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.

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.

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.

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.

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.

Elucidating Multiple Electron-Transfer Pathways for Metavanadate Bioreduction by Actinomycetic Streptomyces microflavus.

While microbial reduction has gained widespread recognition for efficiently remediating environments polluted by toxic metavanadate [V(V)], the pool of identified V(V)-reducing strains remains rather limited, with the vast majority belonging to bacteria and fungi. This study is among the first to confirm the V(V) reduction capability of Streptomyces microflavus, a representative member of ubiquitous actinomycetes in environment. A V(V) removal efficiency of 91.0 ± 4.35% was achieved during 12 days of operation, with a maximum specific growth rate of 0.073 d-1. V(V) was bioreduced to insoluble V(IV) precipitates. V(V) reduction took place both intracellularly and extracellularly. Electron transfer was enhanced during V(V) bioreduction with increased electron transporters. The electron-transfer pathways were revealed through transcriptomic, proteomic, and metabolomic analyses. Electrons might flow either through the respiratory chain to reduce intracellular V(V) or to cytochrome c on the outer membrane for extracellular V(V) reduction. Soluble riboflavin and quinone also possibly mediated extracellular V(V) reduction. Glutathione might deliver electrons for intracellular V(V) reduction. Bioaugmentation of the aquifer sediment with S. microflavus accelerated V(V) reduction. The strain could successfully colonize the sediment and foster positive correlations with indigenous microorganisms. This study offers new microbial resources for V(V) bioremediation and improve the understanding of the involved molecular mechanisms.

Molecular Responses of Dissolved Organic Matter to Anthropogenic Groundwater Recharge: Characteristics, Transformations, and Sensitive Molecules.

The groundwater quality impacts associated with anthropogenic groundwater recharge (AGR) are of great concern for water management. However, the impacts of AGR on the molecular properties of dissolved organic matter (DOM) in aquifers are poorly understood. Herein, Fourier transform ion cyclotron resonance mass spectrometry was used to unravel the molecular characteristics of DOM in groundwaters from recharge areas by reclaimed water (RWRA) and natural water from South-to-North Water Diversion Project (SNWRA). Compared with RWRA groundwater, significantly fewer nitrogenous compounds, more sulfur-containing compounds, higher concentrations of NO3-N, and lower pH were observed in SNWRA groundwater, indicating the occurrence of deamination, sulfurization, and nitrification. The occurrence of these processes was further supported by transformations of more molecules related to nitrogen and sulfur in SNWRA groundwater relative to RWRA groundwater. The intensities of most common molecules in all samples were significantly correlated with the water quality indicators (e.g., Cl- and NO3-N) and fluorescent indicators (e.g., humic-like components (C1%)), indicating that those common molecules may have the potential to track the environmental impact of AGR on groundwater, especially these specific molecules having great mobility and being significantly correlated with other inert tracers like C1% and Cl-. This study is helpful to understand the environmental risks and regional applicability of AGR.

Hydrogeochemical factors controlling the occurrence of chronic kidney disease of unknown etiology (CKDu).

Chronic kidney disease of unknown etiology (CKDu) has posed a serious threat to human health around the world. The link between the prevalence of CKDu and groundwater geochemistry is not well understood. To identify the potential geogenic risk factors, we collected 52 groundwater samples related to CKDu (CKDu groundwater) and 18 groundwater samples related to non-CKDu (non-CKDu groundwater) from the typical CKDu prevailing areas in Sri Lanka. Results demonstrated that CKDu groundwater had significantly higher Si (average 30.1 mg/L, p < 0.05) and F- (average 0.80 mg/L, p < 0.05) concentrations than those of non-CKDu groundwater (average 21.0 and 0.45 mg/L, respectively), indicating that Si and F- were the potential risk factors causing CKDu. The principal hydrogeochemical process controlling local groundwater chemistry was chemical weathering of silicates in Precambrian metamorphic rocks. Groundwater samples were mostly undersaturated with respect to amorphous silica and clay minerals such as talc and sepiolite, which was conducive to silicate weathering and elevated Si concentrations in groundwater. Decreased Ca2+ being facilitated by calcite precipitation and cation exchange between Ca2+ and Na+ favored fluorite dissolution and thus led to high groundwater F- concentrations. Competitive adsorption between [Formula: see text] and F- also enhanced the release of F- from solid surfaces. This study highlights the CKDu potential risk factors regarding groundwater geochemistry and their enrichment factors, which helps in preventing the prevalence of CKDu.

Genome-Resolved Metagenomic Analysis of Groundwater: Insights into Arsenic Mobilization in Biogeochemical Interaction Networks.

High-arsenic (As) groundwaters, a worldwide issue, are critically controlled by multiple interconnected biogeochemical processes. However, there is limited information on the complex biogeochemical interaction networks that cause groundwater As enrichment in aquifer systems. The western Hetao basin was selected as a study area to address this knowledge gap, offering an aquifer system where groundwater flows from an oxidizing proximal fan (low dissolved As) to a reducing flat plain (high dissolved As). The key microbial interaction networks underpinning the biogeochemical pathways responsible for As mobilization along the groundwater flow path were characterized by genome-resolved metagenomic analysis. Genes associated with microbial Fe(II) oxidation and dissimilatory nitrate reduction were noted in the proximal fan, suggesting the importance of nitrate-dependent Fe(II) oxidation in immobilizing As. However, genes catalyzing microbial Fe(III) reduction (omcS) and As(V) detoxification (arsC) were highlighted in groundwater samples downgradient flow path, inferring that reductive dissolution of As-bearing Fe(III) (oxyhydr)oxides mobilized As(V), followed by enzymatic reduction to As(III). Genes associated with ammonium oxidation (hzsABC and hdh) were also positively correlated with Fe(III) reduction (omcS), suggesting a role for the Feammox process in driving As mobilization. The current study illustrates how genomic sequencing tools can help dissect complex biogeochemical systems, and strengthen biogeochemical models that capture key aspects of groundwater As enrichment.

Influence of Legacy Mercury on Antibiotic Resistomes: Evidence from Agricultural Soils with Different Cropping Systems.

Agricultural soils are important reservoirs for antibiotic resistance genes (ARGs), which have close linkage to human health via crop production. Metal stress in environments may function as a selection pressure for antibiotic resistomes. However, there is still a lack of field studies focusing on the effect of historical mercury (Hg) contamination on antibiotic resistomes in agricultural soils. Here, we explored the ARG profile in soils with different cropping systems (paddy and upland) and linked them to legacy Hg exposure. We found that ARG profiles were significantly different between paddy and upland soils. However, both paddy and upland soils with long-term field Hg contamination harbored higher diversity and abundance of ARGs than non-polluted soils. The co-occurrence network reveals significant associations among Hg, Hg resistance genes, mobile genetic elements (MGEs), and ARGs. Together with path analysis showing legacy Hg possibly affecting soil resistomes through the shifts of soil microbiota, Hg resistance genes, and MGEs, we suggest that legacy Hg-induced potential co-selection might elevate the ARG level. Redundancy analysis further supports that legacy Hg pollution had a significant association with ARG variations in the paddy and upland soils (P < 0.01). Collectively, our results highlight the underappreciated role of legacy Hg as a potential persistent selecting agent in contributing to soil ARGs in agroecosystems.

Understanding Microbial Arsenic-Mobilization in Multiple Aquifers: Insight from DNA and RNA Analyses.

Biogeochemical processes critically control the groundwater arsenic (As) enrichment; however, the key active As-mobilizing biogeochemical processes and associated microbes in high dissolved As and sulfate aquifers are poorly understood. To address this issue, the groundwater-sediment geochemistry, total and active microbial communities, and their potential functions in the groundwater-sediment microbiota from the western Hetao basin were determined using 16S rRNA gene (rDNA) and associated 16S rRNA (rRNA) sequencing. The relative abundances of either sediment or groundwater total and active microbial communities were positively correlated. Interestingly, groundwater active microbial communities were mainly associated with ammonium and sulfide, while sediment active communities were highly related to water-extractable nitrate. Both sediment-sourced and groundwater-sourced active microorganisms (rRNA/rDNA ratios > 1) noted Fe(III)-reducers (induced by ammonium oxidation) and As(V)-reducers, emphasizing the As mobilization via Fe(III) and/or As(V) reduction. Moreover, active cryptic sulfur cycling between groundwater and sediments was implicated in affecting As mobilization. Sediment-sourced active microorganisms were potentially involved in anaerobic pyrite oxidation (driven by denitrification), while groundwater-sourced organisms were associated with sulfur disproportionation and sulfate reduction. This study provides an extended whole-picture concept model of active As-N-S-Fe biogeochemical processes affecting As mobilization in high dissolved As and sulfate aquifers.

Refractory Humic-like Substances: Tracking Environmental Impacts of Anthropogenic Groundwater Recharge.

To unravel the crucial components of natural organic matter that respond to the process of anthropogenic groundwater recharge (AGR) from different recharge water sources, dissolved organic matter (DOM) and base-extractable particulate organic matter (POM) in groundwater and surface water were analyzed using excitation-emission matrix spectroscopy coupled with parallel factor analysis (EEM-PARAFAC). The EEM and traditional spectral indices of samples show that the fluorescent intensity, molecular weight, and humification degree of the DOM were relatively higher than those of the POM, and the groundwater in the reclaimed water recharge area (RWRA) was more contaminated than in the south-to-north water recharge area (SNWRA). PARAFAC analysis indicates that the DOM was dominated by an allochthonous humic-like substance (C1), whereas the POM was dominated by tryptophan-like substances associated with microbial activity (C2). Partitioning of PARAFAC components between DOM and POM showed that the humic-like substances (C1 and C4) were more likely to be distributed into a dissolved phase compared to the protein-like substances (C2 and C3), which suggested the potential use of C1 and C4 as a tracking indicator. In particular, the clear gradient distributions along both the hydrogeological profile and different aquifer systems in terms of the concentration and composition of C1 also discriminated between the RWRA and SNWRA with regard to the effects of various AGRs on the groundwater. The association between C1 and water-quality indicators revealed by principal component analysis further indicated that refractory humic-like substances would track the environmental impacts of intentional AGR processes.

Molecular Evidence of Arsenic Mobility Linked to Biodegradable Organic Matter.

Molecular characteristics of natural organic matter (NOM) and their potential connections to arsenic enrichment processes remain poorly understood. Here, we examine dissolved organic matter (DOM) in groundwater and water-soluble organic matter (WSOM) in aquifer sediments being depth-matched with groundwater samples from a typical arid-semiarid basin (Hetao Basin, China) hosting high arsenic groundwater. We used Fourier transform ion cyclotron resonance mass spectrometry to determine molecular characteristics of DOM and WSOM and evaluate potential roles of biodegradable compounds in microbially mediated arsenic mobility at the molecular level. High-arsenic groundwater DOM was generally enriched in recalcitrant molecules (including lignins and aromatic structures). Although potential contribution of recalcitrant compounds to arsenic enrichment cannot be ruled out, preferential degradation of the labile molecules coupled with reduction of Fe(III) (oxyhydr)oxides seemed to dominate arsenic mobilization. Both the number and the intensity of biodegradable compounds (including aliphatic/proteins and carbohydrates) were higher in WSOM than those in DOM in depth-matched high-arsenic groundwater (arsenic >0.67 µmol/L or 50 µg/L). Groundwater arsenic concentration generally increased with the increase in the number and the intensity of unique biodegradable compounds (especially N-containing compounds) in WSOM at matched depths. Anoxic incubations of sediments and deionized water show that more arsenic and Fe(II) were released from aquifer sediments with greater numbers and intensities of consumed biodegradable compounds in WSOM (especially N-containing compounds), with a higher proportion of microbially derived compounds produced. These observations indicate that the biodegradation of aliphatic/proteins and carbohydrates (especially CHON formulas) in WSOM fueling the reductive dissolution of Fe(III) (oxyhydr)oxides predominantly promotes arsenic release from aquifer solids. Our unique data present a better understanding of arsenic mobilization shaped by microbial degradation of labile organic compounds in anoxic aquifers at the molecular level.

High Hexavalent Chromium Concentration in Groundwater from a Deep Aquifer in the Baiyangdian Basin of the North China Plain.

Hexavalent chromium (Cr(VI)) is known to occur naturally in shallow oxic groundwater, typically from aquifers associated with mafic and ultramafic formations, but information on the occurrence of Cr(VI) in deep groundwater from large sedimentary basins is limited. This study shows that groundwater from the Baiyangdian Lake Basin (BYB), home to the future second capital city of China, had high Cr concentration (>10 µg/L, up to 86 µg/L) in the deep aquifer (>150 m), while shallow groundwater had lower Cr concentration (<10 µg/L). Chromium occurred predominantly as Cr(VI) (>95%). Shallow groundwater was characterized by higher Mn and Fe concentrations relative to deep groundwater, likely indicating more reducing conditions. Sequential extraction experiments from aquifer sediments suggest that Cr(VI) may derive from silicate weathering and that Mn oxides in the aquifer play a major role in the formation of Cr(VI) in groundwater. Inverse correlations between Mn and Cr(VI) suggest that reductive dissolution of Mn oxides constrains Cr(VI) mobilization in the shallow groundwater, while oxic-suboxic conditions in the deep aquifer limit Mn solubility, which enhances oxidation of Cr(III) to Cr(VI) and promotes desorption of Cr(VI) under alkaline conditions. This study demonstrates the potential geogenic occurrence of high Cr(VI) concentration in deep groundwater from a nonmafic, large sedimentary basin containing Mn oxides in the aquifer sediments.

The provenance of deep groundwater and its relation to arsenic distribution in the northwestern Hetao Basin, Inner Mongolia.

High-arsenic (As) groundwater has been widely found throughout the world. The source of groundwater would determine spatial distribution of groundwater As. In order to trace the source of high-As deep groundwater (DGW, depths > 50 m), groundwater, sediments, and local bedrock samples were taken to investigate chemical and isotopic compositions in the Hetao Basin, China. Results showed that 87Sr/86Sr in DGW gradually decreased with the increase in As concentrations along the approximate flow path. In recharge-oxic zone (Zone I), DGW was mainly recharged by fissure water, influenced mostly by weathering of phyllite bedrock and meta-basalt. In groundwater flow-moderate reducing zone (Zone II), DGW was mainly related to incongruent dissolution of feldspar. However, in groundwater flow-reducing zone (Zone III), DGW was partly recharged from shallow groundwater (SGW) with depths < 50 m. The mixing contributions of SGW to DGW in Zone III mostly exceeded 80% during groundwater irrigation season. In Zone I, DGW As concentrations were mostly lower than 50 µg/L due to oxic conditions. In Zone II, the weakly alkaline pH and the decreasing Ca/Na resulting from incongruent dissolution of feldspar caused As desorption, which was the major contribution to As mobilization (As mostly > 200 µg/L). In Zone III, the recharge of SGW introduced labile organic matter to support reduction of Fe(III) oxyhydroxides/oxides and predominantly led to As release into groundwater (As > 300 µg/L). This study has provided insights into the source of high-As DGW and the effect of SGW mixing on As mobilization.

Model-Based Interpretation of Groundwater Arsenic Mobility during in Situ Reductive Transformation of Ferrihydrite.

Arsenic (As) release and mobility in groundwater is coupled to the iron (Fe) cycling and the associated transformation of Fe-oxides present in sediments. Recent in situ experiments have provided observations on arsenic mobilization and co-occurring reductive mineral transformation when placing As-loaded ferrihydrite-coated sand for 80 days in wells of an As-contaminated aquifer of Northern China. However, the complex temporal change in solid-associated arsenic and the multiple geochemical processes occurring when the flowing groundwater contacts the As-loaded ferrihydrite-coated sand hamper a detailed evaluation of the experimental data set. In this study, we develop a modeling approach that allows a quantitative interpretation of arsenic release and ferrihydrite transformation observed during the in situ experiments. The model accounts for the interplay of abiotic and biotic geochemical processes (i.e., surface complexation, reductive dissolution, formation of secondary iron minerals, and arsenic sequestration into the newly formed minerals) involved in the transformation of Fe-oxides and controlling arsenic mobility. The results show the capability of the proposed approach to reproduce the temporal trends of solid arsenic and ferrihydrite concentrations, as well as the spatial variability of mineral transformation, observed in different wells using a common set of surface complexation parameters and kinetic rate constants. The simulation outcomes allowed us to disentangle the specific contribution of the different mechanisms controlling the release of arsenic. It was possible to identify an initial rapid but minor release of As (13-23% of the initial surface concentration) due to desorption from ferrihydrite, as well as the reduction of adsorbed As(V) to As(III) upon contact with the flowing anoxic groundwater. Successively, reductive dissolution of ferrihydrite caused the decrease of the amount of the Fe mineral phase and led to a major depletion of solid-associated arsenic. The produced Fe(II) catalyzed the ferrihydrite conversion into more crystalline Fe(III) oxides (i.e., lepidocrocite and goethite) through Ostwald ripening, and resulted in the formation of siderite and mackinawite upon reaction with carbonates and sulfides naturally present in the groundwater. The model results also showed that, whereas the decrease in surface sites during reductive dissolution of ferrihydrite promoted arsenic mobilization, the mineral transformation limited As release through its sequestration into the newly formed secondary mineral phases.

Stimulation of Fe(II) Oxidation, Biogenic Lepidocrocite Formation, and Arsenic Immobilization by Pseudogulbenkiania Sp. Strain 2002.

An anaerobic nitrate-reducing Fe(II)-oxidizing bacterium, Pseudogulbenkiania sp. strain 2002, was used to investigate As immobilization by biogenic Fe oxyhydroxides under different initial molar ratios of Fe/As in solutions. Results showed that Fe(II) was effectively oxidized, mainly forming lepidocrocite, which immobilized more As(III) than As(V) without changing the redox state of As. When the initial Fe/As ratios were kept constant, higher initial Fe(II) concentrations immobilized more As with higher Asimmobilized/Feprecipitated in biogenic lepidocrocite. EXAFS analysis showed that variations of initial Fe(II) concentrations did not change the As-Fe complexes (bidentate binuclear complexes ((2)C)) with a fixed As(III) or As(V) initial concentration of 13.3 µM. On the other hand, variations in initial As concentrations but fixed Fe(II) initial concentration induced the co-occurrence of bidentate binuclear and bidentate mononuclear complexes ((2)E) and bidentate binuclear and monodentate mononuclear complexes ((1)V) for As(III) and As(V)-treated series, respectively. The coexistence of (2)C and (2)E complexes (or (2)C and (1)V complexes) could contribute to higher As removal in experimental series with higher initial Fe(II) concentrations at the same initial Fe/As ratio. Simultaneous removal of soluble As and nitrate by anaerobic nitrate-reducing Fe(II)-oxidizing bacteria provides a feasible approach for in situ remediation of As-nitrate cocontaminated groundwater.

Sulfur Cycling-Related Biogeochemical Processes of Arsenic Mobilization in the Western Hetao Basin, China: Evidence from Multiple Isotope Approaches.

The role of sulfur cycling in arsenic behavior under reducing conditions is not well-understood in previous investigations. This study provides observations of sulfur and oxygen isotope fractionation in sulfate and evaluation of sulfur cycling-related biogeochemical processes controlling dissolved arsenic groundwater concentrations using multiple isotope approaches. As a typical basin hosting high arsenic groundwater, the western Hetao basin was selected as the study area. Results showed that, along the groundwater flow paths, groundwater δ34SSO4, δ18OSO4, and δ13CDOC increased with increases in arsenic, dissolved iron, hydrogen sulfide and ammonium concentrations, while δ13CDIC decreased with decreasing Eh and sulfate/chloride. Bacterial sulfate reduction (BSR) was responsible for many of these observed changes. The δ34SSO4 indicated that dissolved sulfate was mainly sourced from oxidative weathering of sulfides in upgradient alluvial fans. The high oxygen-sulfur isotope fractionation ratio (0.60) may result from both slow sulfate reduction rates and bacterial disproportionation of sulfur intermediates (BDSI). Data indicate that both the sulfide produced by BSR and the overall BDSI reduce arsenic-bearing iron(III) oxyhydroxides, leading to the release of arsenic into groundwater. These results suggest that sulfur-related biogeochemical processes are important in mobilizing arsenic in aquifer systems.

Occurrence and hydrogeochemical characteristics of high-fluoride groundwater in Xiji County, southern part of Ningxia Province, China.

High-F(-) groundwater is widely distributed in Xiji County, which endangers the safety of drinking water. In order to evaluate the key factors controlling the origin and geochemical mechanisms of F(-) enrichment in groundwater at Xiji County, one hundred and five groundwater samples and sixty-two sediment samples were collected. Fluoride concentration in the groundwater samples ranged from 0.2 to 3.01 mg/L (mean 1.13 mg/L), with 17 % exceeding the WHO drinking water guideline value of 1.5 mg/L and 48 % exceeding the Chinese drinking water guideline value of 1.0 mg/L. High-F(-) groundwaters were characterized by hydrochemical types of Na-HCO3 and Na-SO4·Cl, which were found in Quaternary sediment aquifer and in Tertiary clastic aquifer, respectively. Conditions favorable for F(-) enrichment in groundwater included weakly alkaline pH (7.2-8.9), low concentration of Ca(2+), and high concentrations of HCO3 (-) and Na(+). Calcite and fluorite were the main minerals controlling F(-) concentration in groundwaters. The hydrolysis of F-bearing minerals in aquifer sediments was the more important process for F(-) release in Tertiary clastic aquifer, which was facilitated by long residence time of groundwater, in comparison with Quaternary sediment aquifer. Cation exchange would also play important roles, which removed Ca(2+) and Mg(2+) and led to more free mobility of F(-) in groundwater and permitted dissolution of fluorite, especially in Tertiary clastic aquifer. However, evapotranspiration and competing adsorption of B and HCO3 (-) were the more important processes for F(-) enrichment in Quaternary groundwater. Groundwater in Lower Cretaceous aquifer had relatively low F(-) concentration, which was considered to be the potential drinking water resource.

Analytical methods and application of stable isotopes in dissolved organic carbon and inorganic carbon in groundwater.

RATIONALE: The stable isotopes of dissolved organic carbon (DOC) and inorganic carbon (DIC) provide insights into the carbon cycle, biogeochemical processes, and the fate of redox-sensitive elements in groundwater systems. The simultaneous determination of the stable isotope ratios (δ(13)C(DIC) and δ(13)C(DOC) values) in DIC and DOC in water samples would provide better understanding of those processes. METHODS: The conditions for pretreating water samples prior to determining their DIC and DOC stable isotope ratios were optimized with a series of experiments on pre-purging (GasBench needle versus blowing concentrator) and reaction conditions. The carbon stable isotope ratios were determined by isotope ratio mass spectrometry. Sequential determination of the δ(13)C(DIC) and δ(13)C(DOC) values was also carried out using the optimized conditions. National Institute of Standards and Technology (NIST) δ(13)C standards were utilized to verify the precision of the proposed method. RESULTS: The optimized pretreatment conditions for DIC isotope analysis involved pre-purging the empty sample bottle for 60 min using a pressurized helium gas-blowing concentrator and then reacting the sample with 85% H3PO4 for 60 min in a water bath at 60°C. The optimized pretreatment conditions for DOC isotope determination involved pre-purging the sample for 60 min with the pressurized helium gas-blowing concentrator after adding 0.1 mol L(-1) AgNO3 and 85% H3PO4 and then reacting with Na2S2O8 as an oxidant and AgNO3 as a catalyst, in a 100°C water bath for 60 min. CONCLUSIONS: With the optimized methods, the analytical precision of the δ(13)C(DIC) and δ(13)C(DOC) values of the reference samples was 0.02‰. The precision of δ(13)C(DIC) and δ(13)C(DOC) values in groundwater samples was 0.03‰ and 0.17‰, respectively. For the sequential determination of the DIC and DOC carbon isotope ratios, the precision of the δ(13)C(DIC) and δ(13)C(DOC) values in reference samples was better than 0.2‰.