Model-Based Analysis of Arsenic Retention by Stimulated Iron Mineral Transformation under Coastal Aquifer Conditions.

A multitude of geochemical processes control the aqueous concentration and transport properties of trace metal contaminants such as arsenic (As) in groundwater environments. Effective As remediation, especially under reducing conditions, has remained a significant challenge. Fe(II) nitrate treatments are a promising option for As immobilization but require optimization to be most effective. Here, we develop a process-based numerical modeling framework to provide an in-depth understanding of the geochemical mechanisms controlling the response of As-contaminated sediments to Fe(II) nitrate treatment. The analyzed data sets included time series from two batch experiments (control vs treatment) and effluent concentrations from a flow-through column experiment. The reaction network incorporates a mixture of homogeneous and heterogeneous reactions affecting Fe redox chemistry. Modeling revealed that the precipitation of the Fe treatment caused a rapid pH decline, which then triggered multiple heterogeneous buffering processes. The model quantifies key processes for effective remediation, including the transfer of aqueous As to adsorbed As and the transformation of Fe minerals, which act as sorption hosts, from amorphous to more stable phases. The developed model provides the basis for predictions of the remedial benefits of Fe(II) nitrate treatments under varying geochemical and hydrogeological conditions, particularly in high-As coastal environments.

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 (CWS) 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.

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.

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.

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.

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.

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.

Highly bioavailable dust-borne iron delivered to the Southern Ocean during glacial periods.

Changes in bioavailable dust-borne iron (Fe) supply to the iron-limited Southern Ocean may influence climate by modulating phytoplankton growth and CO2 fixation into organic matter that is exported to the deep ocean. The chemical form (speciation) of Fe impacts its bioavailability, and glacial weathering produces highly labile and bioavailable Fe minerals in modern dust sources. However, the speciation of dust-borne Fe reaching the iron-limited Southern Ocean on glacial-interglacial timescales is unknown, and its impact on the bioavailable iron supply over geologic time has not been quantified. Here we use X-ray absorption spectroscopy on subantarctic South Atlantic and South Pacific marine sediments to reconstruct dust-borne Fe speciation over the last glacial cycle, and determine the impact of glacial activity and glaciogenic dust sources on bioavailable Fe supply. We show that the Fe(II) content, as a percentage of total dust-borne Fe, increases from ∼5 to 10% in interglacial periods to ∼25 to 45% in glacial periods. Consequently, the highly bioavailable Fe(II) flux increases by a factor of ∼15 to 20 in glacial periods compared with the current interglacial, whereas the total Fe flux increases only by a factor of ∼3 to 5. The change in Fe speciation is dominated by primary Fe(II) silicates characteristic of glaciogenic dust. Our results suggest that glacial physical weathering increases the proportion of highly bioavailable Fe(II) in dust that reaches the subantarctic Southern Ocean in glacial periods, which represents a positive feedback between glacial activity and cold glacial temperatures.

Arsenic mobilization from iron oxides in the presence of oxalic acid under hydrodynamic conditions.

Oxalic acid potentially enhances pump-and-treat for groundwater As remediation by accelerating mobilization. This study examines how oxalic acid mobilizes As from Fe(III)-oxide coated sand under hydrodynamic conditions. Four columns were packed with metal-substituted ferrihydrite or goethite to 1% Fe, presorbed to 50% As surface coverage, and reacted with pH = 2.2 artificial groundwater amended with 10 mM oxalic acid at 1 m day-1. Arsenic elution was affected by both As and Fe speciation. Although the As(V) columns experienced faster substrate dissolution, As(V) elution was delayed by re-adsorption, whereas As(III) elution was rapid due to pH decrease that prevented re-adsorption. Cr-ferrihydrite and Ni-goethite dissolved both effectively initially but then diverged. The Cr-ferrihydrite columns experienced continuous stoichiometric Fe and Cr release, and As release could be sustained. The Ni-goethite columns initially experienced nonstoichiometric Fe and Ni release, and As release was extensive. Such release, however, was not sustained. We hypothesized that Ni-goethite contained sites with distinct reactivity, and oxalic acid targeted readily-dissolved, sorption-dense sites. Our data indicate that oxalic acid-enhanced pump-and-treat methods would be easier to apply to aquifers dominated by As(III), requiring less amendment to be injected; such oxalic acid-enhanced methods remove reactive sediment Fe and As, potentially preventing future groundwater contamination.

Model-Based Analysis of Arsenic Immobilization via Iron Mineral Transformation under Advective Flows.

Recent laboratory studies have demonstrated that coinjection of nitrate and Fe(II) (as ferrous sulfate) to As-bearing sediments can produce an Fe mineral assemblage containing magnetite capable of immobilizing advected As under a relatively wide range of aquifer conditions. This study combined laboratory findings with process-based numerical modeling approaches, to quantify the observed Fe mineral (trans)formation and concomitant As partitioning dynamics and to assess potential nitrate-Fe(II) remediation strategies for field implementation. The model development was guided by detailed solution and sediment data from our well-controlled column experiment. The modeling results demonstrated that the fate of As during the experiment was primarily driven by ferrihydrite formation and reductive transformation and that different site densities were identified for natural and neoformed ferrihydrite to explain the observations both before and after nitrate-Fe(II) injection. Our results also highlighted that when ferrihydrite was nearing depletion, As immobilization ultimately relied on the presence of magnetite. On the basis of the column model, field-scale predictive simulations were conducted to illustrate the feasibility of the nitrate-Fe(II) strategy for intercepting advected As from a plume. The predictive simulations, which suggested that long-term As immobilization was feasible, favored a scenario that maintains high dissolved Fe(II) concentration during injection periods and thereby converts ferrihydrite to magnetite.

High particulate iron(II) content in glacially sourced dusts enhances productivity of a model diatom.

Little is known about the bioavailability of iron (Fe) in natural dusts and the impact of dust mineralogy on Fe utilization by photosynthetic organisms. Variation in the supply of bioavailable Fe to the ocean has the potential to influence the global carbon cycle by modulating primary production in the Southern Ocean. Much of the dust deposited across the Southern Ocean is sourced from South America, particularly Patagonia, where the waxing and waning of past and present glaciers generate fresh glaciogenic material that contrasts with aged and chemically weathered nonglaciogenic sediments. We show that these two potential sources of modern-day dust are mineralogically distinct, where glaciogenic dust sources contain mostly Fe(II)-rich primary silicate minerals, and nearby nonglaciogenic dust sources contain mostly Fe(III)-rich oxyhydroxide and Fe(III) silicate weathering products. In laboratory culture experiments, Phaeodactylum tricornutum, a well-studied coastal model diatom, grows more rapidly, and with higher photosynthetic efficiency, with input of glaciogenic particulates compared to that of nonglaciogenic particulates due to these differences in Fe mineralogy. Monod nutrient accessibility models fit to our data suggest that particulate Fe(II) content, rather than abiotic solubility, controls the Fe bioavailability in our Fe fertilization experiments. Thus, it is possible for this diatom to access particulate Fe in dusts by another mechanism besides uptake of unchelated Fe (Fe') dissolved from particles into the bulk solution. If this capability is widespread in the Southern Ocean, then dusts deposited to the Southern Ocean in cold glacial periods are likely more bioavailable than those deposited in warm interglacial periods.

Enhanced and stabilized arsenic retention in microcosms through the microbial oxidation of ferrous iron by nitrate.

Magnetite strongly retains As, and is relatively stable under Fe(III)-reducing conditions common in aquifers that release As. Here, laboratory microcosm experiments were conducted to investigate a potential As remediation method involving magnetite formation, using groundwater and sediments from the Vineland Superfund site. The microcosms were amended with various combinations of nitrate, Fe(II) (aq) (as ferrous sulfate) and lactate, and were incubated for more than 5 weeks. In the microcosms enriched with 10 mM nitrate and 5 mM Fe(II) (aq), black magnetic particles were produced, and As removal from solution was observed even under sustained Fe(III) reduction stimulated by the addition of 10 mM lactate. The enhanced As retention was mainly attributed to co-precipitation within magnetite and adsorption on a mixture of magnetite and ferrihydrite. Sequential chemical extraction, X-ray absorption spectroscopy and magnetic susceptibility measurements showed that these minerals formed at pH 6-7 following nitrate-Fe(II) addition, and As-bearing magnetite was stable under reducing conditions. Scanning electron microscopy and X-ray diffraction indicated that nano-particulate magnetite was produced as coatings on fine sediments, and no aging effect was detected on morphology over the course of incubation. These results suggest that a magnetite based strategy may be a long-term remedial option for As-contaminated aquifers.

Changes in iron, sulfur, and arsenic speciation associated with bacterial sulfate reduction in ferrihydrite-rich systems.

Biologically mediated redox processes have been shown to affect the mobility of iron oxide-bound arsenic in reducing aquifers. This work investigates how dissimilatory sulfate reduction and secondary iron reduction affect sulfur, iron, and arsenic speciation. Incubation experiments were conducted with As(III/V)-bearing ferrihydrite in carbonate-buffered artificial groundwater enriched with lactate (10 mM) and sulfate (0.08-10 mM) and inoculated with Desulfovibrio vulgaris (ATCC 7757, formerly D. desulfuricans), which reduces sulfate but not iron or arsenic. Sulfidization of ferrihydrite led to formation of magnetite, elemental sulfur, and trace iron sulfides. Observed reaction rates imply that the majority of sulfide is recycled to sulfate, promoting microbial sulfate reduction in low-sulfate systems. Despite dramatic changes in Fe and S speciation, and minimal formation of Fe or As sulfides, most As remained in the solid phase. Arsenic was not solubilized in As(V)-loaded incubations, which experienced slow As reduction by sulfide, whereas As(III)-loaded incubations showed limited and transient As release associated with iron remineralization. This suggests that As(III) production is critical to As release under reducing conditions, with sulfate reduction alone unlikely to release As. These data also suggest that bacterial reduction of As(V) is necessary for As sequestration in sulfides, even where sulfate reduction is active.

Effect of groundwater iron and phosphate on the efficacy of arsenic removal by iron-amended BioSand filters.

Naturally occurring arsenic in groundwater in Cambodia is a serious health concern. This study tested the efficacy of a BioSand filter amended with iron nails, Kanchan filter, as a household water treatment option with three natural arsenic-bearing groundwater sources of varying compositions and spiked with lab cultured E. coli and MS2. The effectiveness of arsenic and pathogen removal was not constant over time and was highly dependent on the influent composition. The filter was relatively ineffective in treating arsenic contaminated groundwater and effluent arsenic concentrations were between 74 and 2206 microg L(-1), which is higher than accepted drinkng water standards. The overall average arsenic removal was 39.4, 74.9, and 45.4%, respectively, and the extent of arsenic removal was not related to the influent arsenic concentration. The main reasons for poor arsenic removal was due to the combination of high influent P (> 0.5 mg L(-1)) and low Fe (< 5 mg L(-1)) concentrations and that the added iron nails were largely ineffective due to insufficient contact time withthe water. The findings suggest that such amended filters should not be widely deployed until improvements are made to address the consistency and efficacy of treatment In addition, the filter poses some potential health risk associated with the production of elevated nitrate levels in the effluent within the filter, possibly due to nitrification and high levels of ammonia in the groundwater.

Impact of land disturbance on the fate of arsenical pesticides.

Increasing development of historic farmlands raises questions regarding the fate of pesticides applied when these land were in cultivation. We quantified As and Pb budgets in field soils in two orchards where arsenical pesticides were applied in the early 20th century and a third uncontaminated control field. Sequential extractions and X-ray analyses also were used to determine mineral phases. In addition, we measured metal loads in drainages adjacent to the fields and in two common macroinvertebrate taxa within the wetland at the outlet of the drainages. We find that the applied As and Pb have undergone little vertical redistribution; concentrations of As and Pb in the top 25 cm of contaminated orchard soils are higher than in the uncontaminated control field. However, none of the applied lead arsenate (PbHAsO4) remains in its original mineral phase. Instead, the metals are now primarily adsorbed onto fine silt and clay-sized amorphous oxides and organic matter. Further, physical erosion associated with tilling and replanting appears to have mobilized the fine-particulate-bound As and Pb in one orchard. The remobilized metals are found in sediments in the stream channel draining the tilled orchard. It is unclear if the As and Pb transported sediments are biologically active; average macroinvertebrate metal burdens in the wetland are not elevated above those observed elsewhere in the region. However, little of the mobilized metals may have reached the wetland. These results demonstrate that land use change can significantly impact the retention of arsenical pesticides.

Landfill-stimulated iron reduction and arsenic release at the Coakley Superfund Site (NH).

Arsenic is a contaminant at more than one-third of all Superfund Sites in the United States. Frequently this contamination appearsto resultfrom geochemical processes rather than the presence of a well-defined arsenic source. Here we examine the geochemical processes that regulate arsenic levels at the Coakley Landfill Superfund Site (NH), a site contaminated with As, Cr, Pb, Ni, Zn, and aromatic hydrocarbons. Long-term field observations indicate that the concentrations of most of these contaminants have diminished as a result of treatment by monitored natural attenuation begun in 1998; however, dissolved arsenic levels increased modestly over the same interval. We attribute this increase to the reductive release of arsenic associated with poorly crystalline iron hydroxides within a glaciomarine clay layer within the overburden underlying the former landfill. Anaerobic batch incubations that stimulated iron reduction in the glaciomarine clay released appreciable dissolved arsenic and iron. Field observations also suggest that iron reduction associated with biodegradation of organic waste are partly responsible for arsenic release; over the five-year study period since a cap was emplaced to prevent water flow through the site, decreases in groundwater dissolved benzene concentrations at the landfill are correlated with increases in dissolved arsenic concentrations, consistent with the microbial decomposition of both benzene and other organics, and reduction of arsenic-bearing iron oxides. Treatment of contaminated groundwater increasingly is based on stimulating natural biogeochemical processes to degrade the contaminants. These results indicate that reducing environments created within organic contaminant plumes may release arsenic. In fact, the strong correlation (>80%) between elevated arsenic levels and organic contamination in groundwater systems at Superfund Sites across the United States suggests that arsenic contamination caused by natural degradation of organic contaminants may be widespread.

Differential adsorption of molybdate and tetrathiomolybdate on pyrite (FeS2).

Molybdenum is a nutrient important for a variety of biological functions, most notably nitrogen fixation. Molybdenum availability is limited through sorption reactions, particularly in environments rich in sulfide minerals. This study examines the sorption of two major molybdenum species, molybdate (MoO4(2-)) and tetrathiomolybdate (MoS4(2-)), on synthetic pyrite (FeS2) as a function of solution composition. Both MoO4(2-) and MoS4(2-) partitioned strongly on FeS2 under a range of conditions and ionic strengths. Molybdate and tetrathiomolybdate adsorption obeyed a Langmuir isotherm with a calculated site density between 2 and 3 sites/nm2 under acidic and circumneutral conditions, which decreased to less than 1 site/ nm2 at pH 9. Although both MoO4(2-) and MoS4(2-) adsorbed most strongly under moderately acidic conditions, MoO4(2-) readily desorbed while MoS4(2-) remained adsorbed even at high pH. The reversibility of MoO4(2-) adsorption suggests the formation of labile surface complexes while MoS4(2-) likely forms strong inner-sphere complexes. X-ray absorption spectroscopy was used to determine the structure of the surface complexes. Molybdate formed bidentate, mononuclear complexes on FeS2. The Mo-S and Mo-Fe distances for tetrathiomolybdate on pyrite are consistent with the formation of Mo-Fe-S cubane-type clusters. The high affinity of MoS4(2-) for FeS2, as well as its resistance to desorption, supports the hypothesis that thiomolybdate species are the reactive Mo constituents in reduced sediments and may control Mo enrichment in anoxic marine environments.