Sulfate reduction accelerates groundwater arsenic contamination even in aquifers with abundant iron oxides.

Groundwater contamination by geogenic arsenic is a global problem affecting nearly 200 million people. In South and Southeast Asia, a cost-effective mitigation strategy is to use oxidized low-arsenic aquifers rather than reduced high-arsenic aquifers. Aquifers with abundant oxidized iron minerals are presumably safeguarded against immediate arsenic contamination, due to strong sorption of arsenic onto iron minerals. However, preferential pumping of low-arsenic aquifers can destabilize the boundaries between these aquifers, pulling high-arsenic water into low-arsenic aquifers. We investigate this scenario in a hybrid field-column experiment in Bangladesh where naturally high-arsenic groundwater is pumped through sediment cores from a low-arsenic aquifer, and detailed aqueous and solid-phase measurements are used to constrain reactive transport modelling. Here we show that elevated groundwater arsenic concentrations are induced by sulfate reduction and the predicted formation of highly mobile, poorly sorbing thioarsenic species. This process suggests that contamination of currently pristine aquifers with arsenic can occur up to over 1.5 times faster than previously thought, leading to a deterioration of urgently needed water resources.

Determination of Arsenic Content in Water Using a Silver Coordination Polymer.

In this report, we describe a practical method for the colorimetric determination of dissolved inorganic arsenic content in water samples, using a silver coordination polymer as the sensing material. We demonstrate that a crystalline polymer framework can be used to stabilize silver(I) ions, greatly reducing both photosensitivity and water solubility, while still affording sufficient reactivity to detect arsenic in water samples at low parts-per-billion (ppb) levels. Test strips fabricated with the silver-based polymer are shown to be effective for field tests of groundwater under real-world operating conditions and display performance that is competitive with commercially available mercury-based test strips. Spectroscopic methods are also used to probe the reaction products formed, in order to better understand the sensing mechanism. Thus, our work provides the foundation for an improved field test that could be deployed to help manage groundwater usage in regions where arsenic contamination is problematic but sophisticated lab testing is not readily available.

Lead (Pb) concentrations and speciation in residential soils from an urban community impacted by multiple legacy sources.

In many urban areas, elevated soil lead (Pb) concentrations are indicators of community-level Pb exposure. Here, we examine the spatial distribution and speciation of legacy soil Pb contamination in East Chicago, Ind., an industrial center with a wide range of Pb sources including a former lead smelter. In situ X-ray fluorescence spectroscopy (n = 358) revealed widespread soil Pb contamination above the Environmental Protection Agency regulatory limit for soils. This soil contamination was heterogenous across all neighborhoods, and mostly uncorrelated with distance from the former smelting site. Soil Pb levels increased with decreasing median household income in East Chicago's nine neighborhoods (r = -0.73, p = 0.03). Extended X-ray absorption fine structure spectroscopy (n = 44) indicated that the soil Pb was primarily adsorbed to iron and manganese oxides or humic acids, and as Pb hydroxycarbonate regardless of contamination levels. Crystalline insoluble forms of Pb, like pyromorphite, were not detected in significant concentrations. Thus, the unique chemical forms of potential Pb sources to soil, such as paint, ore and slag are not persistent and instead are extensively repartitioned into acid-soluble forms of Pb with greater bioavailability. These findings have implications for remediation efforts and human health as blood Pb levels in this community are significantly elevated.

Fermentation, methanotrophy and methanogenesis influence sedimentary Fe and As dynamics in As-affected aquifers in Vietnam.

High arsenic (As) concentrations in groundwater are a worldwide problem threatening the health of millions of people. Microbial processes are central in the (trans)formation of the As-bearing ferric and ferrous minerals, and thus regulate dissolved As levels in many aquifers. Mineralogy, microbiology and dissolved As levels can vary sharply within aquifers, making high-resolution measurements particularly valuable in understanding the linkages between them. We conducted a high spatial resolution geomicrobiological study in combination with analysis of sediment chemistry and mineralogy in an alluvial aquifer system affected by geogenic As in the Red River delta in Vietnam. Microbial community analysis revealed a dominance of fermenters, methanogens and methanotrophs whereas sediment mineralogy along a 46 m deep core showed a diversity of Fe minerals including poorly crystalline Fe (II/III) and Fe(III) (oxyhydr)oxides such as goethite, hematite, and magnetite, but also the presence of Fe(II)-bearing carbonates and sulfides which likely formed as a result of microbially driven organic carbon (OC) degradation. A potential important role of methane (CH4) as electron donor for reductive Fe mineral (trans)formation was supported by the high abundance of Candidatus Methanoperedens, a known Fe(III)-reducing methanotroph. Overall, these results imply that OC turnover including fermentation, methanogenesis and CH4 oxidation are important mechanisms leading to Fe mineral (trans)formation, dissolution and precipitation, and thus indirectly affecting As mobility by changing the Fe-mineral inventory.

Reduction of iron (hydr)oxide-bound arsenate: Evidence from high depth resolution sampling of a reducing aquifer in Yinchuan Plain, China.

Sediment in fluvial-deltaic plains with high-As groundwater is heterogenous but its characterization of As and Fe oxidation states lacks resolution, and is rarely attempted for aqueous and solid phases simultaneously. Here, we pair high-resolution (> 1 sample/meter) Fe extended fine-structure spectroscopy (EXAFS, n = 40) and As X-ray absorption near-edge spectroscopy (XANES, n = 49) with groundwater composition and metagenomics measurements for two sediment cores and their associated wells (n = 8) from the Yinchuan Plain in northwest China. At shallower depths, nitrate and Mn/Fe reducing sediment zones are fine textured, contain 9.6 ± 5.6 mg kg-1 of As(V) and 2.3 ± 2.7 mg kg-1 of As(III) with 9.1 ± 8.1 g kg-1 of Fe(III) (hydr)oxides, with bacterial genera capable of As and Fe reduction identified. In four deeper 10-m sections, sulfate-reducing sediments are coarser and contain 2.6 ± 1.3 mg kg-1 of As(V) and 1.1 ± 1.0 mg kg-1 of As(III) with 3.2 ± 2.6 g kg-1 of Fe(III) (hydr)oxides, even though groundwater As concentrations can exceed 200 µg/L, mostly as As(III). Super-enrichment of sediment As (42-133 mg kg-1, n = 7) at shallower depth is due to redox trapping during past groundwater discharge. Active As and Fe reduction is supported by the contrast between the As(III)-dominated groundwater and the As(V)-dominated sediment, and by the decreasing sediment As(V) and Fe(III) (hydr)oxides concentrations with depth.

Aquifer-Scale Observations of Iron Redox Transformations in Arsenic-Impacted Environments to Predict Future Contamination.

Iron oxides control the mobility of a host of contaminants in aquifer systems, and the microbial reduction of iron oxides in the subsurface is linked to high levels of arsenic in groundwater that affects greater than 150 million people globally. Paired observations of groundwater and solid-phase aquifer composition are critical to understand spatial and temporal trends in contamination and effectively manage changing water resources, yet field-representative mineralogical data are sparse across redox gradients relevant to arsenic contamination. We characterize iron mineralogy using X-ray absorption spectroscopy across a natural gradient of groundwater arsenic contamination in Vietnam. Hierarchical cluster analysis classifies sediments into meaningful groups delineating weathering and redox changes, diagnostic of depositional history, in this first direct characterization of redox transformations in the field. Notably, these groupings reveal a signature of iron minerals undergoing active reduction before the onset of arsenic contamination in groundwater. Pleistocene sediments undergoing postdepositional reduction may be more extensive than previously recognized due to previous misclassification. By upscaling to similar environments in South and Southeast Asia via multinomial logistic regression modeling, we show that active iron reduction, and therefore susceptibility to future arsenic contamination, is more widely distributed in presumably pristine aquifers than anticipated.

Quantifying Riverine Recharge Impacts on Redox Conditions and Arsenic Release in Groundwater Aquifers Along the Red River, Vietnam.

Widespread contamination of groundwater with geogenic arsenic is attributed to microbial dissolution of arsenic-bearing iron (oxyhydr)oxides minerals coupled to the oxidation of organic carbon. The recharge sources to an aquifer can influence groundwater arsenic concentrations by transport of dissolved arsenic or reactive constituents that affect arsenic mobilization. To understand how different recharge sources affect arsenic contamination-in particular through their influence on organic carbon and sulfate cycling-we delineated and quantified recharge sources in the arsenic affected region around Hanoi, Vietnam. We constrained potential end-member compositions and employed a novel end-member mixing model using an ensemble approach to apportion recharge sources. Groundwater arsenic and dissolved organic carbon concentrations are controlled by the dominant source of recharge. High arsenic concentrations are prevalent regardless of high dissolved organic carbon or ammonium levels, indicative of organic matter decomposition, where the dominant recharge source is riverine. In contrast, high dissolved organic carbon and significant organic matter decomposition are required to generate elevated groundwater arsenic where recharge is largely nonriverine. These findings suggest that in areas of riverine recharge, arsenic may be efficiently mobilized from reactive surficial environments and carried from river-aquifer interfaces into groundwater. In groundwaters derived from nonriverine recharge areas, significantly more organic carbon mineralization is required to obtain equivalent levels of arsenic mobilization within inland sediments. This method can be broadly applied to examine the connection between hydrology, geochemistry and groundwater quality.