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• The carbon isotope curve index (CICI) summarizes the isotope ratios of C 1 - C 3. • Carbon-isotope curves can be divided into Convex, Linear, Concave and Reversed. • In Normal-type gas, leakage and preferential propane biodegradation increase CICI. • In Normal-type gas, migration and mixing with microbial methane decrease CICI. The carbon isotope curve (δ13C n versus 1/n) is often used to evaluate the origin and secondary alteration of hydrocarbon gases, but the factors that influence the carbon isotope curve are not fully understood, limiting its practical application. We define a carbon isotope curve index (CICI) to quantitatively characterize the curve type. Four general curve types are defined: a Normal (δ13C 1 < δ13C 2 < δ13C 3) type and three Reversed types consisting of R 1 (δ13C 1 > δ13C 2 > δ13C 3), R 2 (δ13C 1 < δ13C 2 > δ13C 3), and R 3 (δ13C 1 > δ13C 2 < δ13C 3). CICI is defined as arctan (3Δ13C 3-2 /Δ13C 2-1) × 180/π for Normal and R 2 , –180 + arctan (3Δ13C 3-2 /Δ13C 2-1) × 180/π for R 1 , and 180 + arctan (3Δ13C 3-2 /Δ13C 2-1) × 180/π for R 3. CICI ranges from 0 to 90 for Normal, –180 to –90 for R 1 , –90 to 0 for R 2 , and 90 to 180 for R 3. Normal gases can be divided into three categories: Linear (CICI = 45), Convex (CICI 0 to < 45), and Concave (CICI > 45 to 90). The influence of kerogen type and maturity on CICI is investigated by comparing thermogenic gases generated from different kerogens in both sedimentary basins and pyrolysis experiments. Curves for low-maturity lacustrine and low-to-high-maturity coal gases are mainly Convex. In contrast, curves for high maturity to overmature marine gases are more Concave. The curve type of thermogenic gas changes from Convex to Concave with increasing maturity, and the mixing of gases generated from kerogen-cracking and oil-cracking results in the Concave type. The effect of post-generation alteration processes on CICI was elucidated using data from three field studies. In Normal-type gas, preferential biodegradation of propane and leakage increase CICI, while migration and mixing with microbial methane decrease CICI. Preferential biodegradation of propane and leakage are two other reasons for the Concave type. [ABSTRACT FROM AUTHOR]

The hydrogen isotope composition of methane is an important parameter in natural gas research and provides complementary information to that provided by carbon isotopes. The stable hydrogen isotope ratios of 313 natural gas samples from six of China’s sedimentary basins are used to evaluate the factors that influence the stable hydrogen isotopic composition of methane. An important factor is the δD of organic matter in hydrocarbon source rocks, which is influenced by the sedimentary environment and type of organic matter. Natural gases generated from sapropelic organic matter have relatively less negative δ D CH 4 , while natural gases generated from humic organic matter have relatively more negative δ D CH 4 . The other factor is thermal maturity. Increased thermal maturity leads to δ D CH 4 becoming less negative and there exists a two stage linear relationship between the δ D CH 4 and the logarithm of the vitrinite reflectance ( R o) value for natural gases generated from type III kerogen. The third factor is the environmental conditions of the aqueous medium in the original depositional environment and after sedimentation. Elemental hydrogen from water participates in biochemical processes as organisms grow and is exchanged during the sedimentation and diagenesis of organic matter as well as maturity process of kerogen to generate gases. The influence of the aqueous medium on δ D CH 4 after formation of natural gases can be ignored. Among these factors, the aqueous medium is the key constraining factor. The δ D CH 4 in natural gases can be combined with the use of stable carbon isotopic composition to identify the origins of natural gases and to aid gas-source correlations. [ABSTRACT FROM AUTHOR]

A series of marginal-sea basins and fault-depression basins were formed in eastern China under the background of subduction of the West Pacific plate. Different types of helium-rich natural gas reservoirs (He>1000 ppm, 1 ppm=1 µmol mol−1) have been found in these basins: helium-rich CO2 gas reservoirs, helium-rich N2 gas reservoirs, and helium-rich hydrocarbon gas reservoirs. Based on the analysis of gas geochemical data, the source and accumulation mechanism of helium in these helium-rich natural gas reservoirs were discussed. Helium-rich natural gas has relatively high 3He/4He ratios (0.88–4.91 Ra, average 2.82 Ra). The 3He/4He ratio characteristics of mantle xenoliths and mantle-derived CO2 gas reservoirs indicate that the helium in these helium-rich natural gas reservoirs is mainly mantle-derived (>70%). The original mantle volatile is mainly CO2 with a low helium concentration (He<200 ppm), and the enrichment of mantle-derived helium in the gas reservoir is mainly related to the dissolution and mineralization of CO2. During this process, the CO2/3He ratio decreases from 2×109 to approximately 2×106. As CO2 dissolves and mineralizes, the concentration of conservative gases (He and N2) increases in the remaining CO2 gas proportionally to the loss of CO2. Large amounts of carbonate minerals, such as dawsonite, which are relatively enriched in 13C, are found in CO2 reservoirs in eastern China. The relative enrichment of 12C in residual CO2 gas is important evidence of the dissolution and mineralization of CO2. The relative abundance of mantle-derived helium and N2 gas increases thousands of times during the dissolution and mineralization of CO2, which is the main accumulation mechanism of mantle-derived helium-rich CO2 gas reservoirs and helium-rich N2 gas reservoirs. Helium-rich gas from the mantle is mixed with alkane gas generated by organic matter in the sedimentary basin to form helium-rich hydrocarbon gas reservoirs. [ABSTRACT FROM AUTHOR]

Helium is an exhaustible natural resource and the main commercial helium was separated from helium-rich natural gas. The helium in the sedimentary basin is mainly the radiogenic origin of crustal rocks with high level of uranium and thorium. Data from 242 natural gas samples were used to investigate the distribution and formation mechanism of helium-rich gases in the Sichuan Basin of China. All gas samples show remarkably low 3He/4He ratios with ranging from 0.002 to 0.05 Ra, which represent typical crustal helium. The Weiyuan gas pool in the southern Sichuan Basin possesses high levels of helium (1500–18770 ppm, average 2785.7 ppm) in Precambrian and Cambrian strata. A positive relationship were observed in the helium and nitrogen contents increased with reservoir layer age for all Weiyuan gas samples. Presinian granite was considered as the main helium source for the Weiyuan gas pool. Gaoshiti–Moxi and Weiyuan gas pools belonged to the same ancient gas pool before the Late Cretaceous, but the helium abundance of Gaoshiti–Moxi gas pool is relatively low (200–891 ppm). The change of pressure and fracture system caused by the uplift of Weiyuan structure in the Himalayan orogenesis led to the helium accumulation and enrichment of Weiyuan gas pool. The shale of the Silurian Longmaxi Formation has high contents of uranium and thorium and generated a large amount of helium while forming large quantities of hydrocarbon gases. Generally, the helium abundance of shale gases and conventional gases generated from the Longmaxi Formation ranges from 63 to 1500 ppm and some of the gas pool are sufficient for commercial helium resource exploitation. Therefore, the relative quantities of helium and hydrocarbon gases are act as a key factor influencing the formation of helium-rich natural gas reservoirs. • Helium in the sedimentary basin is mainly the radiogenic origin. • Helium-rich gas is generally the crust-derived heterogenous type. • Presinian granite was the main source of helium in the Weiyuan gas field. [ABSTRACT FROM AUTHOR]

Helium is an important, scarce, and strategic resource that is critical to national security and advanced technology development. Although helium originates from mantle degassing and the radioactive decay of uranium (U) and thorium (Th) in minerals, commercial helium resources are primarily derived from natural gas reservoirs with He concentrations higher than 1000 ppm. The gas geochemistry characteristics of 920 natural gas samples from nine petroliferous basins in China were used to classify and discuss the enrichment mechanisms of helium. Helium-bearing natural gas reservoirs can be divided into the following three types: basement source-migration-rich accumulation, self-generating and self-preserving, and crust–mantle complex types. The basement source-migration-rich accumulation, which is the most common type of proven helium-rich natural gas reservoir, occurs primarily in inherited anticlines and dome traps located on basement uplifts. Ancient shale systems demonstrate the potential to form helium-rich shale gas that belongs to the self-generating and self-preserving type. Crust–mantle complex helium-rich natural gas reservoirs develop in petroliferous basins in active magmatic–tectonic areas. The origins of helium and hydrocarbon gas are different, but the entrainment of helium during hydrocarbon gas accumulation is a key factor influencing the formation of helium-rich natural gas reservoirs. The nitrogen concentration in helium-rich gas samples is often extremely high, indicating that the nitrogen and the helium are derived from the same source rock or both are extracted from water by migrating gas. • Helium-rich gas includes basement source-migration-rich accumulation, self-generating and self-preserving, and crust–mantle complex types. • Exsoluion gathering of underground dissolved helium is the key mechanism of helium enrichment. • High-quality matching between helium and natural gas is crucial for the helium-rich gas accumulation. [ABSTRACT FROM AUTHOR]

It has been acknowledged that carbonate was identified as the source rocks of a series of oil-gas fields worldwide. For evaluating the carbonate source rocks, total organic carbon (TOC) contents act as an important indicator. However, the acid solution, which has been generated during conventional TOC measurements, contain organic matters. Hence, the released organic matters in acid solution during carbonate decomposition may lead to underestimate the hydorcarbon generation potential. In this study, rock-eval pyrolysis technique was applied to bulk rock and residue after acid treatment. Meanwhile, the organic matters in acid solution were measured by Gas Chromatography-Mass Spectrometer (GC-MS) to investigate the geochemical characteristics. In addition, the hydrocarbon generation and alteration of TOC contents of released organic matters by acid treatment were studied by hydrous pyrolysis experiments. The results show that the acid solution contains organic compounds, including n-alkanes, saturated fatty acids and fatty acid methyl esters. Meanwhile, total organic carbon (TOC) contents and hydrocarbon generation potential (S1+S2) significantly decrease for bulk rocks after acid treatment in low maturity samples. Moreover, organic CO2 (S3) decreased after treating of acid, revealing that acidolysis process can affect and release organic matters containing oxygen-bearing functional groups. The S1, S2, S3, and TOC loss are positive correlation with the proportion of rock loss during acidolysis, indicating that the organic matters in acid solution are associated with carbonate minerals. The organic fractions may exist as adsorption state on the surface of carbonate minerals and (or) exist as organic acid salts. Moreover, the thermal simulation experiments reveal that the organic matter in acid solution, which is not recovered by the conventional measurement approach, could contribute to hydrocarbon generation. [ABSTRACT FROM AUTHOR]

A series of hydrous pyrolysis experiments were conducted to assess the role of sulfate minerals on the chemical and isotopic compositions of light hydrocarbons generated during thermal degradation of kerogen. The shale source rock with low maturity (T max = 425 °C) from Eagle Ford formation in southeast Texas was used in the experiments at 330 °C for the duration of 72 h, while the abundance of gypsum in each experiment varies from 0, 0.5, to 1 wt%. Under experimental conditions, the positive effect of gypsum on the yields of gaseous alkanes (C 1 - C 4) and CO 2 has been explicitly observed, with an exponential relationship between the yield of each gas and the amount of gypsum. While the relative abundance of C 2 - C 4 alkanes has shown an increasing trend with gypsum, the gas dryness (C 1 /∑C 1-4), however, decreased from 73.1% with no gypsum to 49.6% with gypsum of 1 wt%. It was attributed to lower overall yields and corresponding higher increased generation rates of C 2 - C 4 alkanes than methane through thermal cracking of kerogen and other organic compounds. The carbon isotope value of each alkane reached the highest in the experiment with 1 wt% gypsum. Compared to the experiment without gypsum, there was an increase of 11.5‰ for the δ13C value of methane with 1 wt% gypsum. The extent of this 13C enrichment between experiments with different amount of gypsum became less for C 2 to C 4. The δ13C value of CO 2 was the highest among generated gases, ranging from −4.7 to −2.1‰. Combined with chemical compositions of gases, it suggested that enhanced thermal cracking reactions were predominant in generation of light alkanes with the presence of gypsum, whereas dissolution of carbonates was the main source of CO 2. The reactions involving thermochemical sulfate reduction (TSR) were minor (if present) under experimental conditions, most likely due to the small quantity of gypsum (up to 1 wt%) and neutralization of acidity by carbonates. Nonetheless, the changes in chemical and isotopic compositions of light alkanes, which were ultimately caused by the presence of gypsum, need to be incorporated into geochemical proxies for assessing source rocks (maturation in particular) and their generation potential. • Hydrous pyrolysis experiments were conducted to assess the role of gypsum (0-1 wt%) on light hydrocarbon generation. • There is a positive effect on the yield of C 1 - C 4 gaseous alkanes, due to enhanced thermal cracking reactions with gypsum. • Each alkane gas becomes enriched in 13C with gypsum, with the extent of this 13C enrichment being prominent for methane. • The effect of gypsum on chemical and isotopic compositions of light hydrocarbons is important for source rock evaluation. [ABSTRACT FROM AUTHOR]

Determination of the total organic carbon (TOC) from well logs is an important step in formation evaluation of shale reservoirs. The ΔlogR model is one of the most commonly used methods in determining the TOC of the source rocks. Wang et al. (2016) made three revisions on ΔlogR model to enhance the prediction accuracy, one of which is to use a changeable slope of log 10 R t versus porosity logs to replace a fixed value. Based on the original ΔlogR model and Wang's revision, we propose an improved model for a better TOC estimation in this paper. Specifically, the approximate linear baseline is replaced by a theoretical one. Under this condition, both the slope and resistivity and porosity log values of the baselined rocks vary from depth to depth. The determination of theoretical baseline is presented, and the varied baseline log values are obtained by a simple mathematical technique. In addition to the shale play of Western Canada Sedimentary Basin, two study areas of Sichuan Basin and Ordos Basin in China, were used to assess the applications of the proposed model and its improvement over the original model. The analysis and discussions presented in this paper indicate that the improved model offers more reliable results in shale plays with large lithological variations. Also, the TOC content of the three study areas was estimated using the proposed model. The results showed that the TOC values estimated from well logs and core analysis are in good agreement. [ABSTRACT FROM AUTHOR]