Arsenic Mobilization Research Articles

First-Principles Density Functional Theory Characterisation of the Adsorption Complexes of H3AsO3 on Cobalt Ferrite (Fe2CoO4) Surfaces

The mobility of arsenic in aqueous systems can be controlled by its adsorption onto the surfaces of iron oxide minerals such as cobalt ferrite (Fe2CoO4). In this work, the adsorption energies, geometries, and vibrational properties of the most common form of As(III), arsenous acid (H3AsO3), onto the low-index (001), (110), and (111) surfaces of Fe2CoO4 have been investigated under dry and aqueous conditions using periodic density functional theory (DFT) calculations. The dry and hydroxylated surfaces of Fe2CoO4 steadily followed an order of increasing surface energy, and thus decreasing stability, of (001) < (111) < (110). Consequently, the favourability of H3AsO3 adsorption increased in the same order, favouring the least stable (110) surface. However, by analysis of the equilibrium crystal morphologies, this surface is unlikely to occur naturally. The surfaces were demonstrated to be further stabilised by the introduction of H2O/OH species, which coordinate the surface cations, providing a closer match to the bulk coordination of the surface species. The adsorption complexes of H3AsO3 on the hydroxylated Fe2CoO4 surfaces with the inclusion of explicit solvation molecules are found to be generally more stable than on the dry surfaces, demonstrating the importance of hydrogen-bonded interactions. Inner-sphere complexes involving bonds between the surface cations and molecular O atoms were strongly favoured over outer-sphere complexes. On the dry surfaces, deprotonated bidentate binuclear configurations were most thermodynamically favoured, whereas monodentate mononuclear configurations were typically more prevalent on the hydroxylated surfaces. Vibrational frequencies were analysed to ascertain the stabilities of the different adsorption complexes and to assign the As-O and O-H stretching modes of the adsorbed arsenic species. Our results highlight the importance of cobalt as a potential adsorbent for arsenic contaminated water treatment.

Mobility of arsenic in the growth media of rice plants (Oryza sativa subsp. japonica. ‘Koshihikari’) with exposure to copper oxide nanoparticles in a life-cycle greenhouse study

The increasing arsenic (As) concentration in agriculture media poses increasing risks to both environment and human health. Arsenic mobility determines its bioavailability and entry into the food chain. Nanoparticle application may help to control As mobility in crop cultivation media, and thus decreasing As bioavailability for plants. This research studied the adsorption kinetics of As(V) on copper oxide nanoparticles (nCuO) and nCuO dissolution in a hydroponic solution, and the effects of nCuO on As mobility in a greenhouse system exposed to As(V) addition of 10 mg/kg and nCuO at 0.1–100 mg/L for a life-cycle growth of rice. Arsenic adsorption was dependent on both the total mass and the concentration of nCuO as well as the initial concentration of As(V), while nCuO dissolution was mainly dependent on nCuO concentration regardless of As(V). Arsenic in the simulated paddy was quickly mobilized from soil to aqueous phase during week 1, and further interacted with components in water phase, sediment-water interfacial transition and rice plants. Copper (Cu) and As speciation in the soil were observed by X-Ray Absorption Near Edge Spectrometry. Dissolved Cu was complexed with organic ligands. As(V) was adsorbed to kaolinite, or reduced to As(III) and adsorbed to ferrihydrite. Percent As removal from water phase in the growth container was determined by both nCuO application and As(V) initial concentration. Based on our previous finding that As accumulation in rice grains was significantly decreased by nCuO at 50 mg/L and the results of this study on As adsorption capacity of nCuO and As removal from water due to nCuO application, nCuO at 50 mg/L was proposed to be an appropriate application in rice paddy to immobilize As. Further research is needed in actual agriculture to verify the appropriate nCuO application and get an integrated beneficial effect for rice plants and humans.

Unraveling influences of nitrogen cycling on arsenic enrichment in groundwater from the Hetao Basin using geochemical and multi-isotopic approaches

Sources and co-cycling of nitrogen species in arsenic-prone groundwater remain poorly understood, which could affect arsenic behavior. Here, geochemical and multi-isotopic characteristics of groundwater from various redox environments were investigated to reveal the effects of nitrogen cycling on arsenic mobility in groundwater systems from the Hetao Basin in China. In deep groundwater along an approximate flow path from the alluvial fan (Zone I) through the transition area (Zone II) and to the flat plain (Zone III), a progressive NO3– depletion with gradually increased δ15NNO3 and δ18ONO3 occurred, accompanied by increases in dissolved NH4+, Fe(II), and arsenic concentrations and a decrease in δ15NNH4. Shallow groundwater in the flat plain (Zone IV) covered wider ranges of δ15NNO3 and δ18ONO3 and relatively lower δ15NNH4. Organic nitrogen mineralization contributed primarily to NH4+ release in all zones, and dissimilatory NO3– reduction to NH4+ (DNRA) was an important NH4+ source in Zone IV. While NH4+ loss mainly occurred via nitrification in Zone I, anaerobic NH4+ oxidation was coupled to Fe(III) oxide reduction (Feammox) in Zones II and III and to NO2– reduction (anammox) in Zones II, III, and IV. Groundwater NO3– was reduced via heterotrophic denitrification in Zones II and III, while the DNRA was favored over denitrification in Zone IV with much higher DOC:NO3– molar ratios. Feammox and heterotrophic DNRA increased the dissolved Fe(II) and arsenic concentrations via the enhanced Fe(III) oxide reduction. However, anammox and Fe(II)-fueled autotrophic DNRA decreased their concentrations due to limited Fe(III) oxide reduction and/or enhanced Fe(II) oxidation. The influences of nitrogen cycling on arsenic behavior are mainly mediated by transformations between Fe(III) oxides and dissolved Fe(II). This study provides the first detailed multi-isotopic picture of nitrogen cycling and the relevant effects on arsenic enrichment processes.

Groundwater development leads to decreasing arsenic concentrations in the San Joaquin Valley, California

In the San Joaquin Valley (SJV), California, about 10% of drinking water wells since 2010 had arsenic concentrations above the US maximum contaminant level of 10 μg/L. High concentrations of arsenic are often associated with high pH (greater than 7.8) or reduced geochemical conditions. Although most wells have low arsenic (<3 μg/L) and do not have changing arsenic concentrations, this study found that most wells with concentrations above 10 μg/L had arsenic trends. Overall, about 24% of wells had time-series trends since 2010 and 59% had paired-sample trends since 2000. Most wells had decreasing arsenic trends, even in wells with higher arsenic concentrations. These wells often had co-detections of increasing nitrate and sulfate trends that reflect oxic groundwater likely derived from agricultural recharge. Wells with increasing arsenic trends were deeper or located in the valley trough where aquifer materials are more fine-grained and where reducing conditions favor arsenic mobility. Wells with arsenic trends also tend to be clustered near areas of higher well density. Groundwater pumping in these areas has likely increased the contribution of younger, more oxic groundwater in wells with declining arsenic or, less frequently, increased the contribution of higher pH or reduced groundwater in wells with rising arsenic. Projections of arsenic trends indicate that 37 wells with high arsenic presently will be below 10 μg/L in ten years. Unfortunately, these improvements will be largely offset by 31 wells that are expected to increase above 10 μg/L in addition to expected rises in nitrate in wells where arsenic decreased. This study shows how human-altered flow systems can impact the natural geochemical character of water in both beneficial and deleterious ways.

Effects of different dissolved organic matter on microbial communities and arsenic mobilization in aquifers

Dissolved organic matter (DOM) play key roles in the biotransformation of arsenic in groundwater systems. However, the effects of different types of DOM on arsenic biogeochemistry remain poorly understood. In this study, four typical DOM compounds (acetate, lactate, AQS and humic acid) were amended to high As aquifer sediments to investigate their effects on arsenic/iron biotransformation and microbial community response. Results demonstrated that different DOM drove different microbial community shifts and then enhanced microbially-mediated arsenic release and iron reduction. With labile DOM (acetate and lactate) amendment, the abundance of putative dissimilatory iron and sulfate reducers Desulfomicrobium and Clostridium sensu stricto increased within the first week, and subsequently the anaerobic fermentative bacterial genus Acetobacterium and arsenate/sulfate-reducing bacterial genus Fusibacter became predominant. In contrast, recalcitrant DOM (AQS and humic acid) mainly stimulated the abundances of sulfur compounds respiratory genus Desulfomicrobium and fermentative bacterial genus Alkalibacter in the whole incubation. Accompanied with the microbial community structure and function shifts, dissolved organic carbon concentration and oxidation-reduction potential changed and the arsenic/iron reduction increased, which resulted in the enhanced arsenic mobilization. Collectively, the present study linked DOM type to microbial community structure and explored the potential roles of different DOM on arsenic biotransformation in aquifers.

Arsenic contamination, speciation, toxicity and defense strategies in plants

This review explains the transport, mobility, resistance and detoxification of toxic metalloid arsenic (As) in plants. Arsenic is ubiquitously present in Earth’s crust; however, numerous human interventions such as rapid industrialization use of As-based pesticides, insecticides and discharge of industrial wastes in water bodies leads to cumulative increase in As in the environment and has become a global challenge. Arsenic exists in different organic and inorganic forms, but inorganic forms such as pentavalent arsenate (AsV) and trivalent arsenite (AsIII) are more toxic and actively taken up by plants. Its toxicity is marked by generation of reactive oxygen species (ROS) that are capable of degrading various biomolecules of the cellular systems. To keep the ROS under the limit, plants have an array of enzymatic antioxidants such as superoxide dismutase (SOD), peroxidase (POD), catalase (CAT), ascorbate peroxidase (APX), glutathione reductase (GR) and glutathione-S-transferase (GST); and non-enzymatic antioxidant like ascorbate, proline, and cysteine. Contrary to this, As-hyper-accumulator plants survive under high concentration of As through the strenuous action of Asv reduction into AsIII followed by the vacuolar compartmentalization of complex or inorganic As. Hence, this review focuses on the potential sources of As in the environment, its speciation and toxicity, and tolerance strategies in plants.

Microbially mediated mobilization of arsenic from aquifer sediments under bacterial sulfate reduction

Understanding the biogeochemical processes controlling arsenic (As) mobilization under bacterial sulfate reduction (BSR) in aquifer sediments is essential for the remediation of high As groundwater. Here, we conducted microcosm experiments with shallow aquifer sediments from the Jianghan Plain (central Yangtze River Basin) under the stimulation of exogenous sulfate. Initially, co-increases of As(III) (from 0.0 to 88.5μg/L), Fe(II) (from 0.5 to 6.0mg/L), and S(-II) (from 0.0 to 90.0μg/L) indicated the concurrent occurrence of sulfate, Fe(III), and arsenate reduction. The corresponding increase of the relative abundance of OTUs classified as sulfate-reducing bacteria, Desulfomicrobium (from 0.5 to 30.6%), and dsrB gene abundance indicated the strong occurrence of BSR during the incubation. The underlying mechanisms of As mobilization could be attributed to the biotic and abiotic reduction of As-bearing iron (hydro)oxides either through the iron-reducing bacteria or the bacterially generated sulfide, which were supported by the variations in solid speciation of Fe, S, and As. As the incubation progressed, we observed a transient attenuation followed by a re-increase of aqueous As, due to the limited abundance of newly-formed Fe-sulfide minerals with a weak ability of As sequestration. Moreover, the formation of thioarsenate (H2AsS4-) during the mobilization of As from the sediments was observed, highlighting that BSR could facilitate As mobilization through multiple pathways. The present results provided new insights for the biogeochemical processes accounting for As mobilization from sediments under BSR conditions.

Machine Learning Predictions of pH in the Glacial Aquifer System, Northern USA.

A boosted regression tree model was developed to predict pH conditions in three dimensions throughout the glacial aquifer system of the contiguous United States using pH measurements in samples from 18,386 wells and predictor variables that represent aspects of the hydrogeologic setting. Model results indicate that the carbonate content of soils and aquifer materials strongly controls pH and, when coupled with long flowpaths, results in the most alkaline conditions. Conversely, in areas where glacial sediments are thin and carbonate‐poor, pH conditions remain acidic. At depths typical of drinking‐water supplies, predicted pH >7.5—which is associated with arsenic mobilization—occurs more frequently than predicted pH <6—which is associated with water corrosivity and the mobilization of other trace elements. A novel aspect of this model was the inclusion of numerically based estimates of groundwater flow characteristics (age and flowpath length) as predictor variables. The sensitivity of pH predictions to these variables was consistent with hydrologic understanding of groundwater flow systems and the geochemical evolution of groundwater quality. The model was not developed to provide precise estimates of pH at any given location. Rather, it can be used to more generally identify areas where contaminants may be mobilized into groundwater and where corrosivity issues may be of concern to prioritize areas for future groundwater monitoring.

Microbial mobilization of arsenic from iron-bearing clay mineral through iron, arsenate, and simultaneous iron-arsenate reduction pathways

Clay minerals are an important host for arsenic in many arsenic-affected areas. The role of bioreduction of structural Fe(III) in clay minerals in the mobilization of arsenic from clay minerals, however, still remains unclear. In this study, Fe(III) reducing bacterium, As(V) reducing bacterium, and Fe(III)-As(V) reducing bacterium were employed to investigate the possible bioreduction pathways for arsenic release from Nontronite NAu-2. Results demonstrated that microbial reduction controlled arsenic mobilization from NAu-2 through Fe(III), As(V), and simultaneous Fe(III)-As(V) reduction pathways. Although the bioreduction of structural Fe(III) led to a negligible dissolution of NAu-2, it triggered a significant release of arsenic from NAu-2. The bioreduction of tetrahedral Fe(III) initiated the release of As(V), and the further bioreduction of octahedral Fe(III) induced the release of As(III) in NAu-2. In addition, bioreduction of As(V) resulted in the desorption and transformation of As(V) from NAu-2. Simultaneous bioreduction of Fe(III) and As(V) led to an almost complete release of As(V) from NAu-2. These findings suggest that simultaneous Fe(III)-As(V) reduction was the dominant pathway governing As(V) release from NAu-2, while structural Fe(III) reduction controlled As(III) release from NAu-2. Therefore, the bioreduction of iron-bearing clay minerals has a great potential for arsenic mobilization in the subsurface environment.

Geochemical mechanisms of natural arsenic mobility in the hydrogeologic system of Lower Katari Basin, Bolivian Altiplano

Arsenic (As) contamination of drinking water is a worldwide problem. The natural origin of As, its mobility, and transport are of paramount interest in Bolivian Altiplano due to its presence in mineral deposits, brines, hot springs, and volcanic rocks. In this study, a geochemical spatial–temporal approach was used to understand the sources and factors that regulate the mobilization and fate of As in water bodies as well as sediments of Lower Katari Basin (LKB). The study reveals that high levels of As (288 µg/L), boron (B) (2473 µg/L), manganese (Mn) (7259 µg/L), and high salinity (23850 µS/cm) are present in shallow drinking water wells, which exceed the guideline values of the Bolivian regulation (NB-512) and WHO. Seasonal changes (mean monthly rainfall in the dry and rainy period: 6–89 mm) and their impact on water quantity (0.9–5.1 m3/s), in addition to the load of solids and liquids of residual origin (Pallina River), pose health risks for the communities at the banks of the Katari River. The hydrogeological study indicates that the groundwater flows from southeast to northwest (SE–NW), which indicate interaction between groundwater and surface water in this region. The spatial distribution of As varies considerably due to geological characteristics of the area as well as due to the heterogeneously distributed evaporites in the sediments (alluvial, fluvial-lacustrine); however, the highest concentrations of As are observed in the alluvial sediments of the northern region. Sequential extraction (BCR) of sediments along with geochemical modeling (mineral saturation indices) indicates that iron (Fe) and aluminum (Al) (hydr)oxides are the most important adsorbent minerals of As in the central and southern region of LKB. The hydrochemistry of water bodies in LKB is strongly influenced by the interaction with the sediment constituents and by the spatial–temporal variations. Therefore, the determination of the distribution of As among the different geochemical fractions was useful to find the relative proportions of As transported by different chemical mechanisms (adsorption/dissolution) and their spatial–temporal variation.

Arsenic Mobilization Process in Shallow Aquifer of Bengal Delta Plain: A Field Scale Study to Identify the Role of Coliform Bacteria

In Bengal Delta Plain (BDP), shallow aquifer (&lt;50 m) is often contaminated with Arsenic (As). The phenomenon is wide spread in nature thought the BDP notable in Nadia district of west Bengal. The present study highlights a primary screening of As, Fe, MPN and FC in monitored shallow wells. The study designed for two different sites (site-A, High As and site-B Low As area). The water quality monitoring results suggest that high As concentration (Range- 103-171 μgL-1) has been noticed in site A when compared with site B (range-53-99 μgL-1). In sites A, the Fe concentration is high and low in site B. The correlation study (r2) between arsenic and iron are also determined. The value of r2is 0.94 for site A and 0.73 for site B. The water quality results suggest that the nature of the monitor aquifer is anoxic in nature with low Eh, DO absent and low NO3- and SO4+. Major anion is HCO3- (376 mgL-1) followed by Cl- (28 mgL-1). However chloride concentration is largely varying in the monitored tube well. Microbial study (MPN &amp; FC count) also indicates some relationship among MPN (r2-0.32) and Fe (r2 -0.24). However the relationship is scatter when As concentration is low. The linear trended has also obtained when both As, MPN and FC are high. The physical observation of plate count (Color reaction in Chromo colt Agar) has also been observed. This is a clear indicator of fecal coli form contamination. The study indicates that the microbial mobilization of As is the key factor for enrichment of As in ground water. The possible sources of the microbes are local land-use pattern (notable pit-latrine). Finally, the study highlights the role of coli forms bacteria (Both facultative and non-facultative) are wide spread in shallow rural aquifer of Bengal. Thus microbial process possibly enriches arsenic in shallow ground water.

Potential of high pH and reduced sulfur for arsenic mobilization – Insights from a Finnish peatland treating mining waste water

Peatlands, used for purification of mining waste waters, have shown efficient solid-phase sequestration of contaminants such as arsenic (As). However, contaminant re-mobilization may occur related to management changes or chemical alteration of original peatland conditions. For a treatment peatland in Finnish Lapland, we here confirm efficient As retention in near-surface peat layers close to the mining waste water inflow, likely due to binding to FeIII-phases. Seven years into operation of the treatment peatland, there appears to be further retention potential, as large areas downstream still had solid-phase As concentrations at background levels. However, via depth-resolved pore water analysis we observed a hotspot 170 m from the inflow at 10–50 cm depth, where As pore water concentrations exceeded input concentrations by a factor of 20, indicating substantial As re-mobilization. At the same spot, a peak of reduced sulfur (S) species was found. Arsenic species detected were arsenite and up to 26% methylated oxyarsenates, 15% methylated and 7.9% inorganic thioarsenates. We postulate that As mobilization is a result of short-term re-equilibration to a changed inflow chemistry after installation of a process water treatment plant and a long-term consequence of changing pore water pH from acidic to near-neutral, releasing reduced S and As. We infer that the co-occurrence of reduced S and As leads to formation of methylated and/or thiolated As species with known low sorption affinity, thereby further enhancing As mobility. Laboratory incubation studies with two peat cores confirmed a high S-induced As mobilization potential, especially when As-Fe-rich, oxic surface layers were incubated anoxically at near-neutral pH. Highest risk of As re-mobilization from this treatment peatland is expected in a scenario in which mining waste water inflow has stopped but the peatland remains flooded, and near-surface layers transition from oxic to anoxic conditions.

Arsenic release and transport during oxidative dissolution of spatially-distributed sulfide minerals

The oxidative dissolution of sulfide minerals, naturally present in the subsurface, is one of the major pathways of arsenic mobilization. This study investigates the release and fate of arsenic from arsenopyrite and löllingite oxidation under dynamic redox conditions. We performed multidimensional flow-through experiments focusing on the impact of chemical heterogeneity on arsenic mobilization and reactive transport. In the experimental setups the As-bearing sulfide minerals were embedded, with different concentrations and spatial distributions, into a sandy matrix under anoxic conditions. Oxic water flushed in the flow-through setups triggered the oxidative dissolution of the reactive minerals, the release of arsenic, as well as changes in pore water chemistry, surface-solution interactions and mineral precipitation. We developed a reactive transport model to quantitatively interpret the experimental results. The simulation outcomes showed that 40% of the arsenic released was reincorporated into a freshly precipitated iron-arsenate phase that created a coating on the mineral surface limiting the dissolution reactions. The faster dissolution rate of löllingite compared to arsenopyrite was responsible for sustaining the continuous release of As-contaminated plumes. The model also allowed shedding light on the spatial distribution, on the temporal dynamics, and on the interactions between arsenic sources (As-bearing minerals) and sinks (freshly formed secondary phases) in flow-through systems.

Coupled anaerobic methane oxidation and reductive arsenic mobilization in wetland soils

Anaerobic methane oxidation is coupled to the reduction of electron acceptors, such as sulfate, and contributes to their biogeochemical cycling in the environment. However, whether arsenate acts as an alternative electron acceptor of anaerobic methane oxidation and how this influences global arsenic transformations remains elusive. Here, we present incubations of arsenate-contaminated wetland soils from seven provinces in China. Using isotopically labelled methane, we find that anaerobic methane oxidation was linked to arsenate reduction at a rate approaching the theoretical arsenic/methane stoichiometric ratio of 4. In microcosm incubations with natural wetland soils, we find that the coupled pathway of anaerobic methane oxidation and arsenate reduction contributed 26 to 49% of total arsenic release from soils, with arsenic in the more soluble and toxic form arsenite. Comparative gene quantification and metagenomic sequencing suggest that the coupled pathway was facilitated by anaerobic methanotrophs, either independently or synergistically with arsenate-reducing bacteria through reverse methanogenesis and respiratory arsenate reduction. Further bioinformatic analyses show that genes coding for reverse methanogenesis and respiratory arsenate reduction are universally co-distributed in nature. This suggests that coupling of anaerobic methane oxidation and arsenate reduction is a potentially global but previously overlooked process, with implications for arsenic mobilization and environmental contamination. The coupling of anaerobic oxidation of methane and arsenate reduction is an important pathway of releasing arsenic from soils, according to incubation experiments of arsenate-contaminated wetland soils.

Arsenic mobilization by anaerobic iron-dependent methane oxidation

Arsenic groundwater contamination threatens the health of millions of people worldwide, particularly in South and Southeast Asia. In most cases, the release of arsenic from sediment was caused by microbial reductive dissolution of arsenic-bearing iron(III) minerals with organic carbon being used as microbial electron donor. Although in many arsenic-contaminated aquifers high concentrations of methane were observed, its role in arsenic mobilization is unknown. Here, using microcosms experiments and hydrogeochemical and microbial community analyses, we demonstrate that methane functions as electron donor for methanotrophs, triggering the reductive dissolution of arsenic-bearing iron(III) minerals, increasing the abundance of genes related to methane oxidation, and ultimately mobilizing arsenic into the water. Our findings provide evidence for a methane-mediated mechanism for arsenic mobilization that is distinct from previously described pathways. Taking this together with the common presence of methane in arsenic-contaminated aquifers, we suggest that this methane-driven arsenic mobilization may contribute to arsenic contamination of groundwater on a global scale.

Aspergillus niger Decreases Bioavailability of Arsenic(V) via Biotransformation of Manganese Oxide into Biogenic Oxalate Minerals.

The aim of this work was to evaluate the transformation of manganese oxide (hausmannite) by microscopic filamentous fungus Aspergillus niger and the effects of the transformation on mobility and bioavailability of arsenic. Our results showed that the A. niger strain CBS 140837 greatly affected the stability of hausmannite and induced its transformation into biogenic crystals of manganese oxalates—falottaite and lindbergite. The transformation was enabled by fungal acidolysis of hausmannite and subsequent release of manganese ions into the culture medium. While almost 45% of manganese was bioextracted, the arsenic content in manganese precipitates increased throughout the 25-day static cultivation of fungus. This significantly decreased the bioavailability of arsenic for the fungus. These results highlight the unique A. niger strain’s ability to act as an active geochemical factor via its ability to acidify its environment and to induce formation of biogenic minerals. This affects not only the manganese speciation, but also bioaccumulation of potentially toxic metals and metalloids associated with manganese oxides, including arsenic.

Arsenic dynamics in paddy soil under traditional manuring practices in Bangladesh.

Fertilization with organic matter (farm yard manure and/or rice straw) is thought to enhance arsenic (As) mobilization into soil porewaters, with subsequent As assimilation by rice roots leading to enhanced translocation to the grain. Here, interlinked experiments (field manuring and soil batch culture) were conducted to find the effect of organic matter at a field application rate practiced in Bangladesh (5t/ha) on As mobilization in soil for paddies impacted by As contaminated groundwater irrigation, a widespread phenomenon in Bangladesh where the experiments were conducted. Total As concentration in a paddy soil (Sonargaon) ranged from 21.9 to 8.1mg/kg down the soil profile and strongly correlated with TOC content. Arsenic, Fe, Mn, and DOC release into soil solution, and As speciation, are intimately linked to OM amendment, soil depth and temporal variation. Organic matter amendments lead to increased mobilization of As into both soil porewaters and standing surface waters. The As speciation in the porewater was dominated by inorganic As (Asi) (arsenite and arsenate), with traces amounts of methylated species (DMAV and MMAV) only being found with OM amendment. It was noted in field trials that OM fertilization greatly enhanced As mobility to surface waters, which may have major implications for the fate of As in paddy agronomic ecosystems.

Bacterially mediated release and mobilization of As/Fe coupled to nitrate reduction in a sediment environment

Metal-reducing bacteria play an important role in the release and mobilization of arsenic from sediments into groundwater. This study aimed to investigate the influence of nitrate on arsenic bio-release. Microcosm experiments consisting of high arsenic sediments and indigenous bacterium Bacillus sp. D2201 were conducted and the effects of nitrate on the mobilization of As/Fe determined. The results show arsenic release is triggered by iron reduction, which is regulated by nitrate. Increasing the nitrate concentration from 0 to 1 and 3 mM decreased Fe(III) reduction by 62.5% and 16.9% and decreased As(V) bio-release by 41.5% and 85.5%, respectively. Moreover, the results of step-wise Wenzel sequential extractions indicate nitrate addition prevents the transformation of poorly crystalline iron oxides to well crystalline iron oxides. Overall, nitrate appears to have a dual effect, inhibiting both iron reduction and arsenic release by incubation strain D2201. This study offers new insights regarding the biogeochemistry of arsenic in groundwater systems.

Altered arsenic availability, uptake, and allocation in rice under elevated temperature

Climate change is expected to increase growing temperatures in rice cultivating regions worldwide. Recent research demonstrates that elevated temperature can increase arsenic concentrations in rice tissue, exacerbating an existing threat to rice quality and human health. However, the specific temperature-induced changes in the plant-soil system responsible for increased arsenic concentrations remain unclear and such knowledge is necessary to manage human dietary arsenic exposure in a warmer future. To elucidate these changes, we established four temperature treatments in climate-controlled growth chambers and grew rice plants (Oryza sativa cv. M206) in pots filled with Californian paddy soil with arsenic concentrations of 7.7 mg kg−1. The four chosen temperatures mimicked IPCC forecasting for Northern California, with a roughly 2.5 °C increase between treatments (nighttime temperatures ~2 °C cooler). We observed that arsenic concentrations in porewater, root iron plaque, and plant tissue increased in response to elevated temperature. There was a positive linear relationship between temperature and rice grain arsenic, almost all of which was present as inorganic As (III). Above-ground allocation patterns were consistent across treatments. We found no upregulation in the gene encoding the OsABCC1 transporter, believed to be important for arsenic sequestration in vacuoles and thereby preventing arsenic transfer to grain. Rice plants grown at higher temperatures had more adsorbed arsenic per unit of iron plaque (measured as [As]/[Fe]), indicating temperature may impact arsenic sorption to root plaque. We present evidence that increased soil mobilization of arsenic was the driving factor responsible for increased arsenic uptake into rice grain. Transpiration, which can increase arsenic transport to roots, was also heightened with elevated temperature but appeared to play a secondary role. Our system had low soil arsenic concentrations typical for California. Our findings highlight that elevated growing temperatures may increase the risk of dietary arsenic exposure in rice systems that were previously considered low risk.

Seasonal Temperature Oscillations Drive Contrasting Arsenic and Antimony Mobilization in a Mining‐Impacted River System

AbstractArsenic (As) and antimony (Sb) speciation and mobility in river systems can be influenced by the redox conditions of benthic and hyporheic zone sediments. However, our understanding of how temperature fluctuations influence riverine As and Sb mobility over diel and seasonal time frames, via moderation of sediment redox conditions, is poorly constrained. Here we compare diel and seasonal water quality data from a river system contaminated with As and Sb with results from sediment‐water incubations conducted at temperatures spanning 8°C to 32°C under low‐dissolved oxygen conditions. Higher incubation temperatures caused faster microbial respiration, lower redox potential, and greater Asaq concentrations, coincident with reduction of As(V), Mn (III/IV), Fe (III), and SO42−. Initial rates of As3+aq formation increased exponentially with temperature (Q10 = 3.3 ± 0.5) and were positively correlated with microbial respiration (r2 = 0.99, P &lt; 0.01). In contrast, Sbaq displayed an initially negative and comparatively weak overall temperature dependence during incubations. In river waters, diel mobilization of reduced species (As3+aq and Fe2+aq) and contrasting attenuation of Sb was coincident with lower redox potential during nightly respiration cycles. Distinct seasonal oscillations in river water Asaq were exponentially correlated with temperature (r2 = 0.68, P &lt; 0.01), whereas Sbaq was not. These characteristics reflect the fundamental role of anaerobic metabolism (as influenced by temperature) within benthic and hyporheic zone sediments as a key driver of contrasting riverine As and Sb mobility. The findings imply that riverine As mobility may be enhanced, while Sb mobility possibly attenuated, by eutrophication or by elevated stream temperatures due to a warming climate.