Lower Paleozoic Marine Research Articles

Distribution and isotopic compositions of phenanthrene and methylphenanthrenes in crude oils: Implications for source input delineation and grouping oil families

This study aimed to identify the origins of crude oils by analyzing the δ13C values of phenanthrene (Phen) and methylphenanthrenes (9-MP and 1-MP) in some selected oils from the Tarim Basin (NW China), Termit Basin (Niger), Bongor Basin (Chad), and Fushan Depression (South China Sea). The study showed that oils with low 9-MP/1-MP ratios (<2.0), phenanthrene (Phen) δ13C values below −30.0‰, and Δ13C(9MP-Phen) and Δ13C(1MP-Phen) values above zero are marine-originated oils, while oils with high 9-MP/1-MP ratios (>2.0), phenanthrene (Phen) δ13C values above −20.0‰, and Δ13C(9MP-Phen) and Δ13C(1MP-Phen) values below zero are terrestrial-originated oils. Oil samples with high 9-MP/1-MP ratios (>2.0), phenanthrene (Phen) δ13C values ranging from −30.0‰ to −20.0‰, and Δ13C(9MP−Phen) and Δ13C(1MP-Phen) plots below zero are mixed-originated oils with higher terrestrial contribution. In contrast, oils with low 9-MP/1-MP ratios, phenanthrene (Phen) δ13C values ranging from −30.0‰ to −20.0‰, and plotting above and below Δ13C(9-MP−Phen) and Δ13C(1-MP−Phen) vice versa, are mixed-originated oils with higher contribution from marine sources.In combination with the geological settings, the results indicated that the oils from the Tarim Basin have three distinct origins. The majority of the oils are marine-sourced oils derived from the Lower-Paleozoic marine carbonate rocks. Oil samples *T2, *T3, and *T4 are mixed-originated oils with higher terrestrial contribution generated from the Mesozoic lacustrine shales/mudstones in the Tarim Basin. The oil samples *T1 (XH1) and *T9 (S94) are from a mixed origin with higher marine material, are derived from Upper-Paleozoic marine shale source rocks in the Tarim Basin. In Termit Basin, most of the selected oils are mixed oils with higher marine organism contribution from YSQ1 and YSQ2 source rocks from the Mesozoic Yogou Shale Formations, except for *T27 oil sample (Douwani-1), which is a mixed oil with higher terrestrial contribution from YSQ3 source rocks of the Mesozoic Yogou Shale Formations. As for the selected oils from Bongor Basin and Fushan Depression, they are mixed oils with higher contributions from aquatic organisms generated from the Mesozoic and Cenozoic lacustrine shale rocks, respectively.This approach allowed to identify for the first time the mixed origin with higher contribution of marine organic matter of the oil samples *T1 (XH1) and *T9 (S94) from the Tarim Basin, and the mixed origin with higher contribution of terrestrial organic matter of the oil sample *T27 (Douwani-1) from the Termit Basin.

The organic petrology of vitrinite-like maceral in the Lower Paleozoic shales: Implications for the thermal maturity evaluation

Vitrinite-like maceral (VLM) is a type of autochthonous, synsedimentary, dispersed organic matter, which is ubiquitous in many Lower Paleozoic marine shales. The VLM reflectance has been used as an alternative tool to evaluate the thermal maturity of pre-Devonian marine sediments lacking a classical vitrinite, however, the existing knowledge about its optical properties and reflectance characteristics is still relatively limited. In this study, the optical properties of VLM were examined by means of organic-petrological methods applied to a series of naturally and artificially matured VLM-rich shales samples and their reflectance crossplots. The strong positive correlation between the true maximum reflectance (Rmax) and bireflectance of VLM indicates the increasing anisotropy of VLM with increasing thermal maturity. VLM shows a linear coalification path in the studied shales. It displays biaxial neutral features in the samples with Rmax ≤ 2%, but shows obvious optically biaxial negative characteristics in the samples with Rmax > 2%. The shape of VLM reflectance indicating surface (VLMRIS) gradually becomes oblate with increasing maturity. These results indicate that VLM exhibits appearance and optical properties similar to vitrinite, and its reflectance can be used as a reliable indicator for thermal maturity evaluation. The equivalent vitrinite reflectance (EqVRo) values, which were calculated based on the mean measured maximum reflectance of VLM (VLMR¯max), evidence that the Niutitang Formation shales from China and Alum shales from Denmark are post-over mature, and the Yurtus Formation shales in Tarim Basin and the Alum shales from Sweden are still within the oil window.

Geological Characteristics and Controlling Factors of Deep Shale Gas Enrichment of the Wufeng-Longmaxi Formation in the Southern Sichuan Basin, China

Abstract To identify the factors controlling high-quality deep shale gas reservoirs and the exploration and development potential of the Lower Paleozoic marine shale in the Sichuan Basin, the sedimentary environment of deep shale was comprehensively analysed using core thin sections, scanning electron microscopy, gamma ray spectrometry logging, and elemental logging data. In addition, the geological conditions of deep shale gas accumulation and the effect of tectonic processes on the preservation conditions are discussed based on the experimental data of mineral composition analysis, geochemical features, and reservoir spatial characteristics. (1) The sedimentary environment changes from an anoxic water environment to an oxygen-rich oxidizing environment from bottom to top in the Wufeng-Longmaxi Formation in southern Sichuan. The deep shale gas reservoir shows overpressure and rich gas characteristics, namely, high formation pressure (2.0~2.2), high porosity (20%~55%), and high gas content (4.0~5.0 m3/t). (2) The favourable sedimentary environment has a higher hydrocarbon generation potential and deposits of rich organic matter and siliceous particles. During the hydrocarbon generation process, the rich organic matter generates a large number of organic pores and a large specific surface area, which provides the main reservoir and adsorption space for free and adsorbed shale gas. A large number of biogenic siliceous particles provide a solid rock support framework for the shale reservoir, thereby maintaining excellent reservoir physical properties. (3) Late and small stratigraphic uplifts result in a short shale gas escape time and favourable preservation conditions. Additionally, the small-scale faults and a high-angle intersection between the fracture strike and the geostress direction are conducive to the preservation of shale gas. (4) A high formation pressure coefficient, a sedimentary environment rich in organic siliceous deep-water continental shelf microfacies, and a relatively stable tectonic structure are conducive to the accumulation of deep shale gas.

Pore Characteristics and Gas Preservation of the Lower Cambrian Shale in a Strongly Deformed Zone, Northern Chongqing, China

The Lower Paleozoic marine shale in southern China has undergone several strong tectonic transformations in an extensive region outside the Sichuan Basin. Although some shale strata underwent strong deformation, they still contain a significant amount of shale gas. The gas preservation mechanism in the strongly deformed shale has become the focus of attention. In this paper, the Lower Cambrian gas-bearing shale samples with a strong deformation taken from an exploration well in northern Chongqing, China, were investigated on their pore types and structure, with the aim to reveal the reason for the gas preservation. The pore types of the Lower Cambrian shale are dominated by microfractures and interparticle (interP) pores occurring mainly between clay minerals and between organic matter (OM) and clay minerals, while pores within OM that can be observed by FE-SEM (field emission-scanning electron microscopy) are rare. The shale has a low porosity, with an average of 1.56%, which is mainly controlled by the clay mineral content. The adsorption experiments of low pressure N2 (LPNA) and CO2 (LPCA) indicate that the shale is rich in micropores and small mesopores (&lt;2–3 nm) provided mainly by OM, but mesopores with a size range of 3–50 nm are underdeveloped. The shale, as revealed by LPNA data, has dominant slit-like or plate-like pores and an obvious low-pressure hysteresis (LPH), indicating a low gas diffusion. The deformed shale samples with a removal of OM by oxidation and their isolated kerogen further indicate that the LPH is completely related to OM, without any relationship with minerals, while an undeformed shale sample, taken from another well for a comparison, has no obvious LPH for both of its OM-removed sample and kerogen. Based on a comprehensive analysis of the relative data, it is suggested that the nanopores related to OM and clay minerals in the shale were significantly altered owing to the deformation, with a result of the pores being squeezed into the slit-like shape and converted into micropores. This extraordinary pore structure of the shale formed during the deformation process should be the main preservation mechanism of shale gas.

Behavior of organic matter-hosted pores within shale gas reservoirs in response to differential tectonic deformation: Potential mechanisms and innovative conceptual models

Remarkable breakthroughs have been achieved in exploration of marine shale gas, acting as important cleaner energy resources in complex tectonic regions, encouraging us to accurately estimate different reservoir capacity of tectonically deformed gas shales. In particular, organic matter (OM) pore system, acting as the most important storage space for high-over-mature marine gas-shale reservoirs in South China has not yet been specifically targeted and comparatively studied in a regional and differential tectonic deformation regime. A set of shale drilling core samples from the Upper Silurian to Lower Ordovician Wufeng-Longmaxi Formations in the Sichuan Basin and its periphery were targeted by a multi-methodical approach utilizing organic geochemistry and mineralogical investigations, FE-SEM observation and digital image processing and extraction, and combined fluid intrusion (N2 and CO2 adsorption analysis). From undeformed shales (UDS) through slightly deformed shales (SDS) to intensely deformed shales (IDS), an obviously and progressively “Triple Jump” reduction in multi-scale pore volume and specific surface areas, and characteristic parameters for OM pores including the plane porosity (Phi) (the average dropped from 23.14% to 10.33%), the equivalent circle diameter (ECD) (the average dropped from 28.38 nm to 10.09 nm), the perimeter over area (PoA) (the average rose from 0.1126 to 0.2718), and the dominant pore diameter (DOM size) (the average dropped from 113.80 nm to 20.78 nm). The reactivation of seepage channels and intrusion of brittle minerals are proposed as two main microscopic forcing mechanisms, updated and innovative conceptual models are proposed to reconstruct an OM pore response processes under a differential tectonic deformation regime in panoramic view for Lower Paleozoic marine gas shale reservoirs of China. Thus, an evolution of spatial resolution spanning a total of three different scales respectively as structural styles, shale reservoir architectures, and microscopic petrological compositions are together portrayed.

Tectonic evolution analysis constrained jointly by in-situ calcite U-Pb dating and apatite fission track for southwestern Ordos Basin

The lower Paleozoic strata of Ordos Basin is rich in oil and gas resources. The Lower Paleozoic marine carbonate in the southwestern Ordos Basin is characterized by large thickness and high abundance of organic matter. The source rocks are in dry gas window.However, the tectonic evolution has not been well evaluated. The timing of the earlier tectonic events is a key scientific problem and needs to be addressed timely.In this study, under the constraints of detailed field investigations, microstructure characteristics, in-situ trace element analysis and regional deposition-burial evolution history, the secondary calcite in-situ U-Pb dating is combined with apatite fission-track time-temperature simulation curves of the Lower Paleozoic carbonate strata and its fault facture zone to reveal four tectonic events including the Late Ordovician, Late Triassic, Late Jurassic and end of the Early Cretaceous-Cenozoic.A hydrothermal event occurred at the Late Ordovician 452±13 Ma, which might be linked to the subduction and closure of the Proto-Tethys Ocean during the Caledonian period.A limited Indosinian tectono-thermal event occurred at 214±22 Ma, which might be caused by the regional fault movement.The intense tectonic activities during the Yanshanian and Himalayan periods induced a strong uplift and denudation.The southwestern Ordos Basin experienced multi-stage complex tectonic evolution and the caprock was seriously damaged, leaving rather unfavorable preservation conditions for hydrocarbon.This study conducts a novel tectonic evolution analysis by combining low-temperature thermochronology with in-situ U-Pb dating of fault-related calcite, providing a new way to analyze tectonic evolution and later transformation process at the margin of complex superimposed basins.

Role of zooclasts in the kerogen type and hydrocarbon potential of the lower Paleozoic Alum Shale

This study investigates the role of zooclasts in the bulk organic matter composition, kerogen type, and hydrocarbon generation potential of the lower Paleozoic marine Alum shale in Baltoscandia, northwestern Europe. The results show that graptolite periderm is composed of non-granular cuticles and granular filling. The graptolite cuticle is non-fluorescing and has a well-polishing measurable surface, while the graptolite granular fraction is semi-translucent and has brownish fluorescence, suggesting remaining hydrocarbon generation potential. The graptolite granular fraction shows similar optical characteristics to fluorescing diagenetic solid bitumen. Both the graptolite granular fraction and diagenetic solid bitumen have low intensity yellow to brown fluorescence and contribute to generative potential (Rock-Eval S2). The sum of semi-quantitative zooclastic cuticle (non-granular graptolite cuticle, chitinozoan cuticle, and vitrinite-like) and diagenetic solid bitumen content, obtained from maceral point-counting, correlates with the non-generative organic carbon content. Enrichment of zooclastic cuticle in the samples is displayed as enrichment of inert organic carbon, and hence bulk geochemical kerogen of type III. This refractory carbon-rich maceral enrichment results represents autochthonous ‘refractory organic carbon dilution’ and will lead to Hydrocarbon Index (HI) underestimation. Confined hydrous pyrolysis was used to compare the hydrocarbon generation process of a zooclastic cuticle-lean sample (0.2 vol%) and a zooclastic cuticle-rich (1.6 vol%) sample. Results indicate that there are four stages of hydrocarbon generation in the artificial maturation of unconventional source rock of the Alum Shale. The zooclastic cuticle-lean sample has higher hydrocarbon generation potential and more oil-prone than the zooclastic cuticle-rich sample, which is gas-prone and generates more CO2. This difference in hydrocarbon generation is attributed to differences in the organic constituent composition.

Thermal evolution behavior of the organic matter and a ray of light on the origin of vitrinite-like maceral in the Mesoproterozoic and Lower Cambrian black shales: Insights from artificial maturation

The overmature Precambrian to Lower Paleozoic marine shales from China contain relatively simple organic matter (OM) composition, which is dominated by in-source solid bitumen (i.e., solid bitumen in the hydrocarbon source rocks). The thermal evolution behavior of the original OM and the determination of thermal maturity in the Precambrian to Cambrian marine shales have been challenging for decades. The vitrinite-like maceral (VLM) is widely present in these marine shales, and its origin is still unknown. To address these issues, the immature Proterozoic Xiamaling shales from China and the immature Cambrian Alum shales from Sweden, and a Chinese immature Carboniferous coal were heat-treated at temperature range of 300 °C to 550 °C. The carbonized residue of the artificially matured samples was examined for their morphological and reflectance variation, and the results were compared with data on the other overmature natural shales from China and Sweden.OM components are similar in the Xiamaling and Alum immature oil shales, consisting of filamentous algae, matrix bituminite, bituminite, VLM and liptodetrinite, and rare thucholites are present in the Xiamaling shales. The algal-derived OM decomposed gradually due to hydrocarbon generation at 300–350 °C. OM is mainly composed of the in-source solid bitumen in the artificially heated shales after 350 °C, similar to the overmature Precambrian to Cambrian natural shales, and the in-source solid bitumen gradually loses its mass with increasing thermal maturity. The in-source solid bitumen is derived from the thermal cracking of the retained oil or the direct conversion of algal-derived liptinite macerals (e.g., the bituminite) or their mixture. VLM in the Xiamaling oil shales can not be observed after 350 °C, but VLM is still present in the Alum oil shales. It can be inferred that there is a different source of VLM in these shales, and VLM in the Xiamaling oil shales contains more volatile material. The VLM in the Xiamaling shales may be biodegradation products of liptinites under anoxic environments. The origin of VLM in the Cambrian Alum shales requires further study to be verified, although it is certain that graptolites are not its sources. The reflectance of in-source solid bitumen (SBRo) increases with heat-treated temperature in both the Xiamaling shales and the Alum shales, but at different rates, which may be due to the difference of the original kerogen composition in these shales. VLM reflectance (VLMRo) and SBRo in sections perpendicular to bedding can be used to determine the maturation level of the Precambrian-Cambrian sediments. Their relation to equivalent vitrinite reflectance (EqVRo) can be expressed by the following equations: EqVRo = 1.07 × VLMRo – 0.18, EqVRo = 0.87 × SBRo + 0.25 (in the Precambrian sediments) and EqVRo = 1.15 × SBRo + 0.01 (in the Cambrian sediments).

Alteration of organic macerals by uranium irradiation in lower Paleozoic marine shales

Measuring the degree of organic matter (OM) alteration caused by uranium (U) irradiation is important in the effective evaluation of the hydrocarbon potential and thermal maturity of U-rich source rocks. This study investigates OM alteration in the Baltoscandian U-rich, lower Paleozoic Alum shale obtained from three research wells in the thermally immature parts of eastern Sweden and western Estonia. The results show a marked increase in the proportion of refractory, non-generative organic carbon (NGOC) in the U-rich shale. Fluorescence spectrometry of unicellular alginites and lamalginites show a reduction of up to 95.6% in fluorescence relative intensity (RI) with increase in U content from 29 to 401 ppm. Fluorescence spectra of the liptinites exhibit a marked “red shift” as expressed by increase in red(R)/green(G) quotients. This change in fluorescence properties of the liptinites is associated with up to 77.6% decrease in hydrogen index (HI) and hence loss of hydrocarbon generation potential. Furthermore, organic molecules show significant loss of aromatic moieties as well as aliphatic constituents resulting in a more condensed macromolecular structure. The measured random reflectance of solid bitumen (BRo) appears to be significantly elevated in micro scale proximity to the U-containing minerals. The heterogeneous distribution of U-containing minerals and the contact with solid bitumen attributes to the wider range of BRo values and lead to the overall increase in mean BRo in samples with high U contents. In contrast, Ro values of zooclast macerals (GRo, e.g., graptolite, chitinozoans and vitrinite-like fragments) appear to be less influenced by U irradiation and hence are a more reliable maturity indicator in U- rich lower Paleozoic shales.

Characteristics of pore structures from the Lower Paleozoic shale gas reservoirs in northern Guizhou, South China

Pore structure in shale is an important factor influencing the storage capacity of a shale gas reservoir and the effect of shale gas development. Taking the core and outcrop shale samples from the Lower Cambrian Niutitang Formation and Lower Silurian Longmaxi Formation as the object of the research, combined with the scanning electron microscope, high pressure mercury injection, CO2 and N2 gas adsorption experiments, we investigated the porosity, pore types, pore structure, and pore size distribution of the Lower Paleozoic shale gas reservoirs in northern Guizhou, South China. The results indicated that there are developed various genetic types of micro-nano pores in the Lower Paleozoic marine shale in northern Guizhou, which provide the main reservoir spaces for shale gas. The porosity of the Lower Paleozoic shale in northern Guizhou is 1.30%–13.37% in range, and the average is 4.56%. The inter-granular pore, organic matter pore and intra-granular pore are most common. Micropore (<2 nm) and mesopore (2–50 nm) are the main reservoir storage space for shale gas. The specific surface area of micropore plus mesopore in the Lower Paleozoic shale accounts for 94.3% of the total specific surface area, and their pore volume accounts for 59.1% of the total pore volume in northern Guizhou. The pore size of the Lower Paleozoic shale is mainly distributed in 0.4–0.7 nm, 3–10 nm and 0.05–200 μm. The pore structure is the parallel-plate pore with slit shape, two-ends-opened tube pore and ink-bottle shape pore. There are significant differences in the porosity and pore size between the Longmaxi Formation shale and the Niutitang Formation shale. The average porosity and average pore size of the Longmaxi Formation shale is 6.4% and 4.71 nm, while the Niutitang Formation shale is 5.3% and 4.23 nm, respectively. The pore structure of the Lower Paleozoic shale gas reservoir is mainly influenced by organic matter abundance, thermal maturity, mineral composition of shale. The porosity and micropore volume of shale show an increasing trend, with the increase of total organic carbon content and quartz content. The porosity and pore volume of shale have a decreasing trend, with the increase of thermal maturity level and clay mineral content.

An integrated platform for thermal maturity assessment of polyphase, long-lasting sedimentary basins, from classical to brand-new thermal parameters and models: An example from the on-shore Baltic Basin (Poland)

Paleo-thermometers in sedimentary basins often drive to misleading thermal modelling when applied alone or only on potentially productive Paleozoic source rocks. Different paleo-thermal and thermo-chronological data have been used as constraints to model the Silurian to Cenozoic succession of a recently drilled well in the onshore portion of the Baltic Basin, in northern Poland. This dataset provides an integrated platform for thermal maturity assessment contributing to the highly debated reconstruction of the thermal history of the Baltic Basin in the last decade. The well stratigraphy consists of a Lower Paleozoic marine clayey and arenaceous/calcareous succession, about 1000 m thick that is unconformably overlain by a 2000 m thick Permian to Cenozoic sequence, developed in a continental to shallow marine environment. Optical microscopy, FT-IR and Raman spectroscopy analysis of organic matter have been coupled with (U–Th)/He data to produce a robust vitrinite reflectance profile and constrain the 1D thermal modelling of the well. In addition, such a thermal maturity profile was validated by an independent thermal modelling calibrated by the smectite illitization kinetics. Both models identify high heat flow conditions (up to 1.7 HFU) at the end of Mesozoic. The Lower Paleozoic succession entered the late oil window of HC generation during this last heating event.

Developmental characteristics and controlling factors of natural fractures in the lower paleozoic marine shales of the upper Yangtze Platform, southern China

This work elucidates the developmental characteristics and controlling factors of natural fractures, and their effects on the shale gas content in the lower Paleozoic marine shales of the upper Yangtze Platform, southern China. These objectives have been achieved by systematic observations and descriptions of fractures in outcrops and drilling cores, as well as experimental tests on samples from the corresponding fractured intervals. The types of natural macro-fractures observed in both the Niutitang and Wufeng-Longmaxi shales mainly include vertical tension fractures, high-angle shear fractures, bed-parallel slip fractures and bedding fractures, with bedding fractures accounting for the largest proportion. In addition, Field Emission-Scanning Electron Microscopy (FE-SEM) images show that interlayer, inter-particle, intra-particle and organic matter-associated fractures are the primary types of micro-fractures. Tectonism is one of the dominant factors in fracture development, but other factors also have a strong influence, such as TOC content, mineral composition and shale-bed thickness. Under similar tectonic settings, the development of fractures is mainly influenced by the TOC content. For the Wufeng-Longmaxi shale, fracture abundance is positively correlated with the TOC content. However, the TOC content in Niutitang shale displays a positive correlation with fracture density only when the TOC content is less than 6%; when the TOC content is greater than 6%, the correlation is shown to be negative. Shale with higher quartz or lower clay contents exhibits greater fracture development. Furthermore, the shale-bed thickness has a negative influence on the fracture development, which can be essentially attributed to the change in mineral composition of shale. Natural fractures provide reservoir spaces for free gas and are favorable for the desorption of adsorbed gas; therefore, the better shale fractures are developed, the greater the gas content will likely be.

ОСОБЛИВОСТІ ХІМІЧНОГО СКЛАДУ ОКЕАНІЧНОЇ ВОДИ РАННЬОГО ПАЛЕОЗОЮ (за даними досліджень рідких включень у галіті ордовицького солеродного басейну Ордос, Китай)

The fluid inclusions in the marine Middle Ordovician halite of the Majiagou Salt Formation of the Ordos Basin (China) have been investigated. In addition to the primary inclusions the secondary ones of several generations were also detected. The fluid inclusions brine chemistry of halite was studied using an ultramicrochemical (UMCA) method, and the homogenization temperature of fluid inclusions was determined in a special thermal chamber designed by V. A. Kalyuzhny At the post-sedimentation stage, the studied salt strata were exposed to high temperature (58–72 °C) and high (up to several tens of MPa) pressure. Although there are opinions of the inability of primary inclusions in such halite to determine the physical and chemical conditions of sedimentation, however, the informative value of primary inclusions in halite of the Majiagou Formation has remained. The preservation of the integrity (and thus the informative value) of primary inclusions in halite is evidenced by the same chemistry of their brines, which differs from that of secondary inclusions The sedimentation brines of the basin were concentrated to the middle of halite stage and points to the Na-K-Mg-Ca-Cl seawater. The physical and chemical conditions of evaporites formation are not known enough. Currently, the results of the brine chemistry of primary fluid inclusions in marine halite are the best indicators of seawater composition in the Phanerozoic. It is established that the magnesium content in the brines of the Lower Paleozoic basins is lower comparing to modern seawater of the corresponding concentration, and the potassium ion concentration is higher. The chemical composition of the concentrated seawater from which the halite was crystallized in the Ordovician salt basin of Ordos, with the exception of the calcium ion content, is similar to the seawater chemistry of the Cambrian and Silurian basins, which indicates the relative constancy of Early Paleozoic seawater chemistry. Age-related changes in the chemical composition of seawater are always consistent with many quantitatively or qualitatively characterized processes of the Earth’s crust evolution. So we believe that the causes that led to more than twice the potassium content of Riphean-Devonian clays, unlike the younger ones, it were also the reason for the increase in potassium content in the Lower Paleozoic marine brines. The studies conducted also clarify the limits of oscillation of calcium ion content, which determines the type of seawater. Its content in the sedimentary brines of the Ordos basin of the Middle Ordovician reaches 66 g/l at the middle of halite stage. Therefore, at the beginning of the stage of halite precipitation, its content should be approximately 20 g/l (considering its theoretical content of 10 g/l with the modern composition of the atmosphere). Apparently, the cause of the abnormally high calcium content in the early Paleozoic Ocean was the direct flow of it with hydrothermal solutions into the ocean during the activation of global tectonics of the Earth and the increase of solubility of carbonates of continents and ocean floor due to high carbon dioxide atmospheric content.

Fractureability evaluation of shale gas reservoirs

ABSTRACT There are abundant shale gas resources in the Lower Paleozoic marine organic shale strata of the upper Yangtze region, South China. However, affected by multi-period tectonic activities, leading to poor exploitation of the Lower Paleozoic marine shale gas in the complex tectonic zone. Therefore, this study proposes fracturability index (FI) based on shale brittleness, fracture toughness, and stress decay rate. Therefore, this study combines logging data and rock mechanics experiments to obtain the rock mechanics parameters of the Fenggang block shale reservoir. Based on Young’s modulus, fracture toughness and critical strain energy release rate, combined with the analytic hierarchy process, the shale fracturability index is proposed to guide the exploration and development of shale gas. The fracturability index of the Longmaxi Formation shale in the study area is 0.34 ~ 0.72. The fracturability of the middle and lower part of the Longmaxi Formation shale is obviously better than that of the upper part. In general, shale reservoirs with high brittleness index, low fracture toughness, and low critical strain energy release rate have high fracturability.

The reservoir characteristics of marine shale and its effect on the adsorption of methane in Northern Guizhou

The reservoir characteristics of the Lower Paleozoic marine shale in Fenggang block of northern Guizhou are evaluated from three aspects: gas-bearing characteristics, petrological characteristics and reservoir space by a series of experimental data. The effect of total organic carbon content, kerogen type and clay mineral content on shale adsorption capacity is discussed. The results show that the reservoir characteristics of the Wufeng-Longmaxi Formation shale in the study area are conducive to the enrichment of shale gas. In the case of quantitative clay minerals, the chlorite content has a significant adverse effect on the methane adsorption of the samples. The shale gas methane adsorption has an excellent increasing trend with the increase of total organic carbon content. The type II1 organic matter is more conducive to the adsorption of methane than the type I organic matter.

Structural evolution of organic matter and implications for graphitization in over-mature marine shales, south China

Abstract To characterize the degree of organic matter graphitization in the over mature lower Paleozoic marine shales from South China, a suite of kerogen samples covering different maturity (Ro% ranging from 1.2% to 4.2%) were analyzed by Laser Raman microprobe (LRM), Transmission electron microscope (TEM) and Fourier transform infrared spectroscopy (FTIR) techniques. Chemical structures and related major changes caused by thermal evolution history were systematically discussed. The results indicate that with the thermal maturity increasing, the aliphatic side chains fall off gradually, and the aromatic rings increase continuously. The ordered structure of shales continues to enhance, leading to the increasing of graphitization degree. The parameters of LRM (i.e. position of G and D bands, peak position difference (RBS), full width at half maximum (FWHM) and intensity ratio (ID/IG)) highlight the “turning point” at maturity level around RmcRo% = 3.5%, which represents the chemical structure jump of the kerogen. This chemical structure jump can be characterized by the continuous decreasing of amorphous carbon before the RmcRo% exceeded 3.5% and the sharp increasing degree of aromatic conjugation after that point. TEM analysis indicates that the carbon layers of shale samples with RmcRo% exceeds 3.5% show better ordering and continuity than that of low maturity shale samples. The FTIR analysis suggests that there are relatively high aromatics C C chains and very few aromatic C-H chains in the high maturity samples. This critical chemical structure jump at RmcRo% = 3.5% could be interpreted as the structure of organic matter begins to transform from amorphous carbon to crystalline graphite in shales. Due to the increasing degree of graphitization, graphitized shale is characterized by stable chemical structure, condensed and orderly carbon layer constructure, and ultra-low resistivity.

Overpressure generation and evolution in Lower Paleozoic gas shales of the Jiaoshiba region, China: Implications for shale gas accumulation

Abstract Overpressured shale gas plays have been found in the Lower Paleozoic marine shales of Jiaoshiba region in the Sichuan basin, China. The black shales from the Upper Ordovician Wufeng Group (O3w) and the lower part of Lower Silurian Longmaxi Group (S1l) are the producing reservoirs. Overpressure is widespread in the O3w-S1l shales with the pressure coefficient up to 1.74. Fluid inclusion microthermometric and Raman spectroscopic techniques, PVT and basin modeling are used to investigate overpressure generation and evolution in the O3w-S1l shales. The results show that thermocatalytic dry gas generation is the main genetic mechanism for overpressure development in the O3w-S1l shales with specific characteristics as follows: (1) the maximum burial depth of overpressured shales is more than 6200 m without anomalously low density and high primary porosity according to wireline log and core data; (2) the over-mature O3w-S1l shales with the mean TOC values ranging from 3.36 wt% to 4.48 wt% and the vitrinite reflectance values of 2.7%–2.9% Ro determined by kerogen FTIR (Fourier transform infrared spectroscopy) characteristics, has excellent potential to produce dry gas; (3) overpressured reservoirs are characterized by high gas saturations, and the pressure coefficients positively correlate with gas saturation; (4) the abnormally high pressures recorded in the fluid inclusions are coincident with high homogenization temperatures, which is supportive of overpressure occurring during dry gas generation and provides convincing in-situ evidence for gas generation overpressuring. The calculated pore-fluid pressures for methane inclusions within the maximum buried O3w-S1l shales are approximately 90.3–139.4 MPa, suggesting that gas generation produced a maximum pressure gradient of 23.1 MPa/km, which is equivalent to the lithostatic magnitudes. The overpressure evolution in the O3w-S1l shales is noticed to have evolved through four stages: a rapidly increasing overpressure caused by thermocatalytic gas generation (>145-85 Ma), a rapid pressure release (85-61Ma), overpressure preservation (61-20 Ma), and a relatively slow pressure release (20 Ma - present). During post-generation evolution (85 Ma - present) of the O3w-S1l shales, both the overpressure and pressure coefficients decreased with time due to the intensive tectonic uplifts and denudation, and approximately 19.0%–28.5% of the initial total gas content was continuously released until the present-day overpressure state. The study of overpressure evolution in the O3w-S1l shales provides basic information for the further study of the conversion between adsorbed gas and free gas, and the method and technique used in this study to stress the overpressure generation and evolution may be generally applied to other overpressured or normally pressured shale gas systems.

Gyrophyllites cristinae isp. nov. from Lower Ordovician Shallow-Marine Deposits of Northwest Argentina

The lower Paleozoic marine siliciclastic succession of the Central Andean Basin, northwestern Argentina, provides a valuable record of the onset of the Great Ordovician Biodiversification Event in western Gondwana. A new ichnospecies of rosette trace fossil, Gyrophyllites cristinae, is documented from lower and upper Tremadocian (Tr1 and Tr2) deposits of this basin. It is characterized by five to six non-overlapping petaloid lobes and can be easily differentiated from the other four formally defined ichnospecies. Gyrophyllites cristinae occurs at the top of hummocky cross-stratified sandstone regularly interbedded with mudstone. These deposits are interpreted as reflecting the alternation of high-energy storm events and low-energy fair-weather conditions immediately below the fair-weather wave base, representing deposition in offshore transition environments. Gyrophyllites has been traditionally interpreted as the product of worms of uncertain taxonomic affinity that mined the sediment in search for food (fodinichnia). The occurrence of Gyrophyllites cristinae in these Ordovician deposits records post-storm colonization. Storms may have increased oxygenation and supplied fresh organic detritus that were exploited by worm-like, surface detritus- or shallow deposit-feeders exploring the uppermost silt-rich fine-grained sediments.

Oil–source-rock correlation of the Lower Paleozoic petroleum system in the Baltic Basin (northern Europe)

The correlation of lower Paleozoic marine source rocks with reservoired oils by biomarkers is complex because of the uniform early Phanerozoic biomass (bacteria and algae) and the lack of land plant and animal input. Accordingly, the main source rocks for the most prolific oil province in the Baltic Basin are still a matter of debate. The 10 source rocks and 15 oil samples from 5 northern European countries bordering the Baltic Sea Basin were analyzed by gas chromatography (GC) with flame ionization detector, GC–mass spectrometry (GCMS), and GCMS/MS to detect acyclic isoprenoids and aliphatic, aromatic, and nitrogen, sulfur, and oxygen biomarkers. Chemometric tools were applied to screen for meaningful source- and age-related biomarkers and to highlight genetics. Extended tricyclic terpane ratios, C24 tetracyclic terpane/C26 tricyclic terpane ratios, and relative C29 sterane concentrations are considered the most promising biomarkers in differentiating Llandovery shales from Cambrian to Ordovician Alum Shale and for correlation with expelled oil. The uranium irradiation–related C26–C28 triaromatic-steroid concentrations provide possible distinguishing criteria for the source potential of the different Alum Shale units. Enhanced oil maturation by volcanic intrusion is highlighted by sterane biomarkers and polycyclic aromatic hydrocarbons. The Alum Shale is here considered the main source rock for oil accumulations in lower Paleozoic reservoirs of the Baltic Basin. Oil seepage occurring in Ordovician limestone was mainly generated by the Middle Cambrian Alum Shale, and Middle Cambrian sandstone reservoirs were mainly sourced by Upper Cambrian and Lower Ordovician Alum Shale with higher maturity. Considerations about the assessment of migration distance are based on carbazole concentrations and C29 sterane isomerization. Advanced studies to unravel detailed lower Paleozoic oil–source-rock correlations are based on meaningful biomarkers, offer approaches to significantly reduce the exploration risk in this area, and could be applied to similar early Paleozoic petroleum systems in other basins.

DIACHRONOUS EVOLUTION OF BACK-ARC BASINS IN THE SOUTH TIANSHAN: INSIGHTS FROM STRUCTURAL, GEOCHRONOLOGICAL AND GEOCHEMICAL STUDIES OF THE WUWAMEN OPHIOLITE MÉLANGE

The South Tianshan is located to the north of the Tarim block and defines the southern margin of the Paleozoic Central Asian Orogenic Belt (CAOB). This study presents new structural data, geochronological and geochemical results for the Wuwamen ophiolite melange in the Chinese segment of the South Tianshan. In the south, the Wuwamen ophiolite melange shows typical block-in-matrix fabrics and occurs in the footwall of a south-dipping thrust fault, hanging wall of which is composed of weakly metamorphosed and deformed Lower Paleozoic marine to deep marine sequences from the South Tianshan. In the north, a southdipping thrust fault juxtaposes the Wuwamen ophiolite melange in its hanging wall against the high-grade and strongly deformed metasedimentary rocks from the Central Tianshan in its footwall.