Hydrous ferric oxide incorporated diatomite for remediation of arsenic contaminated groundwater

Two reactive media [zerovalent iron (ZVI, Fisher Fe0) and amorphous hydrous ferric oxide (HFO)-incorporated porous, naturally occurring aluminum silicate diatomite [designated as Fe (25%)-diatomite]], were tested for batch kinetic, pH-controlled differential column batch reactors (DCBRs), in small- and large-scale column tests (about 50 and 900 mL of bed volume) with groundwater from a hazardous waste site containing high concentrations of arsenic (both organic and inorganic species), as well as other toxic or carcinogenic volatile and semivolatile organic compounds (VOC/SVOCs). Granular activated carbon (GAC) was also included as a reactive media since a permeable reactive barrier (PRB) at the subject site would need to address the hazardous VOC/SVOC contamination as well as arsenic. The groundwater contained an extremely high arsenic concentration (341 mg L(-1)) and the results of ion chromatography and inductively coupled plasma mass spectrometry (IC-ICP-MS) analysis showed that the dominant arsenic species were arsenite (45.1%) and monomethyl arsenic acid (MMAA, 22.7%), while dimethyl arsenic acid (DMAA) and arsenate were only 2.4 and 1.3%, respectively. Based on these proportions of arsenic species and the initial As-to-Fe molar ratio (0.15 molAs mole(-1)), batch kinetic tests revealed that the sorption density (0.076 molAs molFe(-1)) for Fe (25%)-diatomite seems to be less than the expected value (0.086 molAs molFe(-1) calculated from the sorption density data reported by Lafferty and Loeppert (Environ. Sci. Technol. 2005, 39, 2120-2127), implying that natural organic matters (NOMs) might play a significant role in reducing arsenic removal efficiency. The results of pH-controlled DCBR tests using different synthetic species of arsenic solution showed that the humic acid inhibited the MMAA removal of Fe (25%)-diatomite more than arsenite. The mixed system of GAC and Fe (25%)-diatomite increased the arsenic sorption speed to more than that of either individual media alone. This increase might be deduced by the fact that the addition of GAC could enhance arsenic removal performance of Fe (25%)-diatomite through removing comparably high portions of NOMs. Small- and large-scale column studies demonstrated that the empty bed contact time (EBCT) significantly affected sorpton capacities at breakthrough (C = 0.5 C0) forthe Fe0/sand (50/50, w/w) mixture, but notfor GAC preloaded Fe (25%)-diatomite. In the large-scale column tests with actual groundwater conditions, the GAC preloaded Fe (25%)-diatomite effectively reduced arsenic to below 50 microg L(-1) for 44 days; additionally, most species of VOC/SVOCs were also simultaneously attenuated to levels below detection.     

Modeling the probability of arsenic in groundwater in New England as a tool for exposure assessment

We developed a process-based model to predict the probability of arsenic exceeding 5 microg/L in drinking water wells in New England bedrock aquifers. The model is being used for exposure assessment in an epidemiologic study of bladder cancer. One important study hypothesis that may explain increased bladder cancer risk is elevated concentrations of inorganic arsenic in drinking water. In eastern New England, 20-30% of private wells exceed the arsenic drinking water standard of 10 micrograms per liter. Our predictive model significantly improves the understanding of factors associated with arsenic contamination in New England. Specific rock types, high arsenic concentrations in stream sediments, geochemical factors related to areas of Pleistocene marine inundation and proximity to intrusive granitic plutons, and hydrologic and landscape variables relating to groundwater residence time increase the probability of arsenic occurrence in groundwater. Previous studies suggest that arsenic in bedrock groundwater may be partly from past arsenical pesticide use. Variables representing historic agricultural inputs do not improve the model, indicating that this source does not significantly contribute to current arsenic concentrations. Due to the complexity of the fractured bedrock aquifers in the region, well depth and related variables also are not significant predictors.     

Testing groundwater for arsenic in Bangladesh before installing a well

Profiles of groundwater and sediment properties were collected at three sites in Bangladesh with an inexpensive sampling device that is deployed by modifying the local manual drilling method. Dissolved As concentrations in the groundwater samples ranging from 5 to 600 microg/L between 5 and 50 m depth closely matched vertical profiles from nearby nests of monitoring wells. In combination with a field kit, the device provides a means of targeting aquifers for the installation of tube wells that meet the drinking water standard for As. The device is also a useful research tool for unraveling the relationships between the As content of groundwater and the complex structure of flood plain and deltaic environments throughout South Asia.     

Preservation of inorganic arsenic species in groundwater

The objective of this research was to develop a robust preservation method for stabilizing inorganic As(IlI/V) species in synthetic and actual groundwaters. Ethylenediaminetetraacetic acid (EDTA), H2SO4, H3PO4, and EDTA-acetic acid (HAc) were evaluated in synthetic groundwater containing 3 mg/L Fe(ll) in the pH range 6.5-8.4 and Eh range -100 to +200 mV at room temperature. In the absence of strong UV light, only EDTA-HAc was found to be an effective preservative under all the experimental conditions tested. A total of 89 samples (including 16 samples in triplicate) from 55 drinking waterwells in Minnesota, California, and North Dakota were preserved with a combination of EDTA-HAc and speciated to evaluate its effectiveness for preserving inorganic arsenic species in actual groundwater samples. The preserved and field-speciated samples were repeatedly speciated and analyzed in the laboratory for up to 85 days after collection. Field-speciated As(lll) concentrations were compared with the As(lll) concentrations in the preserved samples. The results were highly correlated (slope 0.9773, R2 = 0.9986), which indicates that during sample transportation and storage the distribution of arsenic species did not change for samples preserved with EDTA-HAc.     

Chromium-removal processes during groundwater remediation by a zerovalent iron permeable reactive barrier

Solid-phase associations of chromium were examined in core materials collected from a full-scale, zerovalent iron permeable reactive barrier (PRB) at the U.S. Coast Guard Support Center located near Elizabeth City, NC. The PRB was installed in 1996 to treat groundwater contaminated with hexavalent chromium. After eight years of operation, the PRB remains effective at reducing concentrations of Cr from average values >1500 microg L(-1) in groundwater hydraulically upgradient of the PRB to values <1 microg L(-1) in groundwater within and hydraulically downgradient of the PRB. Chromium removal from groundwater occurs at the leading edge of the PRB and also within the aquifer immediately upgradient of the PRB. These regions also witness the greatest amount of secondary mineral formation due to steep geochemical gradients that result from the corrosion of zerovalent iron. X-ray absorption near-edge structure (XANES) spectroscopy indicated that chromium is predominantly in the trivalent oxidation state, confirming that reductive processes are responsible for Cr sequestration. XANES spectra and microscopy results suggest that Cr is, in part, associated with iron sulfide grains formed as a consequence of microbially mediated sulfate reduction in and around the PRB. Results of this study provide evidence that secondary iron-bearing mineral products may enhance the capacity of zerovalent iron systems to remediate Cr in groundwater, either through redox reactions at the mineral-water interface or by the release of Fe(II) to solution via mineral dissolution and/or metal corrosion.     

In situ remediation of arsenic in simulated groundwater using zerovalent iron: laboratory column tests on combined effects of phosphate and silicate

We performed three column tests to study the behavior of permeable reactive barrier (PRB) materials to remove arsenic under dynamic flow conditions in the absence as well as in the presence of added phosphate and silicate. The column consisted of a 10.3 cm depth of 50:50 (w:w, Peerless iron:sand) in the middle and a 10.3 cm depth of a sediment from Elizabeth City, NC, in both upper and lower portions of the 31-cm-long glass column (2.5 cm in diameter) with three side sampling ports. The flow velocity (upflow mode) was maintained at 4.3 m d(-1) during the 3-4-month experiments. As expected, dissolved As concentrations in different positions of the column generally followed the order: column influent > bottom port effluent > middle port effluent > top port effluent > column effluent. The steady-state As removal in the middle Peerless iron and sand mixture zone might be attributed to the continuous supply of corroded iron in the form of iron oxides and hydroxides that served as the sorbents for both As(V) and As(III). Consistent with previous batch study findings, dissolved phosphate (0.5 or 1 mg of P L(-1)) and silicate (10 or 20 mg of Si L(-1)) showed strong inhibition for As(V) and As(III) (1 mg of As(V) L(-1) + 1 mg of As(III) L(-1) in 7 mM NaCl + 0.86 mM CaSO4) removal by Peerless iron in the column tests. The presence of combined phosphate and silicate resulted in earlier breakthrough (C = 0.5C0) and earlier complete breakthrough of dissolved arsenic relative to absence of added phosphate and silicate in the bottom port effluent. Competition between As(V)/As(III) and phosphate/silicate forthe sorption sites on the corrosion products of Peerless iron seems to be the cause of the observations. This effect is especially important in the case of silicate for designing a PRB of zerovalent iron for field use because dissolved silicate is ubiquitous in terrestrial waters.     

Uptake of organic pollutants by silica--polycation-Immobilized micelles for groundwater remediation

Interest has grown in designing new materials for groundwater treatment via "permeable reactive barriers". In the present case, a model siliceous surface, controlled pore glass (CPG), was treated with a polycation (quaternized polyvinyl pyridine, QPVP) which immobilizes anionic/nonionic mixed micelles, in order to solubilize a variety of hydrophobic pollutants. Polymer adsorption on CPG showed atypically slow kinetics and linear adsorption isotherms, which may be a consequence of the substrate porosity. The highest toluene solubilization efficiency was achieved for the silica-polycation-immobilized micelles (SPIM) with the highest polymer loading and lowest micelle binding, a result discussed in terms of the configuration of the bound polymer and the corresponding state of the bound micelles. The ability of SPIM to treat simultaneously a wide range of pollutants and reduce their concentration in solution by 20-90% was demonstrated. Optimization of SPIM systems for remediation calls for a better understanding of both the local environment of the bound micelles and their intrinsic affinities for different hydrophobic pollutants.     

Reliability of a commercial kit to test groundwater for arsenic in Bangladesh

A comparison of field and laboratory measurements of arsenic in groundwater of Araihazar, Bangladesh, indicates that the most widely used field kit correctly determined the status of 88% of 799 wells relative to the local standard of 50 microg/L As. Additional tests showthatthe inconsistencies, mainly underestimates in the 50-100 microg/L As range, can be avoided by increasing the reaction time from 20 to 40 min. Despite this limitation, the field data already compiled for millions of wells by the Bangladesh Arsenic Mitigation and Water Supply Project, in combination with information on well location and depth, should prove to be extremely useful to prioritize interventions in thousands of affected villages.     

Flushing history as a hydrogeological control on the regional distribution of arsenic in shallow groundwater of the Bengal Basin

Whereas serious health consequences of widespread consumption of groundwater elevated in As have been documented in several South Asian countries, the mechanisms responsible for As mobilization in reducing aquifers remain poorly understood. We document here a previously unrecognized and consistent relationship between dissolved As concentrations in reducing groundwater and the phosphate-mobilizable As content of aquifer sediment for a set of precisely depth-matched samples from across Bangladesh. The relationship holds across nearly 3 orders of magnitude in As concentrations and suggests that regional as well as local patterns of dissolved As in shallow groundwater are set by the solid phase according to a remarkably constant ratio of approximately 250 microg/L dissolved As per 1 mg/kg P-mobilizable As. We use this relationship in a simple model of groundwater recharge to propose that the distribution of groundwater As in shallow aquifers of the Bengal Basin could primarily reflect the different flushing histories of sand formations deposited in the region over the past several thousand years.     

34S/32S fractionation during sulfate reduction in groundwater treatment systems: reactive transport modeling

Isotope ratio measurements provide a tool for indicating the relative significance of biogeochemical reactions and for constraining estimates of the extent and rate of reactions in passive treatment systems. In this paper, the reactive transport model MIN3P is used to evaluate sulfur isotope fractionation in column experiments designed to simulate treatment of contaminated water by microbially mediated sulfate reduction occurring within organic carbon-based and iron and carbon-based permeable reactive barriers. A mass dependent fractionation model was used to determine reaction rates for 32S and 34S compounds during reduction, precipitation, and dissolution reactions and to track isotope-dependent mass transfer during SO4 removal. The δ34S values obtained from the MIN3P model were similar to those obtained from the Rayleigh equation, indicating that there was not a significant difference between the conceptual models. Differences between the MIN3P derived α value and the Rayleigh equation derived value were attributed to minor changes in the dissolution and precipitation rate of gypsum and mathematical differences in the fitting models. The results indicated that the prediction of δ34S was fairly insensitive to differences in the fractionation factor at the concentration ranges measured in the current study. However, more significant differences would be expected at low sulfate conditions.     

In situ chemical reduction of Cr(VI) in groundwater using a combination of ferrous sulfate and sodium dithionite: a field investigation

A field study was conducted to evaluate the performance of a ferrous iron based in situ redox zone for the treatment of a dissolved phase Cr(VI) plume at a former industrial site. The ferrous iron based in situ redox zone was created by injecting a blend of 0.2 M ferrous sulfate and 0.2 M sodium dithionite into the path of a dissolved Cr(VI) plume within a shallow medium to fine sand unconfined aquifer formation. Monitoring data collected over a period of 1020 days after more than 100 m of linear groundwater flow through the treatment zone indicated sustained treatment of dissolved phase Cr(VI) from initial concentrations between 4 and 8 mg/L to less than 0.015 mg/L. Sustained treatment is assumed to be primarily due to the reduction of Cr(VI) to Cr(III) by ferrous iron adsorbed to, precipitated on, and/or incorporated into aquifer iron (hydr)oxide solid surfaces within the treatment zone. Precipitated phases likely include FeCO3 and FeS based on saturation index considerations and SEM/EDS analysis. The detection of solid phase sulfites and thiosulfates in aquifer sediments collected from the treatment zone more than 2 years following injection suggests dithionite decomposition products may also play a significant role in the long-term treatment of the dissolved phase Cr(VI).     

Selective remediation of contaminated sites using a two-level multiphase strategy and geostatistics

Selective soil remediation aims to reduce costs by cleaning only the fraction of an exposure unit (EU) necessary to lower the average concentration below the regulatory threshold. This approach requires a prior stratification of each EU into smaller remediation units (RU) which are then selected according to various criteria. This paper presents a geostatistical framework to account for uncertainties attached to both RU and EU average concentrations in selective remediation. The selection of RUs is based on their impact on the postremediation probability for the EU average concentration to exceed the regulatory threshold, which is assessed using geostatistical stochastic simulation. Application of the technique to a set of 600 dioxin concentrations collected at Piazza Road EPA Superfund site in Missouri shows a substantial decrease in the number of RU remediated compared with single phase remediation. The lower remediation costs achieved by the new strategy are obtained to the detriment of a higher risk of false negatives, yet for this data set this risk remains below the 5% rate set by EPA region 7.     

Mechanisms of uranium interactions with hydroxyapatite: implications for groundwater remediation

The speciation of U(VI) sorbed to synthetic hydroxyapatite was investigated using a combination of U LIII-edge XAS, synchrotron XRD, batch uptake measurements, and SEM-EDS. The mechanisms of U(VI) removal by apatite were determined in order to evaluate the feasibility of apatite-based in-situ permeable reactive barriers (PRBs). In batch U(VI) uptake experiments with synthetic hydroxyapatite (HA), near complete removal of dissolved uranium (>99.5%) to <0.05 microM was observed over a range of total U(VI) concentrations up to equimolar of the total P in the suspension. XRD and XAS analyses of U(VI)-reacted HA at sorbed concentrations < or = 4,700 ppm U(VI) suggested that uranium(VI) phosphate, hydroxide, and carbonate solids were not present at these concentrations. Fits to EXAFS spectra indicate the presence of Ca neighbors at 3.81 A. U-Ca separation, suggesting that U(VI) adsorbs to the HA surfaces as an inner-sphere complex. Uranium(VI) phosphate solid phases were not detected in HA with 4700 ppm sorbed U(VI) by backscatter SEM or EDS, in agreement with the surface complexation process. In contrast, U(VI) speciation in samples that exceeded 7000 ppm sorbed U(VI) included a crystalline uranium(VI) phosphate solid phase, identified as chernikovite by XRD. At these higher concentrations, a secondary, uranium(VI) phosphate solid was detected by SEM-EDS, consistent with chernikovite precipitation. Autunite formation occurred at total U:P molar ratios > or = 0.2. Our findings provide a basis for evaluating U(VI) sorption mechanisms by commercially available natural apatites for use in development of PRBs for groundwater U(VI) remediation.     

Statistical modeling of global geogenic arsenic contamination in groundwater

Contamination of groundwaters with geogenic arsenic poses a major health risk to millions of people. Although the main geochemical mechanisms of arsenic mobilization are well understood, the worldwide scale of affected regions is still unknown. In this study we used a large database of measured arsenic concentration in groundwaters (around 20,000 data points) from around the world as well as digital maps of physical characteristics such as soil, geology, climate, and elevation to model probability maps of global arsenic contamination. A novel rule-based statistical procedure was used to combine the physical data and expert knowledge to delineate two process regions for arsenic mobilization: "reducing" and "high-pH/ oxidizing". Arsenic concentrations were modeled in each region using regression analysis and adaptive neuro-fuzzy inferencing followed by Latin hypercube sampling for uncertainty propagation to produce probability maps. The derived global arsenic models could benefit from more accurate geologic information and aquifer chemical/physical information. Using some proxy surface information, however, the models explained 77% of arsenic variation in reducing regions and 68% of arsenic variation in high-pH/oxidizing regions. The probability maps based on the above models correspond well with the known contaminated regions around the world and delineate new untested areas that have a high probability of arsenic contamination. Notable among these regions are South East and North West of China in Asia, Central Australia, New Zealand, Northern Afghanistan, and Northern Mali and Zambia in Africa.     

Removal of methylated arsenic in groundwater with iron filings

Field and laboratory experiments were conducted to study the potential use of Fe filings to remove monomethyl arsenate (MMA) and dimethyl arsenate (DMA) from contaminated waters. Batch experiments show that the affinity of MMAfor Fe filings is comparable to that of inorganic arsenate, but lower than that for arsenite. In contrast, very little DMA was retained by Fe filings or their corrosion products. The wide range of affinities of different As species for Fe filings was confirmed by a series of retention and selective-leaching experiments using small columns and As-spiked groundwater. The effectiveness of Fe filings was also demonstrated with a field deployment at a U.S. Superfund site where groundwater is highly contaminated with both organic and inorganic As species. Over the course of 4 months, a 3 L cartridge of Fe filings removed > 85% of As contained in 16000 L of groundwater containing 1-1.5 mg/L total dissolved As, approximately 30% of which was organic As. The results indicate that Fe filings could be used to treat groundwater contaminated with MMA, which is the main organic form of As at most contaminated sites. Indications of partial demethylation in the column of Fe filings suggest conditions might be optimized further to enhance the removal of DMA.     

Supercritical fluid extraction as a potential mitigation strategy for the reduction of acrylamide level in coffee

The removal of acrylamide from coffee through supercritical CO₂ extraction has been investigated for the first time. Two steps were performed: a pre-roasting treatment and a supercritical extraction process. The main aim of this first work was to investigate the feasibility of the process more than the impact of the treatment on the organoleptic properties of coffee. The efficiency of acrylamide removal was checked by measuring its content in the coffee beans before and after the supercritical treatment. The role of temperature, pressure, extraction time and the addition of a modifier (ethanol) was examined.     

Confounding impacts of iron reduction on arsenic retention

A transition from oxidizing to reducing conditions has long been implicated to increase aqueous As concentrations, for which reductive dissolution of iron (hydr)oxides is commonly implicated as the primary culprit. Confounding our understanding of processes controlling As retention, however, is that reductive transformation of ferrihydrite has recently been shown to promote As retention rather than release. To resolve the role iron phases have in regulating arsenic concentrations, here we examine As desorption from ferrihydrite-coated sands presorbed with As(III); experiments were performed at circumneutral pH under Fe-reducing conditions with the dissimilatory iron reducing bacterium Shewanella putrefaciens strain CN-32 over extended time periods. We reveal that with the initial phase of iron reduction, ferrihydrite undergoes transformation to secondary phases and increases As(III) retention (relative to abiotic controls). However, with increased reaction time, cessation of the phase transitions and ensuing reductive dissolution result in prolonged release of As(III) to the aqueous phase. Our results suggest that As(III) retention during iron reduction is temporally dependent on secondary precipitation of iron phases; during transformation to secondary phases, particularly magnetite, As(III) retention is enhanced even relative to oxidized systems. However, conditions that retard secondary transformation (more stable iron oxides or limited iron reducing bacterial activity), or prolonged anaerobiosis, will lead to both the dissolution of ferric (hydr)oxides and release of As(III) to the aqueous phase.     

Removal of arsenic by bead cellulose loaded with iron oxyhydroxide from groundwater

A new adsorbent, bead cellulose loaded with iron oxyhydroxide (BCF), was prepared and applied for the adsorption and removal of arsenate and arsenite from aqueous systems. The continuing loading process of Fe in the cellulose beads was realized through hydrolization of ferric salts when alkaline solution was added dropwise. Spherical BCF had excellent mechanical and hydraulic properties. Akaganeite (beta-FeOOH), the reactive center of BCF that was stably loaded into the cellulose, had a high sensitivity to arsenite as well as arsenate. The maximum content of Fe in BCF reached 50% (w/w). In this study we investigated the adsorption behavior of arsenite and arsenate on BCF, including adsorption isotherms, adsorption kinetics, the influence of pH and competing anions on adsorption, and column experiments. The adsorption data accorded with both Freundlich and Langmuir isotherms. The adsorption capacity for arsenite and arsenate was 99.6 and 33.2 mg/g BCF at pH 7.0 with an Fe content of 220 mg/ mL. Kinetic data fitted well to the pseudo-second-order reaction model. Arsenate elimination was favored at acidic pH, whereas the adsorption of arsenite by BCF was found to be effective in a wide pH range of 5-11. Under the experimental conditions, the addition of sulfate had no effect on arsenic adsorption, whereas phosphate greatly influenced the elimination of both arsenite and aresenate. Silicate moderately decreased the adsorption of arsenite, but not arsenate. Both batch experiments and column experiments indicated that BCF had higher removal efficiency for arsenite than for arsenate. While the influent contaminant concentration was 500 microg/L in groundwater and the empty-bed contact time (EBCT) for arsenite and arsenate was 4.2 and 5.9 min, breakthrough empty-bed volumes at the WHO provisional guideline value of 10 microg/L were 2200 and 5000, respectively. BCF can be effectively regenerated when elution is done with 2 M NaOH solution. The column experiments for four cycles showed that stable and high removal efficiency of arsenic was sustained by BCF after regeneration.