High Arsenic Aquifers Research Articles

Late Quaternary tectonic uplift and Yellow River evolution create high arsenic aquifers in the Hetao Basin, China

High arsenic (As) groundwater is a global problem primarily originating from As-enriched sediments. The provenance (source) and release mechanisms (sinks) of high As sediment have been identified, but the source-sink transfer is poorly understood, especially the influence of geological and surface processes. In this study, we explore the roles of tectonic movement and Yellow River evolution in provenance formation processes and evaluate the combined effects of provenance and sediment age on the As content of aquifer sediments in the northern Hetao Basin of Inner Mongolia. Based on optically stimulated luminescence (OSL) and 14C dating and detrital zircon U-Pb, As content, and lithological analyses of a 400 m core, we reconstructed As changes over the last 160 ka. Our results show clay deposited in a paleo-lake during the Gonghe movement period in the late Pleistocene (∼100 ka B.P.) is enriched in As (31.8 μg/g) due to significant provenance contributions of the As-bearing Langshan Group under tectonic uplift and mountain erosion. In contrast, clay deposited in the middle Pleistocene (∼160 ka B.P.) has lower As content (7.3 μg/g) due to the Yellow River as the primary provenance. Accordingly, the provenance of basin As forced by tectonic uplift and Yellow River evolution determines the background As of aquifer sediments. After deposition, sediment As content decays over time, with higher decay rates in coarse-grained sands than fine-grained. Overall, both provenance formation and sediment age, representing initial and dynamic states of solid phase As, jointly determine the As content of aquifer sediments. More solid phase As provided by younger sediments from the proximal orogenic provenance and reducing conditions due to frequent river–lake transitions, jointly lead to higher As concentrations in shallow groundwater. The study highlights the potential for using a combined analysis of the tectonic movement-surface processes-environment system to improve understanding of geogenic high As groundwater over global large sedimentary basins in the proximity of young orogenic belts.

New evidence for linking the formation of high arsenic aquifers in the central Yangtze River Basin to climate change since Last Glacial Maximum

The prevalence of arsenic (As)-affected groundwater in the Late Pleistocene and Holocene aquifers leads to serious arsenicosis worldwide. However, the geogenic foundational processes underlying the high As aquifers remain elusive. Here we present joint lines of evidences from chronological, sediment geochemical and geomicrobial analysis that climate change since the Last Glacial Maximum (LGM) initiates the genesis of high As aquifers in the central Yangtze River Basin, which represents Quaternary alluvial-lacustrine floodplains affected by arsenicosis occurrence. Optically stimulated luminescence-based sediments dating and grain size characterization indicate that the LGM depositional boundary also separates the Late-Pleistocene/Holocene high arsenic aquifers from the underlying arsenic-depleted aquifers. Further examination of solid-phase As/Fe/S speciation and associated microbial communities function suggests that the pre-LGM depositional environments characteristic of S metabolism engender the fixation of As in pyrite, whereas during the post-LGM period climate change to warm and humid leads to As repartitioning to Fe/Mn oxides in response to strong chemical weathering. This may have contributed to a dynamic fate of As in the post-LGM depositional environments and thus a highly variable aqueous As concentrations over depth. Our results highlight the important roles of climate change has played in the genesis of high As aquifers, with implications for other LGM-affected regions worldwide as well as for the evolution of high arsenic aquifers under future climate change.

Influence of Sulfate Reduction on Arsenic Migration and Transformation in Groundwater Environment

The sulfate-reducing bacteria-mediated reduction process is considered to be an important mechanism affecting arsenic migration and transformation in anaerobic environments. To investigate the effect of sulfate-reducing bacteria in a high-arsenic aquifer on arsenic migration and transformation, the typical sulfate-reducing bacteria Desulfovibrio vulgaris was selected for micro-cosmic experiments to simulate a groundwater environment with or without sulfate amendment. The reduction of Fe(III) and As(V) by Desulfovibrio vulgaris was identified, and Fe(III) and As(V) were reduced in both sulfate-free and sulfate-containing systems. However, the addition of 1 mM sulfate significantly enhanced Fe(III) and As(V) reduction. Compared with no sulfate addition, 1 mM sulfate increased the reduction rates of Fe(III) and As(V) by 111.9% and 402.2%, respectively. The sulfate process mediated by Desulfovibrio vulgaris also remarkably promoted arsenic release in sediments. These results indicated that sulfate concentration should be considered when sulfate reduction is used as a remediation method for arsenic pollution in groundwater.

New Evidence for Linking the Formation of High Arsenic Aquifers in the Central Yangtze River Basin to Climate Change Since Last Glacial Maximum

New Evidence for Linking the Formation of High Arsenic Aquifers in the Central Yangtze River Basin to Climate Change Since Last Glacial Maximum

An indigenous bacterium Bacillus XZM for phosphate enhanced transformation and migration of arsenate

A number of arsenate-reducing bacteria respire adsorbed As(V), producing As(III) and thus contributing to arsenic mobilization from the solid phase to the aqueous phase. Two arsenate reducing genes, arsC and arrA, were both amplified in an indigenous bacterium Bacillus XZM isolated from high arsenic aquifer sediments. The effect of phosphate input on this novel bacterium in terms of mediating the biogeochemical behavior of arsenic was investigated for the first time. The results show bacterial growth and arsenate reduction appear to increase with the addition of phosphate. Input of 1 mM phosphate reduced the negative effects of As(V) on bacterial growth, resulting in 55–60% greater biomass production compared to lower phosphate inputs (0.01 and 0.1 mM). The data of real-time quantitative PCR (qPCR) indicated arsenate was involved in the expressions of two arsenate reductase genes (arsC and arrA genes) in indigenous bacterium Bacillus XZM. Overall, the addition of phosphate (from 0.1 to 1 mM) resulted in a doubling of arsenate bio-desorption from the sediment into the aqueous medium. Oxidation-reduction potential, as an environmental indicator of the bacterial reduction of metals, declined to −200 mV in the presence of strain XZM and 1 mM phosphate in the microcosm. Phosphate input enhanced arsenic biomigration, indicating the effect of phosphate concentration should be considered when studying the biogeochemical behavior of arsenic.

Dissolved organic matter tracers reveal contrasting characteristics across high arsenic aquifers in Cambodia: A fluorescence spectroscopy study

Organic matter in the environment is involved in many biogeochemical processes, including the mobilization of geogenic trace elements, such as arsenic, into groundwater. In this paper we present the use of fluorescence spectroscopy to characterize the dissolved organic matter (DOM) pool in heavily arsenic-affected groundwaters in Kandal Province, Cambodia. The fluorescence DOM (fDOM) characteristics between contrasting field areas of differing dominant lithologies were compared and linked to other hydrogeochemical parameters, including arsenic and dissolved methane as well as selected sedimentary characteristics. Absorbance-corrected fluorescence indices were used to characterize depth profiles and compare field areas. Groundwater fDOM was generally dominated by terrestrial humic and fulvic-like components, with relatively small contributions from microbially-derived, tryptophan-like components. Groundwater fDOM from sand-dominated sequences typically contained lower tryptophan-like, lower fulvic-like and lower humic-like components, was less bioavailable, and had higher humification index than clay-dominated sequences. Methane concentrations were strongly correlated with fDOM bioavailability as well as with tryptophan-like components, suggesting that groundwater methane in these arsenic-prone aquifers is likely of biogenic origin. A comparison of fDOM tracers with sedimentary OM tracers is consistent with the hypothesis that external, surface-derived contributions to the aqueous DOM pool are an important control on groundwater hydrogeochemistry.

Arsenic concentrations after drinking water well installation: Time-varying effects on arsenic mobilization

Chronic exposure to geogenic arsenic via drinking water is a worldwide health concern. However, effects of well installation and operation on arsenic concentrations and mobilization are not well understood. This knowledge gap impacts both reliable detection of arsenic in drinking water and effective public health recommendations to reduce exposure to arsenic. This study examines changes in arsenic and redox geochemistry over one year following installation of 254 new domestic water wells in three regions of the north-central USA that commonly have elevated arsenic concentrations. Our regions' geologic settings share some important characteristics with other high-arsenic aquifers: igneous bedrock aquifers; or late Pleistocene-age glacial sand and gravel aquifers interbedded with aquitards. Over the study, arsenic concentrations increased by 16% or more in 25% of wells in glacial aquifer regions, and the redox conditions changed towards more reducing. In wells in the bedrock region, there was no significant change in arsenic concentrations, and redox conditions changed towards more oxidizing. Our findings illustrate the importance of understanding short- to moderate-term impacts of well installation and operation on arsenic and aqueous chemistry, as it relates to human exposure. Our study informs water quality sampling requirements, which currently do not consider the implications sampling timing with respect to well installation. Evaluating arsenic concentrations in samples from new wells in the context of general regional pH and redox conditions can provide information regarding the degree of disequilibrium created by well drilling. Our analysis approach may be transferable and scalable to similar aquifer settings across the globe.

Interactions between arsenic adsorption/desorption and indigenous bacterial activity in shallow high arsenic aquifer sediments from the Jianghan Plain, Central China

Exposure to arsenic in the environment is hazardous to biota. Three types of sediments from a shallow, high arsenic aquifer were collected from Jianghan Plain, Central China to investigate interactions between indigenous bacterial activity and arsenic adsorption/desorption. For the same level of bacterial activity, the As(III) or As(V) adsorption rate in sediments decreased from clay loam to loamy sand to silty sand. However, the arsenic desorption rate from these sediments followed the reverse sequence. For the same arsenic speciation and content, bacterial activity decreased from clay loam to loamy sand to silty sand. Overall, arsenic adsorption/desorption rates were related to both bacterial activity and sediment texture. The bacteria present could reduce As(V) to As(III), thereby favoring its release from sediment into solution and increasing the ratio of As(III) to total arsenic. These results indicate indigenous bacteria strongly affect the adsorption/desorption and oxidation-reduction of arsenic, and are actively involved in the dynamic equilibrium of arsenic between sediment and groundwater in this shallow aquifer.

Diversity and abundance of arsenic methylating microorganisms in high arsenic groundwater from Hetao Plain of Inner Mongolia, China.

Arsenic methylation is regarded as an effective way of arsenic detoxification. Current knowledge about arsenic biomethylation in high arsenic groundwater remains limited. In the present study, 16 high arsenic groundwater samples from deep wells of the Hetao Plain were investigated using clone library and quantitative polymerase chain reaction (qPCR) analyses of arsM genes as well as geochemical analysis. The concentrations of methylated arsenic (including monomethylarsonic acid (MMA) and dimethylarsinic acid (DMA)) varied from 2.40 to 16.85 μg/L. Both bacterial and archaeal arsenic methylating populations were detected in the high arsenic aquifer. They were dominated by Proteobacteria, Firmicutes, Gemmatimonadetes, Nitrospirae, Methanomicrobia and a large unidentified group. The abundances of predominant populations were correlated positively to either total organic carbon or total arsenic and arsenite concentrations. The arsM gene abundances in high arsenic groundwater ranged from below detection to 5.71 × 106 copies/L and accounted for 0-3.32‰ of total bacterial and archaeal 16S rRNA genes. The arsM gene copies in high arsenic groundwater showed closely positive correlations with methylated arsenic concentrations. The overall results implied that arsenic methylating microorganisms were abundant and diverse in high arsenic groundwater. This was the first study of arsenic methylating microbial communities in high arsenic groundwater aquifers and might provide useful information for arsenic bioremediation in groundwater systems.

Characteristics and compound-specific carbon isotope compositions of sedimentary lipids in high arsenic aquifers in the Hetao basin, Inner Mongolia

Organic matter, as an electron donor, plays a vital role in As mobilization mediated by microorganisms during reductive dissolution of Fe/Mn oxides in shallow aquifers. However, the specific types and sources of organic matter involved in biogeochemical processes accelerating As mobilization are still controversial. Both sediment and groundwater samples were collected at different depths from aquifers of the Hetao Basin, a typical inland basin hosting high As groundwater. Sedimentary lipids and their compound-specific carbon isotope ratios were analyzed to evaluate characteristics and sources of organic matter. Results show that sedimentary As were well correlated with Fe and Mn oxides, suggesting that As exist as Fe/Mn oxide bound forms. Groundwater As far exceeded the drinking water guide value of 10 μg/L. Moreover, As concentrations in shallow groundwater were relatively higher. Lipids in clay were mainly originated from terrestrial higher plants, while that in fine sand samples were derived from terrestrial higher plants, microorganism and petroleum. Shallow fine sand samples were also characterized by evident in-situ biodegradation. Compound-specific carbon isotope compositions of sedimentary lipids showed that short-chain n-alkanes and n-alkanoic acids had more positive δ13C values compared to long-chain compounds, especially in shallow fine sand samples. δ13CTOC were also low in shallow fine sand samples. These results jointly indicate that these lipids in shallow fine sand samples acted as carbon source for indigenous microorganism and the short-chain components were particularly more vulnerable to biodegradation, which may contribute to high As concentrations in shallow groundwater. The new findings provide the first evidence that short chain length n-alkyl compounds afforded a source of potential electron donors for microbially mediated As mobilization process in the shallow aquifers.

Microbial Community Structure and Arsenic Biogeochemistry in Two Arsenic-Impacted Aquifers in Bangladesh.

ABSTRACTLong-term exposure to trace levels of arsenic (As) in shallow groundwater used for drinking and irrigation puts millions of people at risk of chronic disease. Although microbial processes are implicated in mobilizing arsenic from aquifer sediments into groundwater, the precise mechanism remains ambiguous. The goal of this work was to target, for the first time, a comprehensive suite of state-of-the-art molecular techniques in order to better constrain the relationship between indigenous microbial communities and the iron and arsenic mineral phases present in sediments at two well-characterized arsenic-impacted aquifers in Bangladesh. At both sites, arsenate [As(V)] was the major species of As present in sediments at depths with low aqueous As concentrations, while most sediment As was arsenite [As(III)] at depths with elevated aqueous As concentrations. This is consistent with a role for the microbial As(V) reduction in mobilizing arsenic. 16S rRNA gene analysis indicates that the arsenic-rich sediments were colonized by diverse bacterial communities implicated in both dissimilatory Fe(III) and As(V) reduction, while the correlation analyses involved phylogenetic groups not normally associated with As mobilization. Findings suggest that direct As redox transformations are central to arsenic fate and transport and that there is a residual reactive pool of both As(V) and Fe(III) in deeper sediments that could be released by microbial respiration in response to hydrologic perturbation, such as increased groundwater pumping that introduces reactive organic carbon to depth.

Dissolved fulvic acids from a high arsenic aquifer shuttle electrons to enhance microbial iron reduction

It was demonstrated more than two decades ago that microorganisms use humic substances, including fulvic acid (FA), as electron shuttles during iron (Fe) reduction in anaerobic soils and sediments. The relevance of this mechanism for the acceleration of Fe(III) reduction in arsenic-laden groundwater environments is gaining wider attention. Here we provide new evidence that dissolved FAs isolated from sediment-influenced surface water and groundwater in the Bengal Basin were capable of electron shuttling between Geobacter metallireducens and Fe(III). Moreover, all four Bangladesh sediment-derived dissolved FAs investigated in this study had higher electron accepting capacity (176 to 245μmol/g) compared to aquatic FAs, such as Suwanee River Fulvic Acid (67μmol/g). Our direct evidence that Bangladesh FAs are capable of intermediate electron transfer to Fe(III) supports other studies that implicate electron shuttling by sediment-derived aqueous humics to enhance Fe reduction and, in turn, As mobility. Overall, the finding of greater electron accepting capacity by dissolved FAs from groundwater and other sediment-influenced environments advances our understanding of mechanisms that control Fe reduction under conditions where electron transfer is the rate limiting step.

Sediment biomarker, bacterial community characterization of high arsenic aquifers in Jianghan Plain, China

Representative biomarkers (e.g., n-alkanes), diversity and microbial community in the aquifers contaminated by high concentration of arsenic (As) in different sediment depth (0–30 m) in Jianghan Plain, Hubei, China, were analyzed to investigate the potential mechanism of As enrichment in groundwater. The concentration of As was abundant in top soil and sand, but not in clay. The analysis of the distribution of n-alkanes, CPI values, and wax to total n-alkane ratio (Wax(n)%) indicated that the organic matter (OM) from fresh terrestrial plants were abundant in the shallow sediment. However, n-alkanes have suffered from significant biodegradation from the depth of 16 m to 30 m. The deposition of fresh terrestrial derived organic matters may facilitate the release of As from sediment to groundwater in the sediment of 0–16 m. However, the petroleum derived organic matters may do the favor to the release of As in the deeper section of borehole (16 m to 30 m). The 16S rRNA gene sequences identification indicated that Acidobacteria, Actinomycetes and Hydrogenophaga are abundant in the sediments with high arsenic. Therefore, microbes and organic matters from different sources may play important roles in arsenic mobilization in the aquifers of the study area.

Remediation of High Arsenic Aquifers by Learning from the Nature

Almost 20 years’ multi-disciplinary study on geogenic high arsenic (As) groundwater systems in China has greatly improved our understanding of the major processes controlling hydrogeochemical behavior of As in the subsurface environment. Among them, sorption by Fe(III) oxide/hydroxides was found to be one of the dominant processes retaining As in the aquifer matrix. Managed Aquifer Rehabilitation (MAR) by enhancing Fe(II) oxidation to promote As sorption was proposed and tested in a pilot-scale field experiment. Periodical injection of Fe(II) and ClO− into a high As sandy aquifer triggered formation of new Fe(III) (hydr)oxides coating on sediment particles via advanced heterogeneous oxidation of Fe(II) and concurrent oxidative adsorption of As(III) via co-precipitation and surface complexation with Fe(III) (hydr)oxides. Monitoring results indicate that aqueous As concentration decreased from the initial average value of 78.0μg/L to 9.8μg/L over the 25-day amendment period and leveled off below 10μg/L for the following 30 days. MAR is thus proved to be a cost-effective approach for remediating high As aquifers.

Effects of short-term flooding on arsenic transport in groundwater system: A case study of the Datong Basin

Hydrogeological and geochemical approaches were combined to investigate the impact of a short-term artificial flooding event on arsenic and associated hydrogeochemisty at a field monitoring site of high arsenic aquifers in Datong Basin, northern China. The groundwater levels fluctuated in response to the flooding (the surface water level and groundwater level fluctuated with time in a range of over 80cm and 30cm, respectively), indicating groundwater–surface water interaction. Redox indices, major ions, trace element concentrations, O, H and Sr isotope compositions for surface water and groundwater were determined before and after the flooding. δ2H and δ18O values for all water samples plot close to the global meteoric water line (GMWL); a subset of the samples (shallow wells) averagely increased from −11.78 to −11.26 for δ18O and from −86.59 to −83.49 for δ2H, commensurate with mixing with ~10% surface water. The relationship between compositions of strontium isotope 87Sr/86Sr ratios and Mg concentration also clearly indicates the effect of mixing between groundwater and surface water. Before and after the flooding, there were obvious variations in water chemistry, including arsenic concentrations. Increases and positive correlations between Cl− and Na+, Mg2+, Ca2+ and SO42− following flooding revealed surface water infiltration into groundwater, plus additional input from dissolution of evaporate minerals and/or evaporated pore-water. Organic matter and oxygen are carried into groundwater together with surface water; oxidation of organic matter leads to exhaustion of oxygen and consumption of terminal electron acceptors (e.g. ferric iron, sulfate, nitrate) inducing a more reducing groundwater environment (indicated by decreased ORP values). Consequently, reductive dissolution of iron oxides/hydroxides resulted in an observed elevation of HS, NH4-N, Fe(II), with the concentrations increasing from 5μg/L to 10μg/L, from 0.19mg/L to 0.68mg/L and from 0.06mg/L to 1.86mg/L, respectively. This may explain that the As concentrations were enhanced after surface water flooding (from mean value of 22.6μg/L to 31μg/L). However, a positive correlation was observed between enhance values of As and Cl in the groundwater after flooding is interpreted as reflecting re-dissolution of evaporate crusts and/or saline pore water during infiltration, and this may alone explain the increase in As observed in the groundwater. Surface water As concentration increased to a minor degree following flooding also (from 14μg/L to 15.1μg/L), possibly reflecting return flow of the high As groundwater during a temporary switch to gaining conditions.

Arsenate reduction and mobilization in the presence of indigenous aerobic bacteria obtained from high arsenic aquifers of the Hetao basin, Inner Mongolia

Intact aquifer sediments were collected to obtain As-resistant bacteria from the Hetao basin. Two strains of aerobic As-resistant bacteria (Pseudomonas sp. M17-1 and Bacillus sp. M17-15) were isolated from the aquifer sediments. Those strains exhibited high resistances to both As(III) and As(V). Results showed that both strains had arr and ars genes, and led to reduction of dissolved As(V), goethite-adsorbed As(V), scorodite As(V) and sediment As(V), in the presence of organic carbon as the carbon source. After reduction of solid As(V), As release was observed from the solids to solutions. Strain M17-15 had a higher ability than strain M17-1 in reducing As(V) and promoting the release of As. These results suggested that the strains would mediate As(V) reduction to As(III), and thereafter release As(III), due to the higher mobility of As(III) in most aquifer systems. The processes would play an important role in genesis of high As groundwater.

Abundance and Diversity of Sulfate-Reducing Bacteria in High Arsenic Shallow Aquifers

The abundance, diversity, and relative distribution of sulfate-reducing bacteria (SRB) in high arsenic (As) groundwater aquifers of Hangjinhouqi County in the Hetao Basin, Inner Mongolia was investigated using denaturing gradient gel electrophoresis (DGGE) and quantitative polymerase chain reaction (qPCR) analysis of dsrB genes (encoding dissimilatory sulfite reductase beta-subunit). DGGE results revealed that SRB populations were diverse, but were mainly composed of Desulfotomaculum, Desulfobulbus, Desulfosarcina, and Desulfobacca. The abundance of Desulfobulbus was positively correlated with the ratio of Fe(II)/Fe(III). Although qPCR results showed that the dsrB gene abundance in groundwater samples ranged from below detection to 4.9 × 106 copies/L, and the highest percentage of dsrB gene copies to bacterial 16S rRNA gene copies was 2.1%. Geochemical analyses showed that As(III) content and the ratio of Fe(II) to Fe(III) increased with total As, while sulfate concentrations decreased. Interestingly, the dsrB gene abundance was positively correlated with As concentrations. These results indicate that sulfate reduction occurs simultaneously with As and Fe reduction, and might result in increased As release and mobilization when As is not incorporated into iron sulfides. This study improves our understanding of SRB and As cycling in high As groundwater systems.

Response of growth and superoxide dismutase to enhanced arsenic in two Bacillus species.

Species differences in inorganic arsenic tolerance were investigated by comparing the responses of Bacillus subtilis (B. subtilis) and Bacillus thuringiensis (B. thuringiensis) to elevated concentrations of As(III) and As(V). The cell densities in treatments were always lower during the experiment compared to controls, with the exception of exposure to 1.0 mg As(V) l(-1) on the first day. It was also found that relative growth rate (RGR) of B. thuringiensis was lower than that of B. subtilis. Furthermore, RGR of each Bacillus species was negative correlation with toxicity of inorganic arsenic. However, total cell number still increased in each treatment according to cell density and RGR assays. Superoxide dismutase (SOD) activity of both Bacillus species was promoted by As(III) and As(V), especially under high arsenic concentration condition. In addition, SOD activity of B. thuringiensis was higher than that of B. subtilis during the same exposure time. In lipid peroxidation assay, thiobarbituric acid-reactive substances (TBARS) content of each Bacillus species had a significant increase with increment of arsenic concentration. Moreover, significant difference was observed between the two Bacillus species under high arsenic concentration. TBARS content of B. thuringiensis was higher than that of B. subtilis, indicating that effect of arsenic on cell membranes of B. thuringiensis was much more than that of B. subtilis. These results suggest that the two Bacillus species could adapt and live in high arsenic aquifers, although their growth and cell membranes were affected by As treatment in a way.

Bacterial Diversity and Community Structure in High Arsenic Aquifers in Hetao Plain of Inner Mongolia, China

The bacterial diversity and community structure of high arsenic (As) aquifers was investigated using an integrated approach adopting both geochemistry and molecular biology (polymerase chain reaction (PCR)-denaturing gradient gel electrophoresis (DGGE) and 16S rRNA gene clone library analyses). Nine borehole sediments and one groundwater sample from the living place of a villager (affected by arseniasis) and 12 sediments from a control borehole in Hetao Plain were investigated. The As concentrations ranged from 33.6 to 77.6 mg/kg in high As borehole sediments and 1.5 to 5.8 mg/kg in those samples from the control. The As concentration in the groundwater was 744.8 μg/L. Ratios between As(III) and total As in high As sediments increased gradually with depth and ranged from 0.02 to 0.34. Similarly, the Fe(II)/total Fe presented the same increasing trend with depth. The correlation between TOC contents and total As was positive. High concentrations of total As, S, Fe and TOC were found in clay and low in sand samples. Phylogenetic analysis showed significantly different bacterial communities among high As sediments, control sediments and the high As groundwater. Both DGGE and 16S rRNA gene clone library results showed that the high As sediments were dominated by Thiobacillus, Pseudomonas, Brevundimonas, and Hydrogenophaga, with Thiobacillus being distinctly dominant (63.5%). Whereas the low As sediments were dominated by some other genera including Psychrobacter, Massilia and Desulfotalea. The bacterial populations in the high As groundwater mainly included Pseudomonas, Acinetobacter and Aquabacterium. These results improve our understanding of the bacterial diversity in high As aquifers in Hetao Plain and suggest how specific bacterial populations help mediate the mobilization of As into high As groundwaters.

Multivariate analysis of the heterogeneous geochemical processes controlling arsenic enrichment in a shallow groundwater system

The effects of various geochemical processes on arsenic enrichment in a high-arsenic aquifer at Jianghan Plain in Central China were investigated using multivariate models developed from combined adaptive neuro-fuzzy inference system (ANFIS) and multiple linear regression (MLR). The results indicated that the optimum variable group for the AFNIS model consisted of bicarbonate, ammonium, phosphorus, iron, manganese, fluorescence index, pH, and siderite saturation. These data suggest that reductive dissolution of iron/manganese oxides, phosphate-competitive adsorption, pH-dependent desorption, and siderite precipitation could integrally affect arsenic concentration. Analysis of the MLR models indicated that reductive dissolution of iron(III) was primarily responsible for arsenic mobilization in groundwaters with low arsenic concentration. By contrast, for groundwaters with high arsenic concentration (i.e., > 170 μg/L), reductive dissolution of iron oxides approached a dynamic equilibrium. The desorption effects from phosphate-competitive adsorption and the increase in pH exhibited arsenic enrichment superior to that caused by iron(III) reductive dissolution as the groundwater chemistry evolved. The inhibition effect of siderite precipitation on arsenic mobilization was expected to exist in groundwater that was highly saturated with siderite. The results suggest an evolutionary dominance of specific geochemical process over other factors controlling arsenic concentration, which presented a heterogeneous distribution in aquifers. Supplemental materials are available for this article. Go to the publisher's online edition of the Journal of Environmental Science and Health, Part A, to view the supplemental file.