Regional characteristics of groundwater sulfate source and evolution in the multi-layer aquifer system of the northern Shaanxi coal mine base, northwestern China: Evidence from geochemical and isotopic fingerprints.

Groundwater sulfate contamination in mining areas has attracted widespread attention. However, deciphering the source and evolution of sulfate in large-scale mining areas remains a challenge due to intense anthropogenic influences and complex hydrogeological conditions. In this study, 94 groundwater samples were analyzed by a combination of self-organizing maps, MixSiar model, multi-isotope analyses (δ34S, δ18OSO4, δD and δ18Owater) and hydrogeochemical methods to investigate the regional characteristics of groundwater sulfate source and evolution in China's largest coalfield (the Shenfuyu Coalfield). The results showed that the source and evolution of groundwater sulfate were controlled by human activities (mining and agricultural activities) and hydrogeological conditions. The groundwater sulfate primarily originated from pyrite oxidation, gypsum dissolution and human inputs. For the mining districts with shallow mining depths, pyrite oxidation and fertilizer contributed to groundwater sulfate. In addition, the ground cracks and abandoned mines controlled the BSR and pyrite oxidation processes. In contrast, the gypsum dissolution and cation exchange dominated the sulfate evolution in the mining districts with deep mining depths due to slow groundwater circulation. This study provided new insights into the source and evolution of groundwater sulfate in large coalfields, as well as references for regional water resource utilization and protection.

New insights into the controlling factors of nitrate spatiotemporal characteristics in groundwater of Dagu aquifer in Qingdao, China.

Identifying spatiotemporal variation of groundwater NO3-N and its primary controlling factors are vital for groundwater protection. This study, under the data scarce conditions and based on time series monitoring data in Dagu aquifer, applied methods including hydrochemical ion ratio, multiple linear regression, support vector regression and grey relational analysis and dedicated to revealing primary controlling factors of temporal variation patterns of groundwater NO3-N. The results showed that agricultural and manure fertilizer are the main sources of NO3-N in north and central area (vegetable farming area), and that domestic sewage discharge and manure fertilizer are the main sources of NO3-N in south area (residential and grain planting area). In addition, results identified the dominant influencing factors of variation of NO3-N in different regions, with human wastewater discharge, nitrogen load amount and water-table depth being the dominant factors of variations of NO3-N in north area, human wastewater discharge being the main factor of variations of NO3-N in central area, and irrigation water and human wastewater being the leading factors of variations of NO3-N in south area. Moreover, types of controlling factors can influence the seasonal variations of NO3-N. NO3-N in vegetable farming area that dominantly affected by fertilization generally shows higher concentration and larger variation range of concentration during summer and autumn than that during spring. NO3-N which mainly affected by human wastewater discharge and manure inputs shows minimal seasonal variation of mean concentration. NO3-N in grain area influenced by irrigation could show more significant variations during spring and autumn than that during summer. The conclusions can enhance understandings of major influencing factors on NO3-N variation in local aquifer. Importantly, the dominant roles of water-table depth and irrigation in NO3-N variation of N2 site (vegetable planting area) and S5 site (grain planting area), respectively, were highlighted.

Unraveling the hydrogeochemical characteristics and pollution sources of groundwater in an intensive industrial area, East China.

It is challenging to interpret hydrogeochemical datasets with complex natural and anthropogenic genesis in intensive industrial areas. This paper elucidates the hydrogeochemical characteristics and pollution sources of groundwater in an industrial park, East China, combining the self-organizing map (SOM), hydrochemical graphs, and correlation analysis. The results show that the total dissolved solids of groundwater range from 73.45 to 997.92 mg/L and can be regarded as freshwater. The pH varies greatly from 6.44 to 9.90, most of samples belonging to weakly acidic-weakly alkaline. The groundwater can be classified into five clusters by SOM, representing the non- or least-polluted groundwater (cluster D), high salt groundwater (cluster A), high NH4+-N and HCO3- groundwater (cluster B), high Fe and Mn groundwater (cluster C), and high pH groundwater (cluster E), which were contaminated by industrial salts, historical agriculture activity, industrial reducing substances, and industrial alkali, respectively. The natural evolution of groundwater (cluster D) in the study area is mainly controlled by mineral weathering/dissolution. The contributions of calcite, dolomite, gypsum, halite, and silicate mineral to groundwater solute are 55.8-66.3%, 15.1-18.0%, 9.0-10.7%, 2.5-10.1%, and 2.3-9.4%, respectively, based on the mass conservation. The contaminated groundwaters (all other clusters except for cluster D) have different hydrochemical characteristics associated with the pollution sources. In addition, the relatively reductive environment in quaternary flu-lacustrine sediments favored the formation of high level of Fe, Mn, and NH4+-N in groundwater. This study provides a new insight into the characteristic contaminants and their distributions in groundwater and the associated pollution sources based on the large datasets in an intensive industrial area. The data evaluation methods and results of this study could be useful to the groundwater usage management and pollution control in this area and other industrial areas.

Dynamic characteristics and evolution laws of underground brine in Mahai salt lake of Qaidam Basin during mining process.

In the late stage of underground brine mining in salt lakes, the method of injecting fresh water is often used to extract the salt from the brine storage medium. This method of freshwater displacement breaks the original water-rock equilibrium and changes the evolution process of the original underground brine. To explore the mechanism of salt release in saline water-bearing media under conditions of relatively fresh lake water dissolution, this paper analyzes the changes in the chemical parameters of brine from 168 sampling points in the Mahai salt lake in the Qaidam Basin at three stages (before exploitation, during exploitation, and late exploitation) by correlation analysis, ion ratio analysis, and other methods and investigate the variations in porosity and the evolution laws of brine. The results show that the changes in the main ion content and brine mineralization during the exploitation process are small. The changes in Ca2+ content are significant due to the low solubility of calcium minerals, the precipitation of gypsum during the mixing process, and the adsorption of cations by alternating with Ca2+. Primary intergranular pore skeletons are easily corroded to form secondary pores, which increase the geological porosity. Na+ and Cl- are the dominant ions in the brine in the study area, but the concentration of Ca2 + decreased significantly under the influence of mining, by 41.7% in the middle period and 24.5% in the late period. The correlation between Ca2+ and salinity changes significantly in different mining stages, and the reason for the decrease of Ca2+ may be due to the influence of mineral dissolution, mixing, and anion-cation exchange. The porosity of the layer in the study area showed the opposite trend of Ca2+, and the porosity increased first and then decreased. The innovation of this paper lies in analyzing the reasons and mechanisms of the disturbance of artificial dissolution mining on stratum structure by comparing the hydrochemical characteristics and porosity of underground brine storage media in three different mining stages. The research in this paper provides a theoretical basis for the calculation of brine resource reserves and the sustainable development of underground brine in salt lake areas.

Triple isotopes (δD, δ18O, δ17O) characteristic of river water and groundwater in an arid watershed from Qaidam Basin, Northwestern China: implications for hydrological cycle.

Combining traditional stable isotopes (δD and δ18O) and triple oxygen isotope (δ17O) is conducive to tracing hydrological cycle processes. The application of triple oxygen isotopes primarily focuses on precipitation, which is lacking in river water and groundwater. In this study, the spatial variations of δD, δ18O, δ17O, d-excess and 17O-excess of river water and groundwater in the Golmud River basin as well as the correlation between them were investigated to elucidate water origin and assess the evaporation influence on water bodies during flood season. Spatial changes in δD, δ18O and δ17O of river water exhibit a decrease-increase-stability pattern contrary to that observed for d-excess, 17O-excess has no distinct trend but is higher at both the source and downstream regions. The results show that river water and groundwater originate from precipitation in the mountainous area, and the meltwater in the source region also contribute to the river water with high d-excess and 17O-excess during flood season. The combination of d-excess and 17O-excess reveal that river water is also affected by evaporation and mixing of river water in tributaries. It was found that the river water is recharged in the mountains, undergoes evaporation in the upstream region and leaks into groundwater in the midstream region, which is recharged by the groundwater and evaporated again in the downstream region. This study could provide a more comprehensive understanding of the potential and value of triple oxygen isotopes in the hydrological cycle.

Hydrogeochemical and isotopic evidences of the underlying produced water intrusion into shallow groundwater in an oil production area, Northwest China.

The extensive use of fossil fuels (e.g., oil) poses a hidden danger to groundwater quality. However, inorganic pollution has received limited attention compared to organic pollution. In this study, the potential contaminant sources to shallow groundwater were investigated using hydrochemical (e.g., major and trace elements) and isotopic (δ2H and δ18O) methods at an oil field, northwest China, with emphasis on the identification of produced water (PW; oil production-related water) intrusion. The results showed that the groundwater samples can be chemically and isotopically classified into two groups: Group A (severely polluted) and B (slightly or non- polluted). The hydrochemical characteristics of Group A were similar to that of PW, with a comparable Na+/Cl- ratio and elevated levels of Na+, Ca2+, Cl-, Br-, Sr, Ba, Li, B and total volatile organic compounds (TVOCs; volatile and semi-volatile) concentration, but lower HCO3- and SO42- contents, and depleted δ2H and δ18O, which was not suitable for drinking. Groundwater salinity sources involve mineral dissolution (silicate, carbonate and evaporite), cation exchange and anaerobic microbial degradation, as well as deep PW intrusion (especially in Group A). The Cl mixing model showed that PW contributed 13.63-27.78 % to Group A, supported by the results of the isotope mixing model based on δ2H and δ18O (24.43-33.29 %). An overall pollution conceptual model involves three modes: fracturing, surface infiltration, and groundwater lateral runoff. This study validates the effectiveness of Na, Cl, Br, Sr, Ba, Li and B as favorable tracers for monitoring PW intrusion.

Spatiotemporal successions of N, S, C, Fe, and As cycling genes in groundwater of a wetland ecosystem: Enhanced heterogeneity in wet season.

Microorganisms in wetland groundwater play an essential role in driving global biogeochemical cycles. However, largely due to the dynamics of spatiotemporal surface water-groundwater interaction, the spatiotemporal successions of biogeochemical cycling in wetland groundwater remain poorly delineated. Herein, we investigated the seasonal coevolution of hydrogeochemical variables and microbial functional genes involved in nitrogen, carbon, sulfur, iron, and arsenic cycling in groundwater within a typical wetland, located in Poyang Lake Plain, China. During the dry season, the microbial potentials for dissimilatory nitrate reduction to ammonium and ammonification were dominant, whereas the higher potentials for nitrogen fixation, denitrification, methane metabolism, and carbon fixation were identified in the wet season. A likely biogeochemical hotspot was identified in the area located in the low permeable aquifer near the lake, characterized by reducing conditions and elevated levels of Fe2+ (6.65-17.1 mg/L), NH4+ (0.57-3.98 mg/L), total organic carbon (1.02-1.99 mg/L), and functional genes. In contrast to dry season, higher dissimilarities of functional gene distribution were observed in the wet season. Multivariable statistics further indicated that the connection between the functional gene compositions and hydrogeochemical variables becomes less pronounced as the seasons transition from dry to wet. Despite this transition, Fe2+ remained the dominant driving force on gene distribution during both seasons. Gene-based co-occurrence network displayed reduced interconnectivity among coupled C-N-Fe-S cycles from the dry to the wet season, underpinning a less complex and more destabilizing occurrence pattern. The rising groundwater level may have contributed to a reduction in the stability of functional microbial communities, consequently impacting ecological functions. Our findings shed light on microbial-driven seasonal biogeochemical cycling in wetland groundwater.

Rare earth element behaviors of groundwater in overlying aquifers under the influence of coal mining in northern Ordos Basin, China.

Rare earth elements (REEs) have been used as tracers to reveal the hydrochemical sources and processes in groundwater systems that are usually modified by anthropogenic inputs. However, the REE behaviors in groundwater affected by mining activities have yet to be fully understood. In combination of REE geochemistry with general hydrochemical and isotopic (δ2H and δ18O) methods, this study investigated the concentration and fractionation of REEs in alkaline groundwater from two coal mines with similar aquifer lithology but different mining histories in the Northern Ordos Basin. One of the coal mines started mining in March 2009 (Ningtiaota coal mine, NTT), while the other started mining in December 2018 (Caojiatan coal mine, CJT). Results show that the primary hydrochemical type is HCO3-Ca in NTT groundwater with pH value ranging between 7.68 and 8.60, while CJT groundwater was dominated by the HCO3-Na type with higher pH of 9.09-10.00. The average values of ΣREEs were lower, and the NASC-normalized pattern reflected more intense fractionation in NTT groundwater than those in CJT groundwater. The evident differences are caused by the distinctions in water-rock interaction, complexation of inorganic species, and adsorption of REEs in NTT and CJT groundwater. Furthermore, these processes were closely related to the pH of groundwater that was different in two coal mines, which is likely linked to the different durations of coal mining activities that led to differences in development of rock fractures and pyrite oxidation. It is expected that REEs, combined with other indicators such as pH, can be used to trace and help better understand the hydrochemical changes in groundwater caused by mining.

Deterministic factors modulating assembly of groundwater microbial community in a nitrogen-contaminated and hydraulically-connected river-lake-floodplain ecosystem.

The river-lake-floodplain system (RLFS) undergoes intensive surface-groundwater mass and energy exchanges. Some freshwater lakes are groundwater flow-through systems, serving as sinks for nitrogen (N) entering the lake. Despite the threat of cross-nitrogen contamination, the assembly of the microbial communities in the RLFS was poorly understood. Herein, the distribution, co-occurrence, and assembly pattern of microbial community were investigated in a nitrogen-contaminated and hydraulically-connected RLFS. The results showed that nitrate was widely distributed with greater accumulation on the south than on the north side, and ammonia was accumulated in the groundwater discharge area (estuary and lakeshore). The heterotrophic nitrifying bacteria and aerobic denitrifying bacteria were distributed across the entire area. In estuary and lakeshore with low levels of oxidation-reduction potential (ORP) and high levels of total organic carbon (TOC) and ammonia, dissimilatory nitrate reduction to ammonium (DNRA) bacteria were enriched. The bacterial community had close cooperative relationships, and keystone taxa harbored nitrate reduction potentials. Combined with multivariable statistics and self-organizing map (SOM) results, ammonia, TOC, and ORP acted as drivers in the spatial evolution of the bacterial community, coincidence with the predominant deterministic processes and unique niche breadth for microbial assembly. This study provides novel insight into the traits and assembly of bacterial communities and potential nitrogen cycling capacities in RLFS groundwater.

Spatial variability of source contributions to nitrate in regional groundwater based on the positive matrix factorization and Bayesian model.

Groundwater nitrate (NO3-) pollution has attracted widespread attention; however, accurately evaluating the sources of NO3- and their contribution patterns in regional groundwater is difficult in areas with multiple sources and complex hydrogeological conditions. In this study, 161 groundwater samples were collected from the Poyang Lake Basin for hydrochemical and dual NO3- isotope analyses to explore the sources of NO3- and their spatial contribution using the Positive Matrix Factorization (PMF) and Bayesian stable isotope mixing (MixSIAR) models. The results revealed that the enrichment of NO3- in groundwater was primarily attributed to sewage/manure (SM), which accounted for more than 50 %. The contributions of nitrogen fertilizer and soil organic nitrogen should also be considered. Groundwater NO3- sources showed obvious spatial differences in contributions. Regions with large contributions of SM (>90 %) were located in the southeastern part of the study area and downstream of Nanchang, which are areas with relatively high population density. Nitrogen fertilizer and soil organic nitrogen showed concentrated contributions in paddy soil in the lower reaches of the Gan and Rao Rivers, and these accumulations were mainly driven by the soil type, land use type, and topography. This study provides insight into groundwater NO3- contamination on a regional scale.

Nitrogen species and microbial community coevolution along groundwater flowpath in the southwest of Poyang Lake area, China.

Nitrate and ammonia overload in groundwater can lead to eutrophication of surface water in areas where surface water is recharged by groundwater. However, this process remained elusive due to the complicated groundwater N cycling, which is governed by the co-evolution of hydrogeochemical conditions and N-cycling microbial communities. Herein, this process was studied along a generalized groundwater flowpath in Ganjing Delta, Poyang Lake area, China. From groundwater recharge to the discharge area near the lake, oxidation-reduction potential (ORP), NO3-N, and NO2-N decreased progressively, while NH3-N, total organic carbon (TOC), Fe2+, sulfide, and TOC/NO3- ratio accumulated in the lakeside samples. The anthropogenic influences such as sewage and agricultural activities drove the nitrate distribution, as observed by Cl- vs. NO3-/Cl- ratio and isotopic composition of nitrate. The hydrogeochemical evolution was intimately coupled with the changes in microbial communities. Variations in microbial community structures was significantly explained by Fe2+, NH3-N, and sulfide, while TOC/NO3- controlled the distribution of predicted N cycling gene. The absence of NH3-N in groundwater upstream was accompanied by the enrichment in Acinetobacter capable of nitrification and aerobic denitrification. These two processes were also supported by Ca2+ + Mg2+ vs. HCO3- ratio and isotopic composition of NO3-. The DNRA process downstream was revealed by both the presence of DNRA-capable microbes such as Arthrobacter and the isotopic composition of NH4+ in environments with high concentrations of NH3-N, TOC/NO3-, Fe2+, and sulfide. This coupled evolution of N cycling and microbial community sheds new light on the N biogeochemical cycle in areas where surface water is recharged by groundwater.

Spatial distribution and driving factors of groundwater chemistry and pollution in an oil production region in the Northwest China.

Concerns have been raised on the deterioration of groundwater quality associated with anthropogenic impacts such as oil extraction and overuse of fertilizers. However, it is still difficult to identify groundwater chemistry/pollution and driving forces in regional scale since both natural and anthropogenic factors are spatially complex. This study, combining self-organizing map (SOM, combined with K-means algorithm) and principal component analysis (PCA), attempted to characterize the spatial variability and driving factors of shallow groundwater hydrochemistry in Yan'an area of Northwest China where diverse land use types (e.g., various oil production sites and agriculture lands) coexist. Based on the major and trace elements (e.g., Ba, Sr, Br, Li) and total petroleum hydrocarbons (TPH), groundwater samples were classified into four clusters with obvious geographical and hydrochemical characteristics by using SOM - K-means clustering: heavily oil-contaminated groundwater (Cluster 1), slightly oil-contaminated groundwater (Cluster 2), least-polluted groundwater (Cluster 3) and NO3- contaminated groundwater (Cluster 4). Noteworthily, Cluster 1, located in a river valley with long-term oil exploitation, had the highest levels of TPH and potentially toxic elements (Ba, Sr). Multivariate analysis combined with ion ratios analysis were used to determine the causes of these clusters. The results revealed that the hydrochemical compositions in Cluster 1 were mainly caused by the oil-related produced water intrusion into the upper aquifer. The elevated NO3- concentrations in Cluster 4 were induced by agricultural activities. Water-rock interactions (e.g., carbonate as well as silicate dissolution and precipitation) also shaped the chemical constituents of groundwater in clusters 2, 3, and 4. In addition, SO42--related processes (redox, precipitation of sulfate minerals) also affected groundwater chemical compositions in Cluster 1. This work provides the insight into the driving factors of groundwater chemistry and pollution which could contribute to groundwater sustainable management and protection in this area and other oil extraction areas.

Quantifying sulfidization and non-sulfidization in long-term in-situ microbial colonized As(V)-ferrihydrite coated sand columns: Insights into As mobility.

Sulfide-induced reduction (sulfidization) of arsenic (As)-bearing Fe(III) (oxyhydro)oxides may lead to As mobilization in aquifer systems. However, little is known about the relative contributions of sulfidization and non-sulfidization of Fe(III) (oxyhydro)oxides reduction to As mobilization. To address this issue, high As groundwater with low sulfide (LS) and high sulfide (HS) concentrations were pumped through As(V)-bearing ferrihydrite-coated sand columns (LS-column and HS-column, respectively) being settled within wells in the western Hetao Basin, China. Sulfidization of As(V)-bearing ferrihydrite was evidenced by the increase in dissolved Fe(II) and the presence of solid Fe(II) and elemental sulfur (S0) in both the columns. A conceptual model was built using accumulated S0 and Fe(II) produced in the columns to calculate the proportions of sulfidization-induced Fe(III) (oxyhydro)oxide reduction and non-sulfidization-induced Fe(III) (oxyhydro)oxide reduction. Fe(III) reduction via sulfidization occurred preferentially in the inlet ends (LS-column, 31 %; HS-column, 86 %), while Fe(III) reduction via non-sulfidization processes predominated in the outlet ends (LS-column, 96 %; HS-column, 86 %), and was attributed to the metabolism of genera associated with Fe(III) reduction (including Shewanella, Ferribacterium, and Desulfuromonas). Arsenic was mobilized in the columns via sulfidization and non-sulfidization processes. More As was released from the solid of the HS-column than that of the LS-column due to the higher intensity of sulfidization in the presence of higher concentrations of dissolved S(-II). Overall, this study highlights the sulfidization of As-bearing Fe(III) (oxyhydro)oxides as an important As-mobilizing pathway in complex As-Fe-S bio-hydrogeochemical networks.

Source and evolution of sulfate in the multi-layer groundwater system in an abandoned mine-Insight from stable isotopes and Bayesian isotope mixing model.

The source and evolution of sulfate (SO42-) in groundwater from abandoned mines are widely concerned environmental issues. Herein, major dissolved ions, multi-isotopes (δ34S, δ18Osulfate, δ2H and δ18Owater), machine learning (Self-organizing maps) and Bayesian isotope mixing model were used to identify the source and evolution of SO42- in an abandoned mine (Fengfeng mine, northern China) with a multi-layer groundwater system. Groundwater in the study area was mainly divided into three clusters (Cluster I, Cluster II and Cluster III), dominated by Na-SO4, Ca-SO4 and Ca-HCO3 types, respectively. According to δ2H and δ18Owater, groundwater in the study area mainly originated from atmospheric precipitation. δ34S, δ18Osulfate and SO42- suggested that bacterial sulfate reduction did not affect the SO42- isotopic composition. Dual SO42- isotopes, and MixSIAR model revealed that the main source of SO42- in the study area was pyrite oxidation/gypsum dissolution, accounting for an average of 57.4 % (gypsum), 71.24 % (pyrite oxidation) and 52.93 % (pyrite oxidation) of SO42- in the samples of Clusters I-III, respectively. Combined with the hydrochemical diagrams, the evolution of SO42- in different clusters of samples was derived. Cluster I was mainly gypsum dissolution; In contrast, Clusters II and III were mainly pyrite oxidation accompanied by carbonate dissolution, and Cluster II was also influenced by cation exchange. These findings will help in developing management strategies for protecting groundwater quality, which will provide a reference for the study of solute sources and S cycling in abandoned mines.

Fractionation of levofloxacin and ofloxacin during their transport in NOM-goethite: Batch and column studies.

Adsorption and transport of levofloxacin (LEV) and ofloxacin (OFL) enantiomers in a matrix containing goethite and natural organic matter (NOM) were investigated using batch and column experiments. In batch studies, competition and enantioselectivity were observed in the adsorption of LEV and OFL. Enantioselectivity upon adsorption was investigated by comparing changes in the enantiomer fraction (EF) (the ratio of LEV to the sum of LEV and OFL remaining in the solution) after and before adsorption. At pH < 7, there was hardly any selectivity in adsorption of OFL and LEV to goethite. At pH > 7, OFL showed a stronger adsorption than LEV to goethite, and this preference remained when NOM samples of Leonardite humic acid (LHA) and Elliott Soil fulvic acid (ESFA) were added. However, when Suwannee River NOM (SRNOM) was added, the preference was reversed, and LEV was adsorbed more strongly. In single systems, the presence of different types of NOM increased adsorption of LEV and OFL, especially LEV. In column studies, preloaded NOM decreased the transport of LEV and OFL through goethite-coated sand. The EF values in the effluent increased with retention time and reached the largest values (0.59-0.72) at around 1.5 pore volume (PV), and then decreased again, reaching a stable value at 5.0-30.0 PV. Both batch and column experiments showed that, fractionation of LEV and OFL occurred during adsorption and transport in the presence of NOM-goethite complexes, which would eventually affect their environmental fate.

Hydrogeochemical evolution induced by long-term mining activities in a multi-aquifer system in the mining area.

The hydrogeochemical evolution of groundwater is related to and affected by long-term mining activities, which may deteriorate the quality of groundwater. The Fengfeng mine in Handan, North China has a 30-y history of coal mining with long-term mining activities and complex geological conditions, resulting in a complex hydrogeochemical environment in the mining region. In this study, the hydrogeochemical evolution mechanism of groundwater in a multi-aquifer system in the Fengfeng Mining Area was investigated using machine learning (self-organizing maps combined with K-means clustering) and sulfur and oxygen isotopes (δ34SSO4 and δ18OSO4). The hydrogeochemical characteristics of different aquifers in the mining area changed to different degrees after mining compared with the characteristics before mining. The spatiotemporal variations in groundwater components were found to be controlled by pyrite oxidation, gypsum dissolution, and carbonate dissolution, which are affected by mining activities. Pyrite oxidation primarily occurred in the Carboniferous thin-layer limestone aquifer (CLA) and Permian sandstone aquifer (PSA). The hydrogeochemical evolution in the Ordovician limestone aquifer (OLA), the main aquifer in the study area, was affected by leakage recharge from CLA and PSA caused by mining activities. The results showed that owing to the effects of long-term mining, the altered groundwater flow system affected the evolution of groundwater components in each aquifer, particularly the sulfate concentration. This study reveals a distinct hydrogeochemical evolution induced by mining activities, which can provide a basis for groundwater resource management in mining areas.

Geochemical fingerprint and spatial pattern of mine water quality in the Shaanxi-Inner Mongolia Coal Mine Base, Northwest China.

The spatial distribution of mine water quality and geochemical controls must be investigated for water safety and ecosystem protection in Shaanxi-Inner Mongolian Coal Mine Base (SICMB). Based on 122 mine water samples collected from 14 mining areas, self-organizing maps (SOM) combining with principal component analysis (PCA) derived that the mine water samples were classified into seven clusters. Clusters 1 and 3 (C1 and C3) samples were dominant by HCO3-Ca and mixed types, which were distributed in the recharge area of the middle SICMB. In this area, the active groundwater circulation contributed to the good water quality. Cluster 2 (C2) samples were characterized by HCO3-Na type, mainly distributed in the discharge area of the middle SICMB. These samples were threatened by heavy fluorine contamination and high residual sodium carbonate (RSC) because of slow groundwater flow in this area. Clusters 4 and 5 (C4 and C5) samples, distributed in the northeast and middle SICMB, were characterized by high Cl- concentration and light fluorine contamination. They were influenced by anthropogenic input through faults or underground mining. In contrast, Clusters 6 and 7 (C6 and C7) samples with high salinity and sulfate were distributed in the southwest SICMB. The deep groundwater circulation enhanced water-rock interaction and contributed to poor water quality. These findings are beneficial to the management of mine water resources in the SICMB and provide an insight to investigate the mine water quality in large spatial scale.

Insights into moisture sources and evolution from groundwater isotopes (2H, 18O, and 14C) in Northeastern Qaidam Basin, Northeast Tibetan Plateau, China.

Knowledge of moisture sources is of great significance for the understanding of groundwater recharge and hydrological cycle. However, it is often difficult to identify the moisture sources and evolution especially in the areas with complex climate system. Isotopes in groundwater that acts as a climate archive provide a unique perspective on the moisture sources and evolution. In this study, the stable isotopes (2H, 18O) of precipitation and groundwater, radioactive isotope (14C) of groundwater, water vapor trajectory modeling (HYSPLIT models) and d-excess based on mass balance model were employed to reveal the groundwater origin, moisture source and evolution in the northeastern Qaidam Basin, northeast Tibetan Plateau, China. The stable isotopic compositions indicate that the precipitation in the mountainous areas is the main origin of groundwater. The spatiotemporal variation of groundwater d-excess together with HYSPLIT modeling suggest that the moisture sources in the northeastern Qaidam Basin have been controlled by the Westerlies and did not alter obviously with time, whereas Delingha with relatively low elevation is influenced by both the Westerlies and local recycled moisture. More than 80 % water vapor derives from the northwest of study area for the plain and mountainous area, except for the mountainous area of Delingha, where approximately 23 % water vapor originates from the surface water evaporation in the plain area. The water vapor with high d-excess formed in the plain area is transported to the mountainous area and mixed with advected water vapor, resulting in the large d-excess of groundwater in Delingha. The moisture recycling fraction in precipitation for the mountainous area of Delingha is estimated to be about 2.0 % by using d-excess-based mass balance model. The results of the study could be helpful to the understanding of hydrological cycle of the area and elsewhere.

Hydrochemical assessments and driving forces of groundwater quality and potential health risks of sulfate in a coalfield, northern Ordos Basin, China.

Groundwater is the primary water source in coalfields under arid and semiarid climates. However, the problem of excessive concentrations of sulfate, which is a constant component in coalfields, and its potential health risks are often neglected in Northwest, China. To determine the groundwater quality, health threats, and driving forces of sulfate in coal mine groundwater, this study performed hydrochemical and isotopic analyses of 61 groundwater samples from a typical coalfield in northwestern China. We found that phreatic groundwater had lower total dissolved solid (TDS) and freshwater hydrochemical types (mainly Ca-HCO3 and Ca-Na + K-HCO3 types). In contrast, confined groundwater showed saline affinity (Na + K-SO4 type) and high TDS values, and the quality was unacceptable for drinking, with EWQI values larger than 100, which could be attributed to its high SO42- concentration. In addition, confined groundwater was also unsuitable for irrigation with high values of electric conductivity (EC), sodium absorption ratio (SAR), and Na%. Combining with isotopic analysis (δD, δ18Owater, δ34S and δ18Osulfate), the sulfate of confined and phreatic groundwater was controlled by gypsum dissolution and irrigation activities. As for public human health, SO42- poses potential non-carcinogenic risks to various populations, especially children. Therefore, the impact of geogenic and anthropogenic factors should be paid attention to, including the reduction of the use of sulfur-containing fertilizers and discharge of sulfur-containing sewage; and the water treatment should be carried out. Importantly, there is a need to adopt a strategy of water supply from multiple sources to ensure human health.

Surface-subsurface hydrological processes of rainwater harvesting project in karst mountainous areas indicated by stable hydrogen and oxygen isotopes.

Rainwater harvesting (RWH) projects in a decentralized way are significant measures to deal with the water scarcity dilemma in rural areas of the karst mountains in Southwest China at present. Due to the differences in cistern construction features and geomorphological positions, the water sources of cisterns were characterized by marked spatial variability, and the recharge stability of cisterns was strongly influenced by precipitation seasonality. Nevertheless, in hydrological processes on karst hillsides, the identification of different runoff types of RWH has not been sufficiently studied. The stable isotopes of hydrogen and oxygen of eleven cisterns and epikarst springs in subtropic cockpit karst landforms were monitored from 2020 to 2021 to investigate the runoff characteristics in RWH. Evaporative fractionation in different hydrological cycles is the predominant factor regulating the stable isotopic signature of cistern water. The results indicated that the typical roles that occurred in the recharge process contributed differently to water harvesting, with surface runoff (SR) and subsurface runoff (SSR) contributing much more than rainwater (RW) and epikarst runoff (ER). Three mixing patterns were proposed by end-member analysis in which SR + SSR, ER, and RW were three end members with indicators of isotopic value and the total dissolved solids (TDS). The recharge of SR + SSR was the predominated source, which contributed to 64% of the total water resources collected through RWH in the rainy season. In addition, the influence of various runoffs on the recharge stability of the cistern can be reflected by the multiple statistical analysis of isotopic fluctuation. Poor recharge stability is caused by excessive SR + SSR, whereas a higher percentage of ER and RW leads to better recharge stability. The applied method of hydrological process analysis is significant to the cistern water resources management in rural areas of the karst mountains.