Association of Water Arsenic With Incident Diabetes in U.S. Adults: The Multi-Ethnic Study of Atherosclerosis and the Strong Heart Study.

OBJECTIVE: We examined the association of arsenic in federally regulated community water systems (CWSs) and unregulated private wells with type 2 diabetes (T2D) incidence in the Strong Heart Family Study (SHFS), a prospective study of American Indian communities, and the Multi-Ethnic Study of Atherosclerosis (MESA), a prospective study of racially and ethnically diverse urban U.S. communities. RESEARCH DESIGN AND METHODS: We evaluated 1,791 participants from SHFS and 5,777 participants from MESA who had water arsenic estimates available and were free of T2D at baseline (2001-2003 and 2000-2002, respectively). Participants were followed for incident T2D until 2010 (SHFS cohort) or 2019 (MESA cohort). We used Cox proportional hazards mixed-effects models to account for clustering by family and residential zip code, with adjustment for sex, baseline age, BMI, smoking status, and education. RESULTS: T2D incidence was 24.4 cases per 1,000 person-years (mean follow-up, 5.6 years) in SHFS and 11.2 per 1,000 person-years (mean follow-up, 14.0 years) in MESA. In a meta-analysis across the SHFS and MESA cohorts, the hazard ratio (95% CI) per doubling in CWS arsenic was 1.10 (1.02, 1.18). The corresponding hazard ratio was 1.09 (0.95, 1.26) in the SHFS group and 1.10 (1.01, 1.20) in the MESA group. The corresponding hazard ratio (95% CI) for arsenic in private wells and incident T2D in SHFS was 1.05 (0.95, 1.16). We observed statistical interaction and larger magnitude hazard ratios for participants with BMI <25 kg/m2 and female participants. CONCLUSIONS: Low to moderate water arsenic levels (<10 µg/L) were associated with T2D incidence in the SHFS and MESA cohorts.

Contribution of arsenic and uranium in private wells and community water systems to urinary biomarkers in US adults: The Strong Heart Study and the Multi-Ethnic Study of Atherosclerosis.

BACKGROUND: Chronic exposure to inorganic arsenic (As) and uranium (U) in the United States (US) occurs from unregulated private wells and federally regulated community water systems (CWSs). The contribution of water to total exposure is assumed to be low when water As and U concentrations are low. OBJECTIVE: We examined the contribution of water As and U to urinary biomarkers in the Strong Heart Family Study (SHFS), a prospective study of American Indian communities, and the Multi-Ethnic Study of Atherosclerosis (MESA), a prospective study of racially/ethnically diverse urban U.S. communities. METHODS: We assigned residential zip code-level estimates in CWSs (µg/L) and private wells (90th percentile probability of As >10 µg/L) to up to 1485 and 6722 participants with dietary information and urinary biomarkers in the SHFS (2001-2003) and MESA (2000-2002; 2010-2011), respectively. Urine As was estimated as the sum of inorganic and methylated species, and urine U was total uranium. We used linear mixed-effects models to account for participant clustering and removed the effect of dietary sources via regression adjustment. RESULTS: The median (interquartile range) urine As was 5.32 (3.29, 8.53) and 6.32 (3.34, 12.48) µg/L for SHFS and MESA, respectively, and urine U was 0.037 (0.014, 0.071) and 0.007 (0.003, 0.018) µg/L. In a meta-analysis across both studies, urine As was 11% (95% CI: 3, 20%) higher and urine U was 35% (5, 73%) higher per twofold higher CWS As and U, respectively. In the SHFS, zip-code level factors such as private well and CWS As contributed 46% of variation in urine As, while in MESA, zip-code level factors, e.g., CWS As and U, contribute 30 and 49% of variation in urine As and U, respectively. IMPACT STATEMENT: We found that water from unregulated private wells and regulated CWSs is a major contributor to urinary As and U (an estimated measure of internal dose) in both rural, American Indian populations and urban, racially/ethnically diverse populations nationwide, even at levels below the current regulatory standard. Our findings indicate that additional drinking water interventions, regulations, and policies can have a major impact on reducing total exposures to As and U, which are linked to adverse health effects even at low levels.

Elevated arsenic concentrations in groundwater of the Upper Indus Plain of Pakistan across a range of redox conditions.

Groundwater of the Ravi River floodplain is particularly elevated in arsenic (As) on both sides of the Pakistan-India border. To understand this pattern, 14 sites were drilled to 12-30 m depth across floodplains and doabs of Pakistan after testing over 20,000 wells. Drill cuttings were collected at 1.5 m intervals, 132 of which were sand overlain by 77 intervals of clay and/or silt. Radiocarbon dating of clay indicates deposition of the aquifer sands tapped by wells 20-30 kyr ago. Most (85 %) of the sand samples were gray in color, indicating partial reduction to Fe(II) oxides, whereas most (92 %) of the clay and/or silt samples were orange. Associations between groundwater electrical conductivity, dissolved Fe, sulfate, and nitrate suggest that wells can be elevated (>10 µg/L) in As in the region due to either reductive dissolution of Fe oxides, evaporative concentration, or alkali desorption. In the Ravi floodplain, 47 % of 6445 wells tested contain >10 µg/L As compared to only 9 % of 14,165 tested wells in other floodplains and doabs. The As content of aquifer sands in the Ravi floodplain of Pakistan averages 4 ± 4 mg/kg (n = 66) and is higher than the average of 2 ± 2 mg/kg (n = 51) for aquifer sands outside the Ravi. Synchrotron spectroscopy and column-based speciation indicate predominance of As(V) over As(III) in both aquifer sands and groundwater. Whereas multiple processes may be responsible for elevated levels of As in groundwater across the region, spatial heterogeneity in groundwater As concentrations in the Ravi floodplain seems linked to variations in As concentrations in aquifer sands. Regulation by the solid phase may limit variations in groundwater As over time in response to natural and human-induced changes in hydrology. This means spatial heterogeneity could be taken advantage of to lower the exposure across the region with more testing and targeted drilling.

Geospatial Assessment of Racial/Ethnic Composition, Social Vulnerability, and Lead Water Service Lines in New York City.

BACKGROUND: The state of New York expects to receive $115 million in 2022 alone from the U.S. Infrastructure Investment and Jobs Act to support the replacement of lead water service lines. OBJECTIVES: Our objective was to determine the number and proportion of potential lead water service lines across New York City (NYC) and to evaluate the association between census tract-level racial/ethnic composition, housing vulnerability, and child lead exposure vulnerability with service line type (Potential Lead, Unknown) for n=2,083 NYC tracts. METHODS: We conducted a descriptive analysis assessing water service line material recorded in the NYC Department of Environmental Protection's Lead Service Line Location Coordinates database. We used conditional autoregressive Bayesian Poisson models to assess the relative risk [RR; median posterior estimates, and 95% credible interval (CrI)] of service line type per 20% higher proportion of residents in a given racial/ethnic group and per higher housing vulnerability and child lead exposure vulnerability index scores corresponding to the interquartile range. We also evaluated the associations in flexible natural cubic spline models. RESULTS: Out of 854,672 residential service line records, 136,891 (16.0%) were Potential Lead, and 227,443 (26.6%) were Unknown. In fully adjusted models, higher proportions of Hispanic/Latino residents and higher child lead exposure vulnerability were associated with Potential Lead service lines in flexible spline models and linear models [RR=1.15 (95% CrI: 1.11, 1.21) and RR=1.11 (95% CrI: 1.02, 1.20), respectively]. Associations were modified by borough; Potential Lead service lines were associated with higher proportions of non-Hispanic White and non-Hispanic Asian residents in the Bronx and Manhattan, and with higher proportions of non-Hispanic Black residents in Queens. DISCUSSION: NYC has a high number of Potential Lead and Unknown water service lines. Communities with a high proportion of Hispanic/Latino residents and those with children who are already highly vulnerable to lead exposures from numerous sources are disproportionately impacted by Potential Lead service lines. These findings can inform equitable service line replacement across New York state and NYC. https://doi.org/10.1289/EHP12276.

Impact of lowering the US maximum contaminant level on arsenic exposure: Differences by race, region, and water arsenic in NHANES 2003-2014.

Our objective was to evaluate regional and sociodemographic inequalities in water arsenic exposure reductions associated with the US Environmental Protection Agency's Final Arsenic Rule, which lowered the arsenic maximum contaminant level to 10 µg/L in public water systems. We analyzed 8544 participants from the 2003-14 National Health and Nutrition Examination Survey (NHANES) reliant on community water systems (CWSs). We estimated arsenic exposure from water by recalibrating urinary dimethylarsinate (rDMA) to remove smoking and dietary contributions. We evaluated mean differences and corresponding percent reductions of urinary rDMA comparing subsequent survey cycles to 2003-04 (baseline), stratified by region, race/ethnicity, educational attainment, and tertile of CWS arsenic assigned at the county level. The overall difference (percent reduction) in urine rDMA was 0.32 µg/L (9%) among participants with the highest tertile of CWS arsenic, comparing 2013-14 to 2003-04. Declines in urinary rDMA were largest in regions with the highest water arsenic: the South [0.57 µg/L (16%)] and West [0.46 µg/L, (14%)]. Declines in urinary rDMA levels were significant and largest among Mexican American [0.99 µg/L (26%)] and Non-Hispanic White [0.25 µg/L (10%)] participants. Reductions in rDMA following the Final Arsenic Rule were highest among participants with the highest CWS arsenic concentrations, supporting legislation can benefit those who need it the most, although additional efforts are still needed to address remaining inequalities in CWS arsenic exposure.

Prevalence of Methylated Arsenic and Microbial Arsenic Methylation Genes in Paddy Soils of the Mekong Delta.

Microbially mediated inorganic-methylated arsenic (As) transformation in paddy soil is crucial to rice safety; however, the linkages between the microbial As methylation process and methylated As species remain elusive. Here, 62 paddy soils were collected from the Mekong River delta of Cambodia to profile As-related functional gene composition involved in the As cycle. The soil As concentration ranged from <1 to 16.6 mg kg-1, with average As contents of approximately 81% as methylated As and 54% as monomethylarsenate (MMAs(V)) in the phosphate- and oxalate-extractable fractions based on As sequential extraction analysis. Quantitative PCR revealed high arsenite-methylating gene (arsM) copy numbers, and metagenomics identified consistently high arsM gene abundance. The abundance of As-related genes was the highest in bacteria, followed by archaea and fungi. Pseudomonas, Bradyrhizobium, Burkholderia, and Anaeromyxobacter were identified as bacteria harboring the most genes related to As biotransformation. Moreover, arsM and arsI (As demethylation) gene-containing operons were identified in the metagenome-assembled genomes (MAGs), implying that arsM and arsI could be transcribed together. The prevalence of methylated As and arsM genes may have been overlooked in tropical paddy fields. The As methylation-demethylation cycle should be considered when manipulating the methylated As pool in paddy fields for rice safety.

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.

Integrated effects of bioturbation, warming and sea-level rise on mobility of sulfide and metalloids in sediment porewater of mangrove wetlands.

Global warming and sea-level rise exert profound impacts on coastal mangrove ecosystems, where widespread benthic crabs change sediment properties and regulate material cycles. How crab bioturbation perturbs the mobilities of bioavailable arsenic (As), antimony (Sb) and sulfide in sediment-water systems and their variability in response to temperature and sea-level rise is still unknown. By combining field monitoring and laboratory experiments, we found that As was mobilized under sulfidic conditions while Sb was mobilized under oxic conditions in mangrove sediments. Crab burrowing greatly enhanced oxidizing conditions, resulting in enhanced Sb mobilization and release but As sequestration by iron/manganese oxides. In control experiments with non-bioturbation, the more sulfidic conditions triggered the contrasting situation of As remobilization and release but Sb precipitation and burial. Moreover, the bioturbated sediments were highly heterogeneous for spatial distributions of labile sulfide, As and Sb as presented by 2-D high-resolution imaging and Moran's Index (patchy at the <1 cm scale). Warming stimulated stronger burrowing activities, which led to more oxic conditions and further Sb mobilization and As sequestration, whilst sea-level rise did the opposite via suppressing crab burrowing activity. This work highlights that global climate changes have the potential to significantly alter element cycles in coastal mangrove wetlands by regulating benthic bioturbation and redox chemistry.

Cross-sectional associations between drinking water arsenic and urinary inorganic arsenic in the United States: NHANES 2003-2014.

BACKGROUND: Inorganic arsenic is a potent carcinogen and toxicant associated with numerous adverse health outcomes. The contribution of drinking water from private wells and regulated community water systems (CWSs) to total inorganic arsenic exposure is not clear. OBJECTIVES: To determine the association between drinking water arsenic estimates and urinary arsenic concentrations in the 2003-2014 National Health and Nutrition Examination Survey (NHANES). METHODS: We evaluated 11,088 participants from the 2003-2014 NHANES cycles. For each participant, we assigned private well and CWS arsenic levels according to county of residence using estimates previously derived by the U.S. Environmental Protection Agency and U.S. Geological Survey. We used recalibrated urinary dimethylarsinate (rDMA) to reflect the internal dose of estimated water arsenic by applying a previously validated, residual-based method that removes the contribution of dietary arsenic sources. We compared the adjusted geometric mean ratios and corresponding percent change of urinary rDMA across tertiles of private well and CWS arsenic levels, with the lowest tertile as the reference. Comparisons were made overall and stratified by census region and race/ethnicity. RESULTS: Overall, the geometric mean of urinary rDMA was 2.52 (2.30, 2.77) µg/L among private well users and 2.64 (2.57, 2.72) µg/L among CWS users. Urinary rDMA was highest among participants in the West and South, and among Mexican American, Other Hispanic, and Non-Hispanic Other participants. Urinary rDMA levels were 25% (95% confidence interval (CI): 17-34%) and 20% (95% CI: 12-29%) higher comparing the highest to the lowest tertile of CWS and private well arsenic, respectively. The strongest associations between water arsenic and urinary rDMA were observed among participants in the South, West, and among Mexican American and Non-Hispanic White and Black participants. DISCUSSION: Both private wells and regulated CWSs are associated with inorganic arsenic internal dose as reflected in urine in the general U.S.

Nationwide geospatial analysis of county racial and ethnic composition and public drinking water arsenic and uranium.

There is no safe level of exposure to inorganic arsenic or uranium, yet recent studies identified sociodemographic and regional inequalities in concentrations of these frequently detected contaminants in public water systems across the US. We analyze the county-level association between racial/ethnic composition and public water arsenic and uranium concentrations from 2000-2011 using geospatial models. We find that higher proportions of Hispanic/Latino and American Indian/Alaskan Native residents are associated with significantly higher arsenic and uranium concentrations. These associations differ in magnitude and direction across regions; higher proportions of non-Hispanic Black residents are associated with higher arsenic and uranium in regions where concentrations of these contaminants are high. The findings from this nationwide geospatial analysis identifying racial/ethnic inequalities in arsenic and uranium concentrations in public drinking water across the US can advance environmental justice initiatives by informing regulatory action and financial and technical support to protect communities of color.

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.

Sociodemographic inequalities in uranium and other metals in community water systems across the USA, 2006-11: a cross-sectional study.

BACKGROUND: The US Environmental Protection Agency (EPA) currently sets maximum contaminant levels (MCLs) for ten metals or metalloids in public drinking water systems. Our objective was to estimate metal concentrations in community water systems (CWSs) across the USA, to establish if sociodemographic or regional inequalities in the metal concentrations exist, and to identify patterns of concentrations for these metals as a mixture. METHODS: We evaluated routine compliance monitoring records for antimony, arsenic, barium, beryllium, cadmium, chromium, mercury, selenium, thallium, and uranium, collected from 2006-11 (2000-11 for uranium; timeframe based on compliance monitoring requirements) by the US EPA in support of their second and third Six-Year Reviews for CWSs. Arsenic, barium, chromium, selenium, and uranium (detectable in >10% records) were included in the main analyses (subgroup and metal mixture analyses; arsenic data reported previously). We compared the mean, 75th percentile, and 95th percentile contaminant concentrations and the percentage of CWSs with concentrations exceeding the MCL across subgroups (region, sociodemographic county-cluster, size of population served, source water type, and CWSs exclusively serving correctional facilities). We evaluated patterns in CWS metal concentration estimate profiles via hierarchical cluster analysis. We created an online interactive map and dashboard of estimated CWS metal concentrations for use in future analyses. FINDINGS: Average metal concentrations were available for a total of 37 915 CWSs across the USA. The total number of monitoring records available was approximately 297 000 for arsenic, 165 000 for barium, 167 000 for chromium, 165 000 for selenium, and 128 000 for uranium. The percentage of analysed CWSs with average concentrations exceeding the MCL was 2·6% for arsenic (MCL=10 µg/L; nationwide mean 1·77 µg/L; n=36 798 CWSs), 2·1% for uranium (MCL=30 µg/L; nationwide mean 4·37 µg/L; n=14 503 CWSs), and less than 0·1% for the other metals. The number of records with detections was highest for uranium (63·1%). 75th and 95th percentile concentrations for uranium, chromium, barium, and selenium were highest for CWSs serving Semi-Urban, Hispanic communities, CWSs reliant on groundwater, and CWSs in the Central Midwest. Hierarchical cluster analysis revealed two distinct clusters: an arsenic-uranium-selenium cluster and a barium-chromium cluster. INTERPRETATIONS: Uranium is an under-recognised contaminant in CWSs. Metal concentrations (including uranium) are elevated in CWSs serving Semi-Urban, Hispanic communities independent of location or region, highlighting environmental justice concerns. FUNDING: US National Institutes of Health Office of the Director, US National Institutes for Environmental Health Sciences, and US National Institute of Dental and Craniofacial Research.

In vitro and in silico bioaccessibility of urban dusts contaminated by multiple legacy sources of lead (Pb).

Lead contamination from gasoline, paint, pesticides, and smelting have unique chemical structures. Recent investigations into Pb speciation in urban soils and dusts from multiple sources have revealed emerging forms which differ from the initial sources. This results from reactions with soil constituents leading to transformation to new forms for which the bioaccessibilities remain uninvestigated. We investigated the in vitro and in silico bioaccessibility of these emerging forms in three physiologically relevant milieux: artificial lysosomal fluid (ALF), simulated epithelial lung fluid (SELF), and simulated gastric fluid (SGF). Species were validated using extended X-ray absorption fine structure spectroscopy. Results highlight diverse bioaccessibilities which are form and compartmentally-dependent. In ALF the bioaccessibility trend was humate-bound Pb (86%) > hydrocerussite (79%) > Fe oxide-bound Pb (47%) > galena (10%) > pyromorphite (4%) > Mn oxide-bound Pb (2%). Humate-bound Pb, hydrocerussite, Fe and Mn oxide-bound Pb were 100% bioaccessible in SGF while pyromorphite and galena were 26%, and 8%, respectively. Bioaccessibility in SELF was very low (< 1%) and significantly lower than ALF and SGF (p < 0.001). In silico bioaccessibilities modeled using equilibrium solubilities in extraction solutions were in good agreement with empirical measurements. These emerging forms of Pb have a wide range of bioaccessibilities that can influence their toxicity and impact on human health.

Groundwater fluoride across the Punjab plains of Pakistan and India: Distribution and underlying mechanisms.

Chronic exposure from drinking well-water with naturally high concentrations of fluoride (F-) has serious health consequences in several regions across the world including South Asia, where the rural population is particularly dependent on untreated groundwater pumped from private wells. An extensive campaign to test 28,648 wells was conducted across the Punjab plains of Pakistan and India by relying primarily on field kits to document the scale of the problem and shed light on the underlying mechanisms. Groundwater samples were collected from a subset of 712 wells for laboratory analysis of F- and other constituents. A handful of sites showing contrasting levels of F- in groundwater were also drilled to determine if the composition of aquifer sediment differed between these sites. The laboratory data show that the field kits correctly classified 91% of the samples relative to the World Health Organization guideline for drinking water of 1.5 mg/L F-. The kit data indicate that 9% of wells across a region extending from the Indus to the Sutlej rivers were elevated in F- relative to this guideline. Field data indicate an association between the proportion of well-water samples with F- > 1.5 mg/L and electric conductivity (EC) > 1.5 mS/cm across six floodplains and six intervening doabs. Low Ca2+ concentrations and elevated bicarbonate (HCO3- > 500 mg/L) and sodium (Na+ > 200 mg/L) in high F- groundwater suggest regulation by fluorite. This could be through either the lack of precipitation or the dissolution of fluorite regulated by the loss of Ca2+ from groundwater due to precipitation of calcite and/or ion exchange with clay minerals. Widespread salinization of Punjab aquifers attributed to irrigation may have contributed to higher F- levels in groundwater of the region. Historical conductivity data suggest salinization has yet to be reversed in spite of changes in water resources management.

Surface Flooding as a Key Driver of Groundwater Arsenic Contamination in Southeast Asia.

Chronic exposure to groundwater contaminated with geogenic arsenic (As) poses a significant threat to human health worldwide, especially for those living on floodplains in South and Southeast (S-SE) Asia. In the alluvial and deltaic aquifers of S-SE Asia, aqueous As concentrations vary sharply over small spatial scales (10-100 m), making it challenging to identify where As contamination is present and mitigate exposure. Improved mechanistic understanding of the factors that control groundwater As levels is essential to develop models that accurately predict spatially variable groundwater As concentrations. Here we demonstrate that surface flooding duration and interannual frequency are master variables that integrate key hydrologic and biogeochemical processes that affect groundwater As levels in S-SE Asia. A machine-learning model based on high-resolution, satellite-derived, long-term measures of surface flooding duration and frequency effectively predicts heterogeneous groundwater As concentrations at fine spatial scales in Cambodia, Vietnam, and Bangladesh. Our approach can be reliably applied to identify locations of safe and unsafe groundwater sources with sufficient accuracy for making management decisions by solely using remotely sensed information. This work is important to evaluate levels of As exposure, impacts to public health, and to shed light on the underlying hydrogeochemical processes that drive As mobilization into groundwater.

In situ arsenic immobilisation for coastal aquifers using stimulated iron cycling: Lab-based viability assessment.

Arsenic (As) is one of the most harmful and widespread groundwater contaminants globally. Besides the occurrence of geogenic As pollution, there is also a large number of sites that have been polluted by anthropogenic activities, with many of those requiring active remediation to reduce their environmental impact. Cost-effective remedial strategies are however still sorely needed. At the laboratory-scale in situ formation of magnetite through the joint addition of nitrate and Fe(II) has shown to be a promising new technique. However, its applicability under a wider range of environmental conditions still needs to be assessed. Here we use sediment and groundwater from a severely polluted coastal aquifer and explore the efficiency of nitrate-Fe(II) treatments in mitigating dissolved As concentrations. In selected experiments >99% of dissolved As was removed, compared to unamended controls, and maintained upon addition of lactate, a labile organic carbon source. Pre- and post experimental characterisation of iron (Fe) mineral phases suggested a >90% loss of amorphous Fe oxides in favour of increased crystalline, recalcitrant oxide and sulfide phases. Magnetite formation did not occur via the nitrate-dependent oxidation of the amended Fe(II) as originally expected. Instead, magnetite is thought to have formed by the Fe(II)-catalysed transformation of pre-existing amorphous and crystalline Fe oxides. The extent of amorphous and crystalline Fe oxide transformation was then limited by the exhaustion of dissolved Fe(II). Elevated phosphate concentrations lowered the treatment efficacy indicating joint removal of phosphate is necessary for maximum impact. The remedial efficiency was not impacted by varying salinities, thus rendering the tested approach a viable remediation method for coastal aquifers.

Persistent arsenate-iron(iii) oxyhydroxide-organic matter nanoaggregates observed in coal.

Understanding how natural nanoaggregates of iron (Fe) and organic matter (OM), currently identified in organic rich soil or peat, interact with metals and metalloids is environmentally significant. Coal is also organic-rich and exemplifies anoxic sedimentary environments with Fe usually as pyrite and not oxides. Here, we analyze the local structure of Fe (6880-21 700 mg kg-1) and As (45-5680 mg kg-1) in representative Guizhou coal samples using X-ray absorption near-edge structure and extended X-ray absorption fine structure (XANES and EXAFS) to illustrate how Fe(iii) and As(v) are preserved in coal formed from reduced, organic-rich precursors. Arsenic XANES indicates that >80% of As exists as As(v) with <14% of As associated with sulfides in 5 Guizhou coal samples, confirming published but unexplained results. An As-Fe shell at 3.25-3.29 Å in the As EXAFS suggests that this As(v) is adsorbed on Fe(iii) oxyhydroxides as evidenced by Fe EXAFS in these coal samples. Significantly, lower Fe-Fe coordination numbers (CN) of 0.6-1.1 relative to those in 2-line ferrihydrite (CN = 1.6) and goethite (CN = 2.1) suggest that these Fe(iii) oxyhydroxides are likely Fe-OM nanoaggregates protected by OM encapsulation and adsorption of arsenate. Such structurally stabilized composites of As(v)-Fe(iii)-OM may be more widely distributed and allow oxidized As and Fe to persist in other organic-rich, reducing environments.

Unraveling biogeochemical complexity through better integration of experiments and modeling.

The evolution of groundwater quality in natural and contaminated aquifers is affected by complex interactions between physical transport and biogeochemical reactions. Identifying and quantifying the processes that control the overall system behavior is the key driver for experimentation and monitoring. However, we argue that, in contrast to other disciplines in earth sciences, process-based computer models are currently vastly underutilized in the quest for understanding subsurface biogeochemistry. Such models provide an essential avenue for quantitatively testing hypothetical combinations of interacting, complex physical and chemical processes. If a particular conceptual model, and its numerical counterpart, cannot adequately reproduce observed experimental data, its underlying hypothesis must be rejected. This quantitative process of hypothesis testing and falsification is central to scientific discovery. We provide a perspective on how closer interactions between experimentalists and numerical modelers would enhance this scientific process, and discuss the potential limitations that are currently holding us back. We also propose a data-model nexus involving a greater use of numerical process-based models for a more rigorous analysis of experimental observations while also generating the basis for a systematic improvement in the design of future experiments.

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.

Spatial relationship between well water arsenic and uranium in Northern Plains native lands.

Arsenic and uranium in unregulated private wells affect many rural populations across the US. The distribution of these contaminants in the private wells of most American Indian communities is poorly characterized, and seldom studied together. Here, we evaluate the association between drinking water arsenic and uranium levels in wells (n = 441) from three tribal regions in North Dakota and South Dakota participating in the Strong Heart Water Study. Groundwater contamination was extensive; 29% and 7% of wells exceeded maximum contaminant levels for arsenic and uranium respectively. 81% of wells had both arsenic and uranium concentrations at one-tenth of their human-health benchmark (arsenic, 1 µg/L; uranium 3 µg/L). Well arsenic and uranium concentrations were uncorrelated (rs = 0.06); however, there appeared to be a spatial correlation of wells co-contaminated by arsenic and uranium associated with flow along a geologic contact. These findings indicate the importance of measuring multiple metals in well water, and to understand underlying hydrogeological conditions. The underlying mechanisms for the prevalence of arsenic and uranium across Northern Plains Tribal Lands in the US, and in particular the occurrence of both elevated arsenic and uranium in drinking water wells in this region, demands further study.