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The use of the sulphate mass balance (SMB) between precipitation and soil water as a supplementary method to estimate the diffuse recharge rate assumes that the sulphate in soil water originated entirely from atmospheric deposition; however, the origin of sulphate in soil and groundwater is often unclear, especially in loess aquifers. This study analysed the sulphur (δ34S‐SO4) and oxygen (δ18O‐SO4) isotopes of sulphate in precipitation, water‐extractable soil water, and shallow groundwater samples and used these data along with hydrochemical data to determine the sources of sulphate in the thick unsaturated zone and groundwater of a loess aquifer. The results suggest that sulphate in groundwater mainly originated from old precipitation. When precipitation percolates through the unsaturated zone to recharge groundwater, sulphates were rarely dissolved due to the formation of CaCO3 film on the surface of sulphate minerals. The water‐extractable sulphate in the deep unsaturated zone (>10 m) was mainly derived from the dissolution of evaporite minerals and there was no oxidation of sulphide minerals during the extraction of soil water by elutriating soil samples with deionized water. The water‐extractable concentration of SO4 was not representative of the actual SO4 concentration in mobile soil water. Therefore, the recharge rate cannot be estimated by the SMB method using the water‐extractable concentration of SO4 in the loess areas. This study is important for identifying sulphate sources and clarifying the proper method for estimating the recharge rate in loess aquifers. [ABSTRACT FROM AUTHOR]

High-temperature geothermal systems in China, such as those found in Tenchong and Tibet, are common. A similar system without obvious manifestations found in the Tashkorgan basin in the western Xinjiang Autonomous Region, however, was not expected. The results from borehole measurements and predictions with geothermometers, such as quartz, Na-K and Na-K-Mg, indicate that the reservoir temperature is approximately 250–260 °C. Geothermal water is high in Total Dissolved Solids (>2.5 g/L) and SiO 2 content (>273 mg/L), and the water type is Cl·SO 4 -Na, likely resulting from water-rock interactions in the granodiorite reservoirs. Based on isotope analysis, it appears to be recharged by local precipitation and river water. Evidence from the relationships between major ions and the Cl and molar Na/Cl ratio suggests mixing between deep geothermal water and shallow cold groundwater during the upwelling process. Mixing ratios calculated by the relationship between Cl and SiO 2 show that the proportion from cold end-members are 96–99% and 40–90% for riparian zone springs and geothermal water from boreholes, respectively. Active regional tectonic and Neo-tectonic movements in the Pamir syntax as well as radioactive elements in the granodiorite reservoir of the Himalayan stage provide basis for the high heat flow background (150–350 mW/m 2 ). NNW trending fault systems intersecting with overlying NE faults provide circulation conduits with high permeability for geothermal water. [ABSTRACT FROM AUTHOR]

Nitrate pollution is a severe problem in areas with intensive agricultural activities. This study focuses on nitrate occurrence and its constraints in a selected alluvial fan using chemical data combined with environmental isotopic tracers (O, H, and N). Results show that groundwater nitrate in the study area is as high as 258.0 mg/L (hereafter NO) with an average of 86.8 mg/L against national drinking water limit of 45 mg/L and a regional baseline value of 14.4 mg/L. Outside of the riparian zone, nitrate occurrence is closely related to groundwater circulation and application of chemical fertilizer. High groundwater nitrate is found in the recharge area, where nitrate enters into groundwater through vertical infiltration, corresponding to high H and enriched O in the water. In the riparian zone, on the contrary, the fate of groundwater nitrate is strongly affected by groundwater level. Based on two sampling transects perpendicular to the riverbank, we found that the high level of nitrate corresponds to the deeper water table (25 m) near the urban center, where groundwater is heavily extracted. Groundwater nitrate is much lower (<12.4 mg/L) at localities with a shallow water table (5 m), which is likely caused by denitrification in the aquifer. [ABSTRACT FROM AUTHOR]

The baseline quality of pre-drilling shallow groundwater is essential for the evaluation of potential environmental impacts of shale gas development. The Xishui region in the northern Guizhou Province of Southwest China has the potential for shale gas development but there is a lack of commercial production. As for the future environmental concerns in this undeveloped area, this study presented the hydrochemical and isotopic characteristics of shallow groundwater and its dissolved gas before shale gas development and determined the sensitive monitoring indicators. Results showed that shallow groundwater with an average pH of 7.73 had low total dissolved solids (TDS) ranging between 102 and 397 mg/L, with the main water chemistry types of HCO3-Ca and HCO3-Ca·Mg. The quality of most groundwater samples satisfied the drinking water standards of China. The mass concentration of dissolved methane in groundwater was below the detection limit (<0.01 mg/L), suggesting the low baseline value of hydrocarbon. The shallow groundwater was mainly recharged by local precipitation based on water isotopes. Water chemistry was modified by the dominant dissolution of carbonate rocks and partial dissolution of clastic rocks, as indicated by δ13C-DIC, 87Sr/86Sr, and δ11B. Evidence from carbon isotopes of dissolved methane and CO2 (δ13C-CH4 and δ13C-CO2) and noble gas isotopes (3He/4He and 4He/20Ne) demonstrated that the biogenic methane mainly originated from acetate fermentation and the dissolved noble gas was a result of the dissolution of air. Based on the geochemical and isotopic differences between shallow groundwater and flowback and produced water (including shale gas) from the Weiyuan and Fuling shale gas fields as well as shale gas from Xishui, this study has provided the sensitive monitoring indicators and methods for identifying potential pollution of regional shallow groundwater related to shale gas development in the future. [ABSTRACT FROM AUTHOR]

• A framework to determine sensitive monitoring and diagnostic indicators. • Authentic formation water originated from seawater and mixed with meteoric water. • Cl, Br, Na, Li, Ba, 87Sr/87Sr, and δ11B are the most sensitive indicators. • About 0.05% of formation water in shallow groundwater can be identified. • A groundwater contamination case has confirmed the effectiveness of the method. Potential environmental impacts on shallow groundwater from shale gas development facilitated by horizontal drilling and hydraulic fracturing is a widely debated "hot topic". In terms of potential aqueous phase contamination (including flowback fluids and produced water), there is a large gap in knowledge of the indicators for routine monitoring and contamination tracing, which should be considered critical and should be prioritized for analysis. Since formation water from shale formations is the main source of flowback fluids and produced water, and there are significant differences in some specific inorganic geochemical and isotopic compositions between shallow groundwater and formation water, this study has provided a framework to determine sensitive monitoring and diagnostic indicators for tracing potential groundwater contamination from produced water using end-member analysis. The results from a case study of the Fuling Gasfield, Sichuan Basin, SW China as the first and largest commercial shale gas development site in China, shows that produced authentic formation water with similar Br/Cl and Na/Cl ratio with seawater and low δ2H and δ18O values compared to the evaporated seawater might originate from evaporated seawater modified by water-rock interactions and be mixed with fresh meteoric water. The inorganic geochemical and isotopic indicators, such as Ba, Li, Na, Cl, Br, 87Sr/86Sr (as ε Sr sw) and δ11B are sensitive to the detection of contamination of fresh shallow groundwater by produced formation water, even in very small fractions (0.05%). Meanwhile, we present a groundwater contamination case related to shale gas development in the Fuling Gasfield. The robust conservative geochemical (Cl and Br) and isotopic (δ11B and ε Sr sw) mass balances show that 0.2–0.9% of formation water entered the shallow groundwater causing contamination. The case has also confirmed the effectiveness of those indicators. Findings from this study may help to improve groundwater monitoring and environmental regulations in countries with shale gas exploration and development. [ABSTRACT FROM AUTHOR]