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.

Geochemical and Temporal Influences on the Enrichment of Acidophilic Iron-Oxidizing Bacterial Communities.

UNLABELLED: Two acid mine drainage (AMD) sites in the Appalachian bituminous coal basin were selected to enrich for Fe(II)-oxidizing microbes and measure rates of low-pH Fe(II) oxidation in chemostatic bioreactors. Microbial communities were enriched for 74 to 128 days in fed-batch mode, then switched to flowthrough mode (additional 52 to 138 d) to measure rates of Fe(II) oxidation as a function of pH (2.1 to 4.2) and influent Fe(II) concentration (80 to 2,400 mg/liter). Biofilm samples were collected throughout these operations, and the microbial community structure was analyzed to evaluate impacts of geochemistry and incubation time. Alpha diversity decreased as the pH decreased and as the Fe(II) concentration increased, coincident with conditions that attained the highest rates of Fe(II) oxidation. The distribution of the seven most abundant bacterial genera could be explained by a combination of pH and Fe(II) concentration. Acidithiobacillus, Ferrovum, Gallionella, Leptospirillum, Ferrimicrobium, Acidiphilium, and Acidocella were all found to be restricted within specific bounds of pH and Fe(II) concentration. Temporal distance, defined as the cumulative number of pore volumes from the start of flowthrough mode, appeared to be as important as geochemical conditions in controlling microbial community structure. Both alpha and beta diversities of microbial communities were significantly correlated to temporal distance in the flowthrough experiments. Even after long-term operation under nearly identical geochemical conditions, microbial communities enriched from the different sites remained distinct. While these microbial communities were enriched from sites that displayed markedly different field rates of Fe(II) oxidation, rates of Fe(II) oxidation measured in laboratory bioreactors were essentially the same. These results suggest that the performance of suspended-growth bioreactors for AMD treatment may not be strongly dependent on the inoculum used for reactor startup. IMPORTANCE: This study showed that different microbial communities enriched from two sites maintained distinct microbial community traits inherited from their respective seed materials. Long-term operation (up to 128 days of fed-batch enrichment followed by up to 138 days of flowthrough experiments) of these two systems did not lead to the same, or even more similar, microbial communities. However, these bioreactors did oxidize Fe(II) and remove total iron [Fe(T)] at very similar rates. These results suggest that the performance of suspended-growth bioreactors for AMD treatment may not be strongly dependent on the inoculum used for reactor startup. This would be advantageous, because system performance should be well constrained and predictable for many different sites.

Characteristics of change in water quality along reclaimed water intake area of the Chaobai River in Beijing, China.

To reveal the basic characteristics and controlling factors of water quality change in the project Wenyu to Chaobai reclaimed water diversion, the water quality in the study area was monitored for one year at seven monitoring sites. Inverse geochemical models of the statistical groups were developed using PHREEQC to elucidate the hydrochemistry characteristics of reclaimed water and the factors. The monitoring results indicated that nitrogen and phosphorus contents were significantly reduced along the river mainly caused by seasonal and location variation. The pH ranged from 7.44 to 9.81. Photosynthesis of algae and denitrification in anaerobic microenvironment ultimately led to a sudden pH increase after the Jian River and the Chaobai River confluence. Mg2+ and SO42- levels dropped obviously in the summer and increased in winter seasons after intersection. Na+ and Cl- are relatively stable, and marked drop in the concentration only after the two rivers meet. And there is a decrease of Ca2+ and HCO3- and increase in CO32- during monitoring period. As a whole, the primary ions and nutrient components, including nitrogen and phosphorus, had high levels in winter. Algae's photosynthesis and respiration were observed to have an impact on the river water quality; there was precipitation-dissolution of minerals and denitrification from upstream to downstream. Inverse geochemical PHREEQC modeling confirmed that there was precipitation of aragonite or calcite, and gypsum or anhydrite in summer, and dissolution in winter; as well as precipitation of dolomite in winter, and cationic exchange and denitrification along the river.

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.

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.

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.

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.

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.

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.

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.

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.

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 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.

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.

Simultaneous analysis of small organic acids and humic acids using high performance size exclusion chromatography.

An accurate and fast method for simultaneous determination of small organic acids and much larger humic acids was developed using high performance size exclusion chromatography. Two small organic acids, i.e. salicylic acid and 2,3-dihydroxybenzoic acid, and one purified humic acid material were used in this study. Under the experimental conditions, the UV peaks of salicylic acid and 2,3-dihydroxybenzoic acid were well separated from the peaks of humic acid in the chromatogram. Concentrations of the two small organic acids could be accurately determined from their peak areas. The concentration of humic acid in the mixture could then be derived from mass balance calculations. The measured results agreed well with the nominal concentrations. The detection limits are 0.05 mg/L and 0.01 mg/L for salicylic acid and 2,3-dihydroxybenzoic acid, respectively. Applicability of the method to natural samples was tested using groundwater, glacier, and river water samples (both original and spiked with salicylic acid and 2,3-dihydroxybenzoic acid) with a total organic carbon concentration ranging from 2.1 to 179.5 mg C/L. The results obtained are promising, especially for groundwater samples and river water samples with a total organic carbon concentration below 9 mg C/L.

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.

The Co-Transport of PFAS and Cr(VI) in porous media.

PFAS and Cr are present at some sites as co-contaminants. The objective of this research was to investigate the co-transport behavior of per- and polyfluoroalkyl substances (PFAS) and hexavalent chromium (Cr(VI)) in porous media. Miscible-displacement experiments were conducted using two soils and an aquifer sediment with different geochemical properties. Perfluorooctane sulfonic acid (PFOS) and perfluorooctanoic acid (PFOA) were employed as model PFAS. The retardation of PFOS was decreased in the presence of Cr(VI). Conversely, the transport and retardation of PFOA was not affected by the presence of Cr(VI). The reduction of PFOS retardation caused by Cr(VI) is likely due to sorption competition for both organic-carbon and inorganic (metal-oxides and clay minerals) domains. The relative contributions of the three soil constituents to PFOS sorption and the potential for competition between PFOS and Cr(VI) is a function of the geochemical composition of the porous media (i.e., organic carbon, metal-oxides and clay minerals). The PFAS had minimal impact on the retention and transport of Cr(VI). To our knowledge, the results presented herein represent the first reported data for PFOS and Cr(VI) co-transport in porous media. The results of this study indicate that the presence of Cr(VI) has the potential to increase the migration potential of PFOS in soil and groundwater, which should be considered when characterizing electroplating facilities, leather tanning facilities, and other co-contaminated sites.