Hydrologic changes induced by groundwater abstraction lead to arsenic mobilization in shallow aquifers.

Intensive groundwater abstraction leads to hydrologic changes of groundwater. Nevertheless, the effects of hydrologic change on groundwater arsenic (As) mobilization remain controversial. Here, we investigated fluctuations in water levels and their effects on As mobilization in the shallow aquifer of the Hetao Basin. Results showed that large groundwater level fluctuations and high horizontal hydraulic gradients occurred in irrigation seasons. In the groundwater near the wetland with higher surface water levels than groundwater levels, biological index values of dissolved organic matter (DOM) ranged from 0.54 to 0.72, and a positive correlation between δ18O values and dissolved organic carbon (DOC) was observed, indicating that groundwater DOM was mainly sourced from surface water. The degradation of allochthone labile DOM drove the reductive dissolution of As-bearing Fe(III) oxides to Fe(II). Both DOC and humification indices of DOM exhibited positive correlations with horizontal hydraulic gradients downstream of the study area, implying that the humified organic matter flushed from aquifer sediments contributed to groundwater DOM. The humified DOM controlled by hydraulic conditions participated in the redox reactions mainly by shuttling electrons to As-bearing Fe(III) oxides. These findings highlight distinct roles of hydrologic changes induced by groundwater abstraction in As mobilization.

Dissimilatory Iodate-Reducing Microorganisms Contribute to the Enrichment of Iodine in Groundwater.

Iodate reduction by dissimilatory iodate-reducing microorganisms (DIRMs) plays a crucial role in the biogeochemical cycling of iodine on Earth. However, the occurrence and distribution of DIRMs in iodine-rich groundwater remain unclear. In this study, we isolated the dissimilatory iodate-reducing bacteriumAzonexus hydrophilusstrain NCP973 from a geogenic high-iodine groundwater of China for the first time. The analysis of genome, transcriptome, and heterologous expression revealed that strain NCP973 uses the dissimilatory iodate-reducing enzyme IdrABP1P2 to reduce dissolved or in situ sediment-bound iodate to iodide. The location of IdrABP1P2 in the conjugative plasmid of strain NCP973 implies that IdrABP1P2 could be spread by horizontal gene transfer and allow the recipient microorganisms to participate in the enrichment of iodide in aquifers. Based on the global iodine-rich groundwater metagenomes and genomes, the identification of idrA showed that phylogenetically diverse DIRMs are widely distributed not only in geogenic high-iodine groundwater of China but also in radionuclide-contaminated groundwater of USA as well as in subsurface cavern waters in Germany and Italy. Moreover, the abundance of idrA was found to be higher in groundwater with a relatively high iodine content. Collectively, these results suggest that terrestrial iodine-affected groundwater systems are another important habitat for DIRMs in addition to marine environments, and their activity in aquifers triggers the mobilization and enrichment of iodine in groundwater worldwide.

Hydrogeochemical differences drive distinct microbial community assembly and arsenic biotransformation in unconfined and confined groundwater of the geothermal system.

High­arsenic (As) groundwater in geothermal aquifers poses a serious threat to public health. Assembly processes governing groundwater microbial community related to As biotransformation are still unexplored in geothermal groundwater across different aquifers. To fill this gap, groundwater microorganisms, community assembly processes, and microbially metabolic coupling of carbon (C), nitrogen (N), phosphorus (P), sulfur (S), and arsenic (As) were investigated in unconfined and confined groundwater in the thermal reservoirs of the Guide Basin. The difference in groundwater hydrogeochemicals led to the heterogeneity of the microbial community and microbially mediated C, N, P, S, and As cycling between unconfined and confined groundwater. Higher temperature and As concentrations, low nutrient supply, and reduced conditions in confined groundwater supported stronger interspecific coexistence and environmental selection, thus promoting the proliferation of As-resistant microorganisms (ARMs) and simplifying the community assemblage. Abundant available nutrient supply and oxidizing conditions supported an increased species diversity and metabolic functionality in unconfined groundwater. S oxidizers, C fixation, and C degradation bacteria potentially contributed to the decreased As concentrations in unconfined groundwater. However, ARMs, ammonification, and anaerobic ammonia-oxidizing bacteria potentially caused As mobilization in confined groundwater. Overall, our results give a comprehensive insight into the interaction between As and microorganisms in geothermal groundwater.

Occurrences of nitrate-contaminated groundwater in the piedmont aquifers: hydrogeochemical characteristics and health risks.

Groundwater nitrate (NO3-) contamination is a global concern. The distribution patterns, enrichment mechanisms, and human health risks of NO3- contaminated groundwater were investigated using 144 groundwater samples collected from domestic and irrigation wells in the piedmonts of the North China Plain (Beijing and Shijiazhuang areas). The results showed that the groundwater was neutral to weakly alkaline, and 47% of the groundwater samples had NO3- concentrations exceeding 50 mg/L, a threshold proposed by world health organization to threaten infants up to 3 months. Groundwater NO3- concentrations were generally higher in the Beijing piedmont than in the Shijiazhuang piedmont and decreased with depth in both piedmonts. High-NO3- (> 50 mg/L) groundwater was distributed sporadically spatially and mainly was of Ca-Mg-HCO3 hydrochemical facies. Stable isotopes (D and 18O) compositions and NO3-/Cl- ratios indicated that NO3- accumulation in groundwater was primarily due to use of N-fertilizers under agricultural practices, and was associated with groundwater recharge sources such as septic tank leakage and re-infiltration of reclaimed irrigation water. Water quality evaluation showed that groundwater quality was highly dependent on NO3- concentration, with entropy-weighted water quality index values increasing linearly with increasing NO3- concentrations. The potential health risk of high-NO3- groundwater was the most serious for infants in both the piedmonts. Therefore, reducing NO3- input from sources and drinking water intake is recommended to minimize the human health risk.

Control of paleoclimate and paleoweathering on chromium contents in a non-ultramafic aquifer hosting high chromium groundwater.

Cr(VI) is a carcinogen with proven mutagenic and genotoxic effects. The effects of the depositional environment (e.g., paleoweathering, paleoclimate, and paleoredox condition) on Cr enrichment in non-ultramafic aquifer solids are unclear. In this study, we presented the sedimentary characteristics of a borehole from a typical non-ultramafic aquifer with high Cr groundwater in Jingbian, central Ordos Basin, China. Chromium was enriched in the K1h sandstone aquifer, especially at depths of 400-500 m, with the highest value of mass transport coefficient (τAl,Cr) up to 92.13% and τAl,Fe up to 33.5%. The provenance of aquifer Cr was predominantly intermediate and felsic igneous rocks with a mafic rock mixture. This mafic source was inferred from Cr-rich granodiorite and mafic/ultramafic rocks in the Yinshan (Daqingshan-Wulashan) Block, northern Ordos Basin. The Cr-rich aquifer in K1h was developed due to a moderate chemical index of alteration (CIA) (mean, 56.7) under relatively warm and humid paleoclimate, as evidenced by high CIA-temperature (CIA-Temp) (mean, 6.79 °C) and paleoclimatic index values (mean, 0.40). Fe-Mn redox cycling in the oxic to suboxic environments contributed to aquifer Cr accumulation. Using path analysis, we identified that paleoclimate created favorable weathering conditions and enrichment of Fe contributed to the formation of high-Cr aquifers. The study reveals the formation of positive Cr anomalies in non-ultramafic aquifers, which is the potential source of groundwater Cr, and highlights the effects of depositional factors on Cr accumulation during aquifer deposition or early diagenesis. It can provide new insights into the natural processes of high-Cr sediments occurring in non-ultramafic aquifers.

Natural Attenuation of Groundwater Uranium in Post-Neutral-Mining Sites Evidenced from Multiple Isotopes and Dissolved Organic Matter.

Although natural attenuation is an economic remediation strategy for uranium (U) contamination, the role of organic molecules in driving U natural attenuation in postmining aquifers is not well-understood. Groundwaters were sampled to investigate the chemical, isotopic, and dissolved organic matter (DOM) compositions and their relationships to U natural attenuation from production wells and postmining wells in a typical U deposit (the Qianjiadian U deposit) mined by neutral in situ leaching. Results showed that Fe(II) concentrations and δ34SSO4 and δ18OSO4 values increased, but U concentrations decreased significantly from production wells to postmining wells, indicating that Fe(III) reduction and sulfate reduction were the predominant processes contributing to U natural attenuation. Microbial humic-like and protein-like components mediated the reduction of Fe(III) and sulfate, respectively. Organic molecules with H/C > 1.5 were conducive to microbe-mediated reduction of Fe(III) and sulfate and facilitated the natural attenuation of dissolved U. The average U attenuation rate was -1.07 mg/L/yr, with which the U-contaminated groundwater would be naturally attenuated in approximately 11.2 years. The study highlights the specific organic molecules regulating the natural attenuation of groundwater U via the reduction of Fe(III) and sulfate.

Anthropogenic impact of rare earth elements on groundwater and surface water in the watershed of the largest freshwater lake in China.

Limited knowledge exists regarding the potential risks associated with anthropogenic release of rare earth elements (REEs) in the environment. This study aimed to investigate REE signatures in the watershed Poyang Lake, the largest freshwater lake in China. Samples of surface water, wastewater, and groundwater were collected from five rivers discharging into the lake. Results revealed wastewater from wastewater treatment plants contained total REE concentrations from 231 to 904 µg/L, exceeding those found in surface water (0.4 to 1.3 µg/L) and groundwater (0.5 to 416 µg/L). Samples with elevated REE were found in Ca-Mg-Cl/SO4 type waters and exhibited an 18OD deviation from local meteoric water line. Wastewater exhibited a higher positive Gd anomaly compared to surface water and groundwater, attributed to anthropogenic input of Gd (Gdanth). The determined Gdanth concentration ranged from 0.04 to 0.21 µg/L, and from 0.06 to 0.37 µg/L, accounting for 4 % to 21 % and 49 % to 84 % of total Gd concentrations in groundwater and surface water, respectively. Gdanth concentration in wastewater (0.19 to 0.43 µg/L) remained constant in effluent after wastewater treatment. Surface water displayed relatively complex normalized REE patterns influenced by anthropogenic activities and natural processes (weathering and complexation), while groundwater exhibited heavy REEs enrichment, due to carbonate solution complexation. Additionally, Gdanth concentration showed a positive correlation with ΣREE, Pb, Ni, and Co concentrations in groundwater, indicating a good pollution tracing potential. Health risk assessment using the hazard quotient (HQ) suggested higher HQGd values in groundwater compared to surface water. Residents in the eastern part of Poyang Lake were found to face higher risks associated with Gd in groundwater compared to the western part, with infants and children at greater risk than adult males and females. These findings offer valuable insights into environmental behavior and health risks of REEs in aquatic systems impacted by human activities.

Enhancing soil petrochemical contaminant remediation through nutrient addition and exogenous bacterial introduction.

Biostimulation (providing favorable environmental conditions for microbial growth) and bioaugmentation (introducing exogenous microorganisms) are effective approaches in the bioremediation of petroleum-contaminated soil. However, uncertainty remains in the effectiveness of these two approaches in practical application. In this study, we constructed mesocosms using petroleum hydrocarbon-contaminated soil. We compared the effects of adding nutrients, introducing exogenous bacterial degraders, and their combination on remediating petroleum contamination in the soil. Adding nutrients more effectively accelerated total petroleum hydrocarbon (TPH) degradation than other treatments in the initial 60 days' incubation. Despite both approaches stimulating bacterial richness, the community turnover caused by nutrient addition was gentler than bacterial degrader introduction. As TPH concentrations decreased, we observed a succession in microbial communities characterized by a decline in copiotrophic, fast-growing bacterial r-strategists with high rRNA operon (rrn) copy numbers. Ecological network analysis indicated that both nutrient addition and bacterial degrader introduction enhanced the complexity and stability of bacterial networks. Compared to the other treatment, the bacterial network with nutrient addition had more keystone species and a higher proportion of negative associations, factors that may enhance microbial community stability. Our study demonstrated that nutrient addition effectively regulates community succession and ecological interaction to accelerate the soil TPH degradation.

Groundwater irrigation induced variations in DOM fluorescence and arsenic mobility.

Dissolved organic matter (DOM) plays a predominant role in groundwater arsenic (As) mobility. However, the temporal-spatial variations in DOM fluorescent characteristics and their effects on As mobility induced by groundwater irrigation remain unclear. To address these issues, groundwater from multilevel and irrigation wells in Zones I and II (with low- and high-As groundwater irrigation, respectively) from the Hetao Basin, China, were monitored in both non-irrigation (NIG) and irrigation (IG) seasons. Upon irrigation, the irrigation return increased the relative abundance of protein- and humic-like DOM in shallow groundwater from Zone I with Ca-type groundwater and Zone II with Na-type groundwater irrigation, respectively. The introduced dissolved oxygen by irrigation return decreased As concentrations by 22 % and 6 % on average in shallow groundwater from Zones I and II, respectively. However, the pumping-induced lateral recharge of lower- and higher-As groundwater led to an average 17 % decrease and 38 % increase in As concentrations in deeper groundwater from the two zones, respectively. The increased degradation of protein-like DOM may also contribute to the elevated As concentrations in deep groundwater from Zone II. The study provides insights into the dependence of irrigation-induced variations in DOM fluorescence and As concentrations on geochemicals of irrigation groundwater and aquifer hydrogeological conditions.

Prediction of arsenic and fluoride in groundwater of the North China Plain using enhanced stacking ensemble learning.

Chronic exposure to elevated geogenic arsenic (As) and fluoride (F-) concentrations in groundwater poses a significant global health risk. In regions around the world where regular groundwater quality assessments are limited, the presence of harmful levels of As and F- in shallow groundwater extracted from specific wells remains uncertain. This study utilized an enhanced stacking ensemble learning model to predict the distributions of As and F- in shallow groundwater based on 4,393 available datasets of observed concentrations and forty relevant environmental factors. The enhanced model was obtained by fusing well-suited Extreme Gradient Boosting, Random Forest, and Support Vector Machine as the base learners and a structurally simple Linear Discriminant Analysis as the meta-learner. The model precisely captured the patchy distributions of groundwater As and F- with an AUC value of 0.836 and 0.853, respectively. The findings revealed that 9.0% of the study area was characterized by a high As risk in shallow groundwater, while 21.2% was at high F- risk identified as having a high risk of fluoride contamination. About 0.2% of the study area shows elevated levels of both of them. The affected populations are estimated at approximately 7.61 million, 34.1 million, and 0.2 million, respectively. Furthermore, sedimentary environment exerted the greatest influence on distribution of groundwater As, with human activities and climate following closely behind at 29.5%, 28.1%, and 21.9%, respectively. Likewise, sedimentary environment was the primary factor affecting groundwater F- distribution, followed by hydrogeology and soil physicochemical properties, contributing 27.8%, 24.0%, and 23.3%, respectively. This study contributed to the identification of health risks associated with shallow groundwater As and F-, and provided insights into evaluating health risks in regions with limited samples.

Geogenic high arsenic elevates the groundwater antibiotic resistomes: A blind spot of resistance in Anthropocene.

Metals/metalloids, being ubiquitous in the environment, can function as a co-selective pressure on antibiotic resistance genes (ARGs) threatening human health. However, the effect of geogenic arsenic (As) on groundwater antibiotic resistomes and their health risks remain largely unknown. Here, we systematically analyzed bacterial communities, pathogenic bacteria, antibiotic resistomes, and in-situ multidrug-resistant isolates with the assessment of the health risk of ARGs and the pathogenicity of their hosts in high As groundwater from the Hetao basin, Northwestern China. We found that long-term geogenic As exposure shifted the assembly of resistomes and resulted in a high abundance and diversity of ARGs in groundwater. Significantly positive associations among As, As cycling genes, ARGs, and mobile genetic elements (MGEs) revealed by network and pathway analyses, together with genetic evidence of As-tolerant multidrug-resistant isolates by whole genomic sequencing, robustly indicate the geogenic As-induced co-selection for antibiotic resistance in groundwater. Variance partitioning analysis further confirmed the determinative role of geogenic As in groundwater resistomes, with As species and As cycling genes as the core abiotic and biotic drivers, respectively. More seriously, geogenic As accelerated the prevalence of high-risk ARGs and multidrug-resistant bacteria. Our findings highlight the significance of geogenic As-induced co-selection for antibiotic resistance in groundwater and the hidden role of geogenic metals/metalloids in increasing antibiotic resistance. This study provides a basis for groundwater management of both high As and ARGs for human health.

How Human Activities Affect Groundwater Storage.

Despite the recognized influence of natural factors on groundwater, the impact of human activities remains less explored because of the challenges in measuring such effects. To address this gap, our study proposes an approach that considers carbon emissions as an indicator of human activity intensity and quantifies their impact on groundwater storage. The combination of carbon emission data and groundwater storage data for 17,152 grid cells over 16 years in 4 typical basins shows that they were generally negatively correlated, whereas both agriculture and aviation had positive impacts on groundwater storage. The longest impact from aviation and agriculture can even persist for 7 years. Furthermore, an increase of 1 Yg CO2/km2 per second in emissions from petroleum processing demonstrates the most pronounced loss of groundwater storage in the Yangtze River Basin (approximately 4.1 mm). Moreover, regions characterized by high-quality economic development tend to have favorable conditions for groundwater storage. Overall, our findings revealed the substantial role of human activities in influencing groundwater dynamics from both temporal and spatial aspects. This study fills a crucial gap by exploring the relationship between human activities and groundwater storage through the introduction of a quantitative modeling framework based on carbon emissions. It also provides insights for facilitating empirical groundwater management planning and achieving optimal emission reduction levels.

Quantifying the impact of anthropogenic emissions and aquatic environmental impacts on sedimentary mercury variations in a typical urban river.

In urban and industrial regions, sedimentary mercury (Hg) serves as the crucial indicator for Hg pollution, posing potential risks to ecology and human health. The physicochemical processes of Hg in aquatic environments are influenced by various factors such as anthropogenic emissions and aquatic environmental impacts, making it challenging to quantify the drivers of total mercury (THg) variations. Here, we analyzed the spatiotemporal variations, quantified driving factors, and assessed accumulation risks of sedimentary THg from the mainstream of a typical urban river (Haihe River). THg in the urban region (37-3237 ng g-1) was significantly higher (t-test, p < 0.01) than in suburban (71-2317 ng g-1) and developing regions (156-916 ng g-1). The sedimentary THg in suburban and developing regions increased from 2003 to 2018, indicating the elevated atmospheric deposition of Hg. Together with the temperature, grain size of sediments, total organic carbon (TOC), the pH and salinity of water, 40 components of parent and substituted polycyclic aromatic hydrocarbons (PAHs) were first introduced to quantify the driver of sedimentary THg based on generalized additive model. Results showed that anthropogenic emissions, including three PAHs components (31%) and TOC (63%), accounted for 94% of sedimentary THg variations. The aquatic environmental impacts accounted for 5% of sedimentary THg variations. The geo-accumulation index of THg indicated moderate to heavy accumulation in the urban region. This study demonstrates that homologous pollutants such as PAHs can be used to trace sources and variations of Hg pollution, supporting their co-regulation as international conventions regulate pollutants.

High biodegradability of microbially-derived dissolved organic matter facilitates arsenic enrichment in groundwater: Evidence from molecular compositions and structures.

Although biodegradation of organic matter is well-known to trigger enrichment of arsenic (As) in groundwater, the effects of DOM sources and biodegradability on As enrichment remain elusive. In this study, groundwater samples were collected from the Hetao basin to identify DOM source and evaluate biodegradability by using spectral and molecular techniques. Results showed that in the alluvial fan, DOM was mainly sourced from terrestrially derived OM, while DOM in the flat plain was more originated from microbially derived OM. Compared to terrestrially derived DOMs, microbially derived DOMs in groundwater, which had relatively higher H/Cwa ratios, NOSC values and more biodegradable molecules, exhibited higher biodegradability. In the flat plain, microbially derived DOMs with higher biodegradability encountered stronger biodegradation, facilitating the reductive dissolution of Fe(III)/Mn oxides and As enrichment in groundwater. Moreover, the enrichment of As depended on the biodegradable molecules that was preferentially utilized for primary biodegradation. Our study highlights that the enrichment of dissolved As in the aquifers was closely associated with microbially derived DOM with high biodegradability and high ability for primary biodegradation.

Ammonium-Enhanced Arsenic Mobilization from Aquifer Sediments.

Ammonium-related pathways are important for groundwater arsenic (As) enrichment, especially via microbial Fe(III) reduction coupled with anaerobic ammonium oxidation; however, the key pathways (and microorganisms) underpinning ammonium-induced Fe(III) reduction and their contributions to As mobilization in groundwater are still unknown. To address this gap, aquifer sediments hosting high As groundwater from the western Hetao Basin were incubated with 15N-labeled ammonium and external organic carbon sources (including glucose, lactate, and lactate/acetate). Decreases in ammonium concentrations were positively correlated with increases in the total produced Fe(II) (Fe(II)tot) and released As. The molar ratios of Fe(II)tot to oxidized ammonium ranged from 3.1 to 3.7 for all incubations, and the δ15N values of N2 from the headspace increased in 15N-labeled ammonium-treated series, suggesting N2 as the key end product of ammonium oxidation. The addition of ammonium increased the As release by 16.1% to 49.6%, which was more pronounced when copresented with organic electron donors. Genome-resolved metagenomic analyses (326 good-quality MAGs) suggested that ammonium-induced Fe(III) reduction in this system required syntrophic metabolic interactions between bacterial Fe(III) reduction and archaeal ammonium oxidation. The current results highlight the significance of syntrophic ammonium-stimulated Fe(III) reduction in driving As mobilization, which is underestimated in high As groundwater.

Seasonal sensitivity of groundwater dissolved organic matter in recognition of chronic kidney disease of unknown etiology: Optical and molecular perspectives.

Chronic kidney disease of unknown etiology (CKDu) has aroused a great concern due to its widespread prevalence in many developing countries. Dissolved organic matter (DOM) has been proved to be associated with CKDu in groundwater. However, the responses of their association to abiotic influencing factors like seasonal variation are not carefully disclosed. Herein, we revealed the seasonal variation of DOM in CKDu related groundwater (CKDu groundwater) and control group (non-CKDu groundwater) collected from Sri Lanka during the dry and wet seasons by excitation-emission matrix spectroscopy and Fourier transform ion cyclotron resonance mass spectrometry. In both CKDu and non-CKDu groundwaters, the input of exogenous DOM during wet season improved the degree of humification and molecular weight of DOM, while oxidative processes during the dry season increased the ratios of oxygen to carbon (O/C). Furthermore, compared with non-CKDu groundwater, more DOM with high O/C enriched in CKDu groundwater during the dry season, indicating stronger oxidative processes in CKDu groundwater. It may result in the enrichment of carboxyl group and induce the enhanced leaching of CKDu-related Si and F-. The receiver operating characteristic (ROC) analysis showed that the CKDu-recognition ability of most optical and molecular indicators was susceptible to seasonal factors and their recognition abilities were stronger in the wet season. The linkage between DOM and CKDu was affected by seasonal factors through the occurrence, mobility, degradation, and toxicity of typical organic molecules (e.g., C17H18O10S). The study provides a new insight into screening pathogenic factors of other endemic diseases related to organic molecules.

Synergetic effects of Mn(II) production and site availability on arsenite oxidation and arsenate adsorption on birnessite in the presence of low molecular weight organic acids.

Manganese oxides and organic acids are key factors affecting arsenic mobility, but As(III) oxidation and adsorption in the coexistence of birnessite and low molecular weight organic acids (LMWOAs) are poorly understood. Herein, As(III) immobilization by birnessite was investigated with/without LMWOAs (including tartaric (TA), malate (MA), and succinic acids (SA) with two, one and zero hydroxyl groups, respectively). In the low-As(III) system with less Mn(II) production, LMWOAs generally inhibited As(III) oxidation. The slower decrease in As(III) concentration in TA-amended batches resulted from stronger bonding interaction between TA and edge sites, evidenced by higher removal of TA than MA and SA in solutions and the higher proportion of shifted C-OH component in solids. In high-As(III) systems with abundant Mn(II) production, higher concentrations of dissolved Mn and Mn(III) in LMWOA-amended batches than in LMWOA-free batches revealed that LMWOA-induced complexing dissolution caused the release of adsorbed Mn(II), which was conducive to As(III) oxidation and As(V) adsorption onto the edge sites. The lowest concentrations of dissolved Mn and Mn(III) in TA-amended batches indicated that the hydroxyl group constrained complexing dissolution. This study reveals that concentrations of produced Mn(II) determined the roles of LMWOAs in As(III) behavior and highlights the impacts of the hydroxyl group on arsenic mobility.

Metabolic coupling of arsenic, carbon, nitrogen, and sulfur in high arsenic geothermal groundwater: Evidence from molecular mechanisms to community ecology.

Groundwater arsenic (As) poses a global environmental problem and is regulated by complex biogeochemical processes. However, the As biogeochemistry and its metabolic coupling with carbon (C), nitrogen (N), and sulfur (S) in high As geothermal groundwater remain unclear. Here, we reported significant shifts in the geothermal groundwater microbiome and its functional ecological clusters along the flow path with increased As levels and dynamic As-C-N-S biogeochemical cycle from the Guide Basin, China. Strong associations among As(III), NH4+, HCO3-, and corresponding functional microbial taxa suggest that microbe-mediated As transformation, ammonification, and organic carbon biodegradation potentially contributed to the As mobilization in the discharge area. And As oxidizers (coupling with denitrification or carbon fixation) and S oxidizers were closely linked to the transformation of As(III) to immobile As(V) in the recharge area. Our study provides a comprehensive insight into the complex microbial As-C-N-S coupling network and its potential role in groundwater As mobilization under hydrological disturbances.

Co-occurrence of arsenic and fluoride in groundwater of Guide basin in China: Genesis, mobility and enrichment mechanism.

Endemic arsenic poisoning and fluorosis caused by primary high arsenic (As) and high fluoride (F-) groundwater have become one of the most serious environmental geological problems faced by the international society. High As and high F- groundwater exists in Neogene confined aquifers in Guide basin, with concentrations of 355 µg/L and 5.67 mg/L, respectively, and showing a co-occurrence phenomenon of As and F- in the groundwater. This poses a double threat to the health of tens of thousands of local residents. In this study, based on the systematic collection of groundwater and borehole sediment samples, analysis of hydrochemistry and isotope indexes, combined with laboratory tests, purpose of this study is to reveal the migration rule and co-enrichment mechanism of As and F- in aquifers, and finally establish a hydrogeochemical conceptual model of the enrichment process of As and F-. The main conclusions are as follows: hydrochemical type of unconfined and confined groundwater in Guide basin is Ca-Na-HCO3 and Na-Cl-HCO3 type, respectively. Main minerals in sediments are quartz and plagioclase. Concentrations of As and F- are lower in unconfined groundwater, but higher in confined groundwater, and which show a gradual increasing trend along the groundwater flow path. The mineralization of natural organic matter in confined aquifer causes iron and manganese oxide minerals containing As to dissolve gradually, which leads to the gradual release of As into groundwater. Large amount of HCO3- produced by mineralization of organic matter precipitate with Ca2+ in groundwater, resulting in reduction of Ca2+ content, promoting the dissolution of fluoride-containing minerals such as fluorite (CaF2), and continuously releasing F- into groundwater. Meanwhile, competitive adsorption reactions in confined aquifers causes more As and F- to be released from mineral surface into groundwater, which gradually migrate and accumulate along groundwater flow. Finally, it is established that a conceptual model for the formation of high As and F- groundwater in the confined aquifer of Guide basin. The research results not only help to improve our understanding of the formation and evolution of groundwater with high As and F- with similar geological background, but also provide scientific basis for rational development and utilization of groundwater, and prevention and control of chronic As and F- poisoning in local and similar areas.

Mechanistic insight into Cr(VI) retention by Si-containing ferrihydrite.

Hexavalent chromium [Cr(VI)] causes serious harm to the environment due to its high toxicity, solubility, and mobility. Ferrihydrites (Fh) are the main adsorbent and trapping agent of Cr(VI) in soils and aquifers, and they usually coexist with silicate (Si), forming Si-containing ferrihydrite (Si-Fh) mixtures. However, the mechanism of Cr(VI) retention by Si-Fh mixtures is poorly understood. In this study, the behaviors and mechanisms of Cr(VI) adsorption onto Si-Fh with different Si/Fe molar ratios was investigated. Transmission electron microscope, Fourier transform infrared spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy, and other techniques were used to characterize Si-Fh and Cr(VI)-loading of Si-Fh. The results show that specific surface area of Si-Fh increases gradually with increasing Si/Fe ratios, but Cr(VI) adsorption on Si-Fh decreases with increasing Si/Fe ratios. This is because with an increase in Si/Fe molar ratio, the point of zero charge of Si-Fh gradually decreases and electrostatic repulsion between Si-Fh and Cr(VI) increases. However, the complexation of Cr(VI) is enhanced due to the increase in adsorbed hydroxyl (A-OH-) on Si-Fh with increasing Si/Fe molar ratio, which partly counteracts the effect of the electrostatic repulsion. Overall, the increase in the electrostatic repulsion has a greater impact on adsorption than the additional complexation with Si-Fh. Density functional theory calculation further supports this observation, showing the increases in electron variation of bonding atoms and reaction energies of inner spherical complexes with the increase in Si/Fe ratio.