dry” gas produced. On the other hand, thermal catalytic degradation contributes significantly to the intermediate and late stages of petroleum generation. The main stage of petroleum genesis in source rocks coincides with the late period of early diagenesis, during which the major mcde of occurrence of oilgenerating source matter is kerogen. The major factors controlling petroleum evolution are temperature, time, and the type of mineral catalytic agents and kerogen.The process of petroleum evolution can be divided into the following stages:(1) Oil and gas forming stage: a) Initial methane gas aubstage--the activity of microorganisms was intensive; formation of kerogen and methane took place. b) Low maturity oil substage. This is the main stage of oil generation.Low-matured oil and wet gas generated via the thermal catalytic degradation of kerogen. (2) Oil and gas maturity stage: a) High maturity oil substage. Both the molecular weight of paraffins and the ratio of oil to gas decrease. b) Final methane gas substage. This is the last period of petroleum evolution, with methane and highly matured bitumens as its final products.     

Three-Dimensional Structural Modelling and Source Rock Evaluation of the Quseir Formation in the Komombo Basin, Egypt

The Quseir Formation consists mainly of dark gray mudstones with a high organic matter content and excellent hydrocarbon-generating potential. The main objectives of this study are to highlight the dominant structural elements in the Komombo Basin, Egypt, and evaluate the geochemical characteristics of the Quseir Formation. Depth maps and a 3D structural model indicate two normal fault trends NW–SE and ENE–WSW. The NW–SE trend is the dominant one that created the primary half-graben system. The depth to the top of the Quseir Formation gradually decreases from the eastern and central parts towards the corners of the basin. The thickness of the Quseir Formation ranges from about 300 to 1000 ft. The 3D facies model shows that the shale has a large probability distribution in the study area, compared with the sandstone and siltstone. The source rock potential varies between good in the western part to very good in the eastern part of the basin. The organic-rich interval is dominated by gas-prone kerogen type III based on TOC and Rock-Eval. The pyrolysis data vitrinite reflectance (%Ro) (0.5–0.74%) and Tmax values (406–454C°) suggest a maturity level that ranges from immature to early maturity stage for hydrocarbon generation.     

Organic Material and Trace Elements of Bituminous Rocks in the Ozank(o)y Field, Ankara, Turkey

Bituminous rocks in the Ozank(o)y (Ankara) field are different from those of the Paleocenecontent of organic material-rich rocks in the Ozank(o)y (Ankara) field is 3.66-40.72 % wt averaging 14.34%. The dominant organic materials are algae/amorphous accompanied by minor amount of herbaceous material (The dominant kerogen type is Type-Ⅰ with a limited amount of Type-Ⅱ kerogen.).The bituminous rocks in the Ozank(o)y field are enriched in heavy metals such as Ni, Mn, As and Cr. In comparison with the average enrichment values of elements, Ni, Mn, As and Cr in bituminous shales of the Ozank(o)y field are as about 4.38, 14.93, 10.90 and 5.58 times as average values. The average concentrations of these heavy metals are also as high as 215 × 10-6, 828 × 10-6, 58.54 × 10-6, and 148× 10-6 respectively. In addition, sorption properties of clay and organic materials are also important for metal enrichments in the bituminous shales.     

Organic Material and Trace Elements of Bituminous Rocks in the Ozankiiy Field, Ankara, Turkey

Bituminous rocks in the Ozankoey （Ankara） field are different from those of the Paleocene- Eocene Mengen and Giineytepe （Bolu） regions in metal enrichment levels. Organic carbon （Corg） content of organic material-rich rocks in the Ozankoey （Ankara） field is 3.66-40.72% wt averaging 14.34%. The dominant organic materials are algae/amorphous accompanied by minor amount of herbaceous material （The dominant kerogen type is Type-I with a limited amount of Type-Ⅱ kerogen.）. The bituminous rocks in the Ozankoey field are enriched in heavy metals such as Ni, Mn, As and Cr. In comparison with the average enrichment values of dements, Ni, Mn, As and Cr in bituminous shales of the Ozankoey field are as about 4.38, 14.93, 10.90 and 5.58 times as average values. The average concentrations of these heavy metals are also as high as 215× 10^-6, 828 × 10^-6, 58.54 × 10^-6, and 148 × 10^-6 respectively. In addition, sorption properties of day and organic materials are also important for metal enrichments in the bituminous shales.     

我国南海北部湾第三系粘土岩中有机物的赋存状态及其与生油关系的探讨

The chemistry of organo-clay in somc Tertiary clay-stones from the northern part of the South China Sea was studied. The preliminary results are summarized as follows : (1) Three basic types of organic matter are distinguished in the claystones after treated with different chemical agents: spluble, combined and insoluble (kerogen). It is suggested that the distribution of organic matter and its conversion to petroleum are closely related with the composition and structure of expansive clay minerals in the claystones. Therefore, more detailed studies of these expansive clay minerals may provide new indices for oil-generating potentiality. (2) It is considered from the study of the state of existence of organic matter and. of organo-clay complexes in tile clay-stones that the accumulation and preservation of organic substances may substantially take the form of organo-clay complexes in the process of sedimentation and burial and that the organo-clay complexes may make considerable contributions to the formation of petroleum hydrocarbons during diagenesis. Studies in this aspect are of great significance in developing new theories conccrning petroleum generation and in localizing oil-generating occurrences.     

New Early Cretaceous Pterosaur-Bird Track Assemblage from Xinjiang, China: Palaeoethology and Palaeoenvironment

A pterosaur-bird track assemblage from a sandstone-siltstone-mudstone sequence of the Lower Cretaceous Tugulu Group of Xinjiang comprises the first pterosaur track record from this province and the largest specimen thus far known from China.The pterosaur tracks are assigned to the ichnogenus Pteraichnus based on the triangular overall-shape,the four elongate digit traces and the robust manual digit trace Ⅲ.Supposed trackmakers were dsungaripterid pterodactyloids whose skeletal remains are well known from the Tugulu Group.The bird tracks that occur on the same surface,are those of typical shorebirds,known from different other localities in southeast Asia.The congruence with Koreanaornis dodsoni described from the same stratigraphic level justifies an assignment to this ichnospecies.This is a further evidence of the co-occurrence of pterosaurs and birds in a typical iakeshore environment with possible seasonal alteration of water supply and aerial exposure indicated by wave ripples,mudcracks and repeated cycles of coarse to fine sediment.Pterosaurs and birds frequented the shoreline and may have fed also on the numerous invertebrates such as the Scoyenia tracemaker that left abundant burrows.     

Pelagic Manganese Nodules--A New Type of Oncolites

Pelagic manganese nodules from the East Pacific Ocean have been studied using polarizing,scanning electron and transmission electron microscopes. It has been revealed that the manganesenodules are composed of cores and stromatolite coatings. The structures and textures of thesenodules are peculiar to oncolite. Consequently, the pelagic manganese nodules are manganeseoncolites. Based on the stromatolites in the coatings, the manganese oncolites from the East Paci-fic Ocean can be divided into two types. One is smooth on surface and dense inside. Its coatingsare composed mainly of Minima. The other has a knobby surface and is loose internally. Itscoatings consist mainly of Admirabilis. The TEM investigation has also revealed that the con-structors of the manganese oncolites are ultra-microbes. The Minima is constructed byMiniactinomyces chinensis sp. nov. and the Admirabilis is built by Spirisosphaerospora pacifica sp.nov.     

甘肃花海盆地下新民堡群的有机地球化学——干酪根的演化问题

Kerogen extracted from drilling cores at the depth between 1357 m and 2998m in a thick homogeneous sedimentary series of the Huahai Basin, Western Gansu, was analyzed by elemental analysis procedure, i.r. spectrophotometry, electron paramagnetic resonance spectrometry, and the reflectance of vitrite determined by microscopephotometer. The following conclusion are given: l) Kerogen in question seems to have been derived from the same type of orgunic matter, mostly of land-plant origin. 2) With the increase of burial depth, kerogen structure in the Lower Xinimgbu(iroup underwent four evolutionary stages: relative stablization, destruction of polynmerie substances, cracking and cracking-repolymerization--relative symmetrization. 3) Hydrocarbons in petroleum were largely generated at the cracking stage of kerogen structure, the critical depth being about 2100 m.     

http://www.sciencedirect.com/science/article/pii/S1674987115000894

In the present paper lignites from the Cambay basin have been studied for their hydrocarbon potential.The samples were collected from three lignite fieldse Vastan, Rajpardi and Tadkeshwar, and were investigated by petrography, chemical analyses and Rock-Eval pyrolysis. The results are well comparable with the empirically derived values. The study reveals that these ‘low rank C' lignites are exceedingly rich in reactive macerals(huminite t liptinite) while inertinite occurs in low concentration. These high volatile lignites generally have low ash yield except in few sections. The Rock-Eval data indicates the dominance of kerogen type-III with a little bit of type-II. The study reveals that the lignites of Vastan(lower and upper seams) and Tadkeshwar upper seam are more gas-prone while Rajpardi and Tadkeshwar lower seams are oil-prone. Further, the fixed hydrocarbons are several times higher than the free hydrocarbons. The relation between TOC and fixed hydrocarbon indicates that these lignites are excellent source rock for hydrocarbon which could be obtained mainly through thermal cracking. The empirically derived values reveal a high conversion(94e96%) and high oil yield(64e66%) for these lignites.