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With the increasing number of shale gas wells being hydraulically fractured with recycled flowback and produced water to reduce the consumption of fresh water, geochemical indicators of hydraulic fracturing flowback fluids (HFFFs) from such wells need to be found to evaluate the potential pollutants caused by shale gas development. To fill this knowledge gap, we analysed 64 HFFF samples from 3 Changning wells (fracked with recycled wastewater) to form a time series and compared them to HFFF samples from 3 Weiyuan wells (fracked with fresh water). We also made comparisons of HFFFs from two types of wells in the Appalachian Basin with reported data. The results indicated that regardless of the fracturing fluid being used, the water‒rock reaction caused by the hydraulic fracturing process resulted in the release of exchangeable phase elements, such as lithium, boron, with relatively depleted δ7Li and δ 11B, and strontium with relatively enriched 87Sr/86Sr values on the shale surface, into the HFFFs. The composition of the injected fracturing fluid affected the strength of the water‒rock reaction, but the effect is negligible, as the fracturing process can still form the unique Sr, Li, and B isotope ratios of the HFFF. Thus, the elemental signatures (B/Cl and Sr/Cl) and isotopic fingerprints (δ 11B, δ7Li, and 87Sr/86Sr) derived from HFFFs can be used to distinguish between HFFFs from wells hydraulically fractured by either fresh water or recycled wastewater and flowback water from conventional oil and gas wells. The results are important for the environmental evaluation of the large number of wells being fracked with recycled wastewater each year. [Display omitted] • δ 11B and 87Sr/86Sr can be used as indicator for HFFF in Changning field. • Hydraulic fracturing caused the release of minerals enriched in 10B, 6Li, and 87Sr. • Shale formation water composition determined the ratio between Na, Ca, Cl, and Br. • Fracturing fluid composition impact the major elements of HFFFs in the first dozens of days. [ABSTRACT FROM AUTHOR]

Abstract: In this study, a simple solvent dilution followed by highly selective and sensitive gas chromatography–triple quadrupole mass spectrometry (GC–MS–MS) detection was employed to quantify diamondoids in crude oils. Runtime parameters, i.e., parent and daughter ions, collision energy (CE) and scan time, were optimized to obtain maximum selectivity and sensitivity for target analytes. Under optimum conditions, the reproducibility and accuracy of the method were tested and found to be satisfactory. Comparison of GC–MS–MS and GC–MS methods for the determination of diamondoids indicates that GC–MS–MS yields higher sensitivity (method quantitation limits of 0.08–0.37μg/goil) and better selectivity than GC–MS (method quantitation limits of 0.78–8.44μg/goil) due to the elimination of matrix ion interferences using the selected reaction monitoring (SRM) mode. In addition, quantitative data confirm that group separation has a considerable effect on the quantification of diamondoids and the effect appears to depend on multiple factors. Two crude oils (TZ261 and TD2) from the Tarim Basin, China were used to evaluate the GC–MS–MS method. The results prove that the GC–MS–MS method is a promising tool for quantitative analysis of diamondoids in crude oils, especially for oil samples with low diamondoid concentrations. [Copyright &y& Elsevier]

[Display omitted] • Pyrolysis experiments on four organic matter types simulate diamondoid evolution. • Principal component analysis explains the main factors affecting diamondoid indices. • PCA-Fisher discriminant analysis model objectively identifies oil source types. • PCA-regression analysis model quantitatively predicts oil thermal maturity. Assessing the origins and thermal maturity of oils is an important issue in applied petroleum geochemistry. In this study, we extracted information regarding the sources and thermal maturity of oils from diamondoid data using multivariate statistical analysis based on four series of thermal simulation experiments conducted on Type I, II, and III kerogens and a crude oil. Using principal component analysis (PCA) and discriminant analysis (DA), we established the relationship between diamondoid indices and kerogen type, which was then used to identify the source of oils in some oil fields in China. PCA and regression analysis (RA) were used to determine the quantitative relationship between diamondoid indices and thermal maturity, which was then used to estimate the thermal maturity of the studied oils. Our results indicate that this approach is effective for determining the source and maturity of oils, particularly for condensates. [ABSTRACT FROM AUTHOR]

By 2013, more than 20 gas fields related to Late Paleozoic coal measures have been discovered in China, primarily distributed in the Bohai Bay, Ordos, Sichuan, and Junggar Basins. The total proven reserve in these gas fields is more than 3200 × 10 9  m 3 , accounting for 30.1% of the proven gas reserves in China. After analyzing the molecular compositions, stable carbon isotopes, and helium isotopes of 375 gas samples, genetic types and origins of the natural gas, as well as the secondary alterations it experienced, are discussed in this study. Most of the natural gas related to the Late Paleozoic coal measures are coal-type gas, with some of the gases from the Sichuan Basin and the Jingbian gas field in the Ordos Basin being oil-type gases generated from marine mudstones in the Permian Longtan Formation and marine carbonates in the Ordovician Majiagou Formation, respectively. The equivalent vitrinite reflectance values based on stable carbon isotopes of natural gases vary from 0.8% to 2.5%, indicating the mature to over mature stage. Positive carbon isotope series (δ 13 C-CH 4  < δ 13 C-C 2 H 6  < δ 13 C-C 3 H 8 ) are observed in most gas samples, and carbon isotope reversals occur in the forms of δ 13 C-CH 4  > δ 13 C-C 2 H 6 and δ 13 C-CH 4  < δ 13 C-C 2 H 6  > δ 13 C-C 3 H 8 . The form of δ 13 C-CH 4  > δ 13 C-C 2 H 6 is primarily resulted from the mixing of oil-type gases of different maturities, while the form of δ 13 C-CH 4  < δ 13 C-C 2 H 6  > δ 13 C-C 3 H 8 is primarily resulted from the mixing of coal-type gases of different maturities. High concentrations of hydrogen sulfide in natural gas from the Sichuan Basin and the Chenghai gas field in the Bohai Bay Basin are resulted from thermochemical sulfate reduction (TSR), which causes, to some extent, the fractionation of carbon isotopes. By contrast, the fractionation of methane carbon isotopes resulting from the TSR effect is not clear. Carbon dioxide from the Bohai Bay and Junggar Basins is primarily biogenic, generated via the thermal decomposition of organic matter, while that from the Ordos Basin, Sichuan Basin, and Chenghai gas field is generated via the thermal decomposition of carbonates. Carbon dioxide related to the TSR effect has also contributed to the Sichuan Basin and Chenghai gas field. [ABSTRACT FROM AUTHOR]

According to the compositional and isotopic analyses of He, CO 2 and CH 4 of 95 gas samples from the Ordos Basin and 76 gas samples from the Bohaibay Basin in China, this study carried out a detailed investigation on the geochemical characteristics of helium and CO 2 from the cratonic and rift basins, especially the cratonic Ordos Basin and rift Bohaibai Basin in China. Compared to the rift Bohaibay Basin, the cratonic Ordos Basin has lower level of helium and CO 2 , lower R/Ra ratio and lower δ 13 C CO2 maximum value. When the content of CO 2 is < 10%, both cratonic and rift basins have organic CO 2 associated with the hydrocarbon generation process and inorganic CO 2 from the thermal decomposition of carbonates or dissolution of organic acid. Rift basin can also have CO 2 > 20% and δ 13 C CO2 of − 6 ± 2‰ or − 4‰ –− 9‰, which is of volcanic-magmatic or mantle-derived origin, while cratonic basin has no such type of CO 2 . The cratonic basins (Ordos, Sichuan) have CO 2 < 5% and relatively smaller variation range of δ 13 C CO2 , i.e., 25.6‰ (− 0.8‰ –− 26.4‰). The rift basins have higher level of CO 2 , R/Ra ratios and δ 13 C CO2 values. The content of CO 2 can reach 100%, the R/Ra ratio can be up to 6.45 and the variation range of δ 13 C CO2 is 34‰ (7‰ –− 27‰). Bigger variation range of δ 13 C CO2 implies stronger tectonic activities, which is not favorable for the gas accumulation. While smaller variation range means more stable structure, which is favorable for the discovery of large gas fields. Sample in the cratonic basin in China generally has CH 4 / 3 He of 10 9 – 10 12 and R/Ra < 0.1 and in the rift basin it has CH 4 / 3 He of 10 5 – 10 13 and R/Ra of 0.1– 6.45. It is concluded that methane with CH 4 / 3 He ≤ 10 8 is of inorganic origin and methane with CH 4 / 3 He ≥ 10 11 is of organic origin. The regression equation for the CH 4 / 3 He-R/Ra in the cratonic basin is: y = 3E + 11e − 46.28x and it is: y = 4E + 10e − 1.791x in the rift basin. Both Ordos and Bohaibay basins found gas wells with He > 0.05%, which has significant commercial values and provides a clue for the exploration of helium-rich gas fields. Traps with R/Ra > 2 is a favorable clue for the discovery of CO 2 gas fields. Seven CO 2 gas fields have been found in the Bohaibay Basin, but no systematic development has been carried out and only some liquid CO 2 has been injected for tight oil from the Huagou CO 2 gas field. [ABSTRACT FROM AUTHOR]

Although the annual production of shale gas in China was 13 × 10 8 m 3 in 2014, a systematic study on geochemical and isotopic characteristics of these unconventional gases has not been well addressed. In the present study, almost all shale gas samples available in China, including marine shale gas from the Wufeng-Longmaxi Formation in the Sichuan Basin (O 3 w–S 1 l) and terrestrial shale gas from Chang 7 Member (T 3 y 7 ) in the Ordos Basin, were collected and analyzed for their geochemical and isotopic compositions. The shale gas from the Wufeng-Longmaxi Shale is dry gas with an average methane content of 98.38% and records a highest content of CH 4 in the world (99.59%), which is consistent with the very high thermal maturity levels of the gas shales that have equivalent vitrinite reflectance (EqVRo) values between 2.4 and 3.6%. The δ 13 C 1 values are correspondingly heavy and record a heaviest δ 13 C 1 values (−26.7‰) for the shale gases found in the world as well. The average values of δ 13 C 1 , δ 13 C 2 and δ 13 C 3 for the Wufeng-Longmaxi shale gas are −31.3‰, −35.6‰, and −47.2‰, respectively, displaying a complete carbon isotopic reversal (i.e., δ 13 C 1 > δ 13 C 2 > δ 13 C 3 ). δ 2 H CH4 and δ 2 H C2H6 has an average value of −148‰ and −173‰, respectively, also yielding a hydrogen isotopic reversal (i.e., δ 2 H CH4 > δ 2 H C2H6 ). The Chang 7 shale has an average TOC content of 13.81% with vitrinite reflectance (VRo) values between 0.7 and 1.2%. The Chang 7 shale gas is wet gas with an average methane content of 84.90% and is rich in heavy gaseous hydrocarbons (C 2 –C 5 ). The respective values of δ 13 C 1 , δ 13 C 2 and δ 13 C 3 are −48.7‰, −36.4‰ and −31.3‰, displaying a positive carbon isotopic distribution pattern (i.e., δ 13 C 1 < δ 13 C 2 < δ 13 C 3 ). The average δ 2 H CH4 , δ 2 H C2H6 and δ 2 H C3H8 values are −256‰, −244‰ and −188‰, respectively, and are characterized by a positive distribution pattern (i.e., δ 2 H CH4 < δ 2 H C2H6 < δ 2 H C3H8 ). The differences in gas wetness and carbon and hydrogen isotopic distribution patterns between the shale gases from the Wufeng-Longmaxi and Chang 7 shale are attributed to variations in thermal maturity levels. CO 2 is present in low content in both the Wufeng-Longmaxi and Chang 7 shale gases, mostly less than 1%. δ 13 C values for the CO 2 in the Wufeng-Longmaxi Formation are between 8.9 and −9.2‰, indicating an inorganic origin from the cracking of carbonate mineral in the shales under high temperatures. In contrast, δ 13 C values of the CO 2 in the Chang 7 shale gas range from −8.2 to −22.7‰, indicating an organic origin from the thermal degradation of organic matter. Helium in both the Wufeng-Longmaxi and Chang 7 shale gases is dominantly of curst origin in terms of their R/Ra ratios that vary from 0.01 to 0.08. Positive carbon isotopic distribution pattern is typical of primitive thermogenic gas. However, it can be converted into complete or partial carbon isotopic reversal patterns due to secondary alteration. The causes that yield carbon isotopic reversal include (1) mixing of gases with the same source but different thermal maturity levels; (2) secondary cracking of oil or wet gas; (3) formation water-involved reactions; (4) gas diffusion; and (5) carbon isotope exchange between alkane gases at high temperature. Among them, carbon isotopic exchange between alkane gases at high temperature is a key factor. Nine plots have been drawn based on the shale gases from China, USA and Canada. Among them, the plot of δ 13 C 2 versus wetness demonstrates a “lying-S” shape with two inflection points on the gas wetness axis. The wetness value of 1.4% represents a critical point from pyrolytic gas (primary cracking gas) to cracking gas (secondary cracking gas) and whereas the wetness value of 6% marks the end of oil generation. On the diagram of wetness versus δ 13 C, shale gases with wetness values greater than 1.6% are characterized by positive carbon isotopic distribution pattern, whereas a complete or partial carbon isotopic reversals are observed for shale gases with wetness values less than 1.6%. [ABSTRACT FROM AUTHOR]