Desorption Of As Research Articles

Monitoring and inverse modelling of hydrogeochemical processes during managed aquifer recharge in Southwestern Bangladesh

Managed Aquifer Recharge (MAR) has been applied as Aquifer Storage, Transfer, and Recovery (ASTR) to provide fresh drinking water for local communities at 99 locations in southwest Bangladesh since 2009. Aerobic freshwater from ponds is filtered and subsequently infiltrated into anaerobic shallow brackish aquifers. At approximately 45% of these sites, relatively higher levels of Fe and As were observed in recovered water, which requires a better understanding of the hydrogeochemical processes that govern the Fe, Mn, and As levels in these MAR systems. Therefore, two representative sites with As above (74 ± 11 μg/L at site GMF11) and below (19 ± 6 μg/L at site JJS91), the Bangladesh drinking water standard of 50 μg/L were weekly monitored on hydrochemical changes from Dec 2017 to Dec 2018. Hydrogeochemical processes occurring during storage were quantified with inverse and forward geochemical mass balance models developed with PHREEQC. The following processes explained the changes in water quality: 1) mixing of infiltration water with native groundwater (∼90%:∼10%); 2) consumption of O2 by a) dissolved Fe2+ that subsequently precipitated as Fe(OH)3 at GMF11 and by b) dissolved and sedimentary organic matter (OM) at site JJS91; 3) reduction of SO4 coupled to the oxidation of OM at both sites; and 4) mixing corrosion and freshening induced cation-exchange (Ca sorption; Na desorption) triggering calcite and siderite dissolution at GMF11. Dissolution of these carbonate minerals occurred to a lesser extent at JJS91, while cation exchange (Na sorption; Ca desorption) suggested that the freshwater was displaced by brackish groundwater because of inadequate infiltration at JJS91. Distinct pH values in recovered water reflected the dominance of Fe2+ versus OM oxidation. Siderite dissolution led to 4.3 ± 3.1 and 1.0 ± 0.5 mg/L Fe in recovered water at GMF11 and JJS91, respectively. Elevated As and Mn levels in recovered water were caused for max. 20% by mixing with native groundwater and for min. 80% by mobilization processes, mainly by desorption of As from Fe-oxides and by the dissolution of Mn-bearing siderite. Recommendations are provided to improve recovered water quality.

Atomic surface control of Ge(100) in MOCVD reactors coated with (Ga)As residuals

Heteroepitaxy of planar, low-defect III-V semiconductor layers on Ge(100) requires a single-domain substrate surface, where dimer rows are aligned in parallel on atomically well-ordered terraces, which are separated by steps of even numbered atomic height. The presence of Ga and As in the sample ambience crucially impacts the preparation of such Ge(100) surfaces. Ga and As are commonly omnipresent, when applying metalorganic chemical vapor deposition (MOCVD), either directly supplied by precursors, in the form of MOCVD reactor residuals, or both. We study the impact of the growth conditions on the Ge(100) surface formation in situ, in dependence on the reactor pre-conditioning, the type of As supply, and/or temperature, utilizing surface-sensitive reflection anisotropy spectroscopy. We benchmark the in situ spectra to in system X-ray photoelectron spectroscopy, low energy electron diffraction and scanning tunneling microscopy. We find that interaction of tertiarybutylarsine (TBAs) with a coating of the inner MOCVD reactor walls by GaAs residuals favors desorption of As from reactor parts resulting in As-dimers on the Ge(100) surface, which are rotated by 90° compared to preparation routes employing TBAs in Ga-free ambience. The optical in situ control enables precise adjustment and switching between distinct Ge(100) surface reconstructions for subsequent III-V heteroepitaxy.

Health risk assessment and source identification of groundwater arsenic contamination using agglomerative hierarchical cluster analysis in selected sites from upper Eastern parts of Punjab province, Pakistan

Geogenic contamination of Arsenic (As) poses major health threat to people living in Indus Plain of Pakistan particularly in Punjab. In this paper, we described in detail the hydrogeochemistry of As contaminated groundwaters in selected sites from Lahore, Kasur and Okara districts and its associated potential health risks. Sampling was done in 2019 and 141 groundwater samples were collected. High variability in As concentrations was observed varying between below detection level (<0.1 µg/L) and 655 µg/L. More than 85% of these samples exceeded WHO limit of 10 µg/L while 30% exceeded national limit of 50 µg/L. The results of statistical analysis and agglomerative hierarchical cluster (HCA) analyses indicate mainly pH-dependent desorption of As from mineral oxide surfaces under alkaline conditions to be responsible for As pollution with some minor controls from NO3 − and Fe-reduction in groundwaters was also seen. Furthermore, higher potential health risks were found to be associated with elevated As levels in terms of estimated average daily dosage (EDI), hazard quotient (HQ) and carcinogenic risk assessment (CR). The average values for HQ for adults, teenagers and children were found to be 9.06, 13.6 and 13.07, respectively. Meanwhile average CR values were found to be 0.004, 0.01, 0.006 mg/Kg/day in adults, teenagers and children respectively. These results suggest an increased risk of adverse health impacts in current study sites and require effective remedial measures at urgent basis.

Arsenic in a groundwater environment in Bangladesh: Occurrence and mobilization

Groundwater with an excessive level of Arsenic (As) is a threat to human health. In Bangladesh, out of 64 districts, the groundwater of 50 and 59 districts contains As exceeding the Bangladesh (50 μg/L) and WHO (10 μg/L) standards for potable water. This review focuses on the occurrence, origin, plausible sources, and mobilization mechanisms of As in the groundwater of Bangladesh to better understand its environmental as well as public health consequences. High As concentrations mainly was mainly occur from the natural origin of the Himalayan orogenic tract. Consequently, sedimentary processes transport the As-loaded sediments from the orogenic tract to the marginal foreland of Bangladesh, and under the favorable biogeochemical circumstances, As is discharged from the sediment to the groundwater. Rock weathering, regular floods, volcanic movement, deposition of hydrochemical ore, and leaching of geological formations in the Himalayan range cause As occurrence in the groundwater of Bangladesh. Redox and desorption processes along with microbe-related reduction are the key geochemical processes for As enrichment. Under reducing conditions, both reductive dissolution of Fe-oxides and desorption of As are the root causes of As mobilization. A medium alkaline and reductive environment, resulting from biochemical reactions, is the major factor mobilizing As in groundwater. An elevated pH value along with decoupling of As and HCO3− plays a vital role in mobilizing As. The As mobilization process is related to the reductive solution of metal oxides as well as hydroxides that exists in sporadic sediments in Bangladesh. Other mechanisms, such as pyrite oxidation, redox cycling, and competitive ion exchange processes, are also postulated as probable mechanisms of As mobilization. The reductive dissolution of MnOOH adds dissolved As and redox-sensitive components such as SO42− and oxidized pyrite, which act as the major mechanisms to mobilize As. The reductive suspension of Mn(IV)-oxyhydroxides has also accelerated the As mobilization process in the groundwater of Bangladesh. Infiltration from the irrigation return flow and surface-wash water are also potential factors to remobilize As. Over-exploitation of groundwater and the competitive ion exchange process are also responsible for releasing As into the aquifers of Bangladesh.

Hydrogeochemical controls on arsenic mobility in an arid inland basin, Southeast of Iran: The role of alkaline conditions and salt water intrusion

Elevated inorganic arsenic concentrations in groundwater has become a major public and environmental health concern in different parts of the world. Currently, As-contaminated groundwater issue in many countries and regions is a major topic for publications at global level. However, there are many regions worldwide where the problem has still not been resolved or fully understood due to inadequate hydrogeochemical investigations. Hence, this study evaluates for the first time the hydrogeochemical behavior of the arid and previously unexplored inland basin of Sirjan Plain, south east (SE) Iran, in order to assess the controlling factors which influence arsenic (As) mobility and its distribution through groundwater resources. Total inorganic arsenic concentration was measured using inductive-coupled plasma optical emission spectrometry (ICP-OES). Arsenic content in groundwater of this region ranged between 2.4 and 545.8 μg/L (mean value: 86.6 μg/L) and 50% of the samples exceeded the World Health Organization (WHO) guideline value of 10 μg/L in drinking water. Groundwater was mainly of Na-Cl type and alkaline due to silicate weathering, ion exchange and evaporation in arid conditions. Elevated As concentrations were generally observed under weakly alkaline to alkaline conditions (pH > 7.4). Multivariate statistical analysis including cluster analysis and bi-plot grouped As with pH and HCO3 and demonstrated that the secondary minerals including oxyhydroxides of Fe are the main source of As in groundwater in this region. The desorption of As from these mineral phases occurs under alkaline conditions in oxidizing arid environments thereby leading to high levels of As in groundwater. Moreover, evaporation, ion exchange and saltwater intrusion were the secondary processes accelerating As release and its mobility in groundwater. Based on the results of this study, desorption of As from metal oxy-hydroxides surfaces under alkaline conditions, evaporation and intrusion of As-rich saline water are considered to be the major factors causing As enrichment in arid inland basins such as those in southeast Iran. This study proposes the regular monitoring and proper groundwater management practices to mitigate high levels of arsenic in groundwater and related drinking water wells of Sirjan Plain.

Competitive adsorption and desorption of arsenate, vanadate, and molybdate onto the low-cost adsorbent materials alum water treatment sludge and bauxite

When low-cost adsorbents are being used to remove contaminant ions (e.g. arsenate, vanadate, and molybdate) from wastewater, competitive adsorption/desorption are central processes determining their removal efficiency. Competitive adsorption of As, V, and Mo was investigated using equimolar oxyanion concentrations in single, binary, and tertiary combinations in adsorption isotherm and pH envelope studies while desorption of previously adsorbed oxyanions was examined in solutions containing single and binary oxyanion combinations. The low-cost adsorbent materials used were alum water treatment sludge (amorphous hydroxy-Al) and bauxite ore (crystalline Al oxides). Adsorption isotherm and pH envelope studies showed that Mo had only a small effect in decreasing adsorption of As and V but V and As had substantial and similar effects in reducing adsorption of the other. As had a greater effect than V in reducing adsorption of Mo and it was concluded that the affinity of oxyanions for the surfaces of water treatment sludge and bauxite followed the order As > V >> Mo. In 0.3M NaCl electrolyte, desorption of previously adsorbed oxyanions amounted to 0.3-3.4% for V and As, and 11-20% for Mo. As had approximately four times greater effect than Mo in increasing desorption of V while V had about three times the effect of Mo in increasing desorption of As. Thus, the order of oxyanions in inducing desorption of the other oxyanions (i.e. As on V and As) was the same as that for adsorption selectivity: As > V >> Mo. Water treatment sludge was a more effective adsorbent than bauxite because it had a greater adsorption capacity for all three anions and, in addition, they were held more strongly so desorption in the background electrolyte was proportionately less. It was concluded that at similar molar concentrations, arsenate would tend to reduce adsorption of vanadate as well as displace vanadate already held on adsorbent surfaces while both anions will compete effectively with molybdate. The limiting factor for simultaneous removal of As, V, and Mo from multielement solutions by adsorption will therefore be the removal of Mo.

Hydrogeochemical and isotopic evaluation of groundwater with elevated arsenic in alkaline aquifers in Eastern Punjab, Pakistan

Geochemical investigation was carried out for delineating factors responsible for the mobilization of arsenic (As) from aquifer material into the groundwater. Four sites along Ravi River, (Samada, Sarai Chimba, Kot Maiga and Chah Fatehwala), were selected based on the blanket survey. Groundwater-rock interaction and evaporation were the key phenomena controlling groundwater chemistry, as shown by the hydrogeochemical data. Groundwater was predominantly Na-Cl type, with other principle facies being Na-HCO3, Na-Ca-HCO3 and Ca-Mg-Cl. The groundwater As concentration ranged between below detection level (2 μg/L) to 548 μg/L with 59% samples exceeding the World Health Organization (WHO) guidelines for As in drinking water (10 μg/L) and 31% having higher concentrations than the National Environmental Quality Standard (NEQS, 50 μg/L). Moderate to high concentrations of SO4−2 averaged at 244 mg/L and moderate NO3− concentrations averaged at 8 mg/L, together with alkaline pH (7.3–8.8) and high Eh values (113–402 mV) suggest partial oxidizing nature of the aquifers. The values for δ 18O and δ 2H in groundwater varied between −9.14 and −5.51‰, and −56.57 to −39.5‰ respectively, and suggests meteoric origin of the groundwater with some evaporative loss. This effect could be partly responsible for elevated levels of pH and salinity in groundwater. Based on geochemical and isotopic composition of groundwater, desorption of As from metal surfaces under alkaline environment might be the factor causing As enrichment in study area.

Desorption of Arsenic Ions from Iron Modified Montmorillonite

Adsorption of metal ions proves to be an effective method in treating wastewater due to its simplicity and flexibility in terms of processing. Particularly, iron-modified montmorillonite (Fe-MMT) has been used to treat arsenic ion contamination. However, the strength of association of the metal ion with the adsorbent has not yet been fully explored. This study aimed to determine the stability of the attachment of As2+ onto Fe-MMT by performing desorption experiments using HCl and EDTA as eluents.The Fe-MMT was synthesized via ion exchange while the adsorption and desorption experiments were performed using a batch set-up. Conditions for adsorption were set constant, while the eluent type and concentration (0.1 M and 0.01 M) were varied during desorption. Arsenic ion concentrations were determined using ICP-OES. SEM images and FTIR spectra of the Fe-MMT were also obtained before and after adsorption-desorption steps. Highest desorptions among the settings were observed in 0.1 M HCl and 0.01 M EDTA with 36.72% and 37.13% desorption capacities, respectively. Since the pH conditions also varied with the eluent type, desorption of As is feasible, though not highly efficient, in both acidic and basic conditions with ion exchange as the dominant mechanism. There is a preference in desorption at 0.1 M in HCl but at 0.01 M in EDTA. Furthermore, no significant change in the morphology was observed. The FTIR spectra showed that the absorbance of Fe-MMT after desorption remains in the same range as the absorbance after adsorption but had lost intensity of some of its peaks, indicating possible interactions with acid.

Subsurface variations in arsenic mineralogy and geochemistry following long-term weathering of gold mine tailings

Variations in arsenic (As) mineralogy and geochemical controls on its mobility were evaluated in subsurface tailings at the historical Montague and Goldenville mine sites in Nova Scotia, Canada. Tailings at these sites contain some of the highest As concentrations in Nova Scotia and are located in close proximity to local communities. Pore water in the subsurface tailings is characterized by circumneutral to alkaline pH (6.2 to 8.7) and mildly reducing to oxidizing redox conditions (+130 mV to +347 mV). Bulk chemistry, scanning electron microscopy, and synchrotron micro-X-ray diffraction analyses showed As mineral hosts differ with depth. The deepest tailings (max. 2 m) are in direct contact with partially decomposed vegetation, which supports reducing conditions and the precipitation of authigenic As and Fe sulfides. Under reducing conditions, dissolved As concentrations are also controlled by desorption of As from dissolution of Fe and Mn oxides and the sorption or co-precipitation of As with carbonates. These geochemical controls differ from those influencing dissolved As concentrations under oxidizing conditions. In the near surface, As mobility is controlled by oxidative dissolution of primary arsenopyrite, precipitation of secondary Fe arsenates, Fe oxyhydroxides and Mn oxides, secondary Ca-Fe arsenates, and sorption onto Fe oxyhydroxides and gangue minerals. Some of these mineral species are stable under different conditions yet occur in close association, indicating the importance of microenvironments. The results of this study show that the weathering characteristics of these tailings vary with depth, leading to the formation of new As hosts that are distinct from those observed in the near surface. Identification of these As hosts provides an understanding of current controls on As mobility and has implications for future reprocessing and/or remediation efforts.

Redox processes and occurrence of arsenic in a volcanic aquifer system of Kumamoto Area, Japan

Sources, distributions, and controlling factors for mobilization of arsenic (As) in Kumamoto basin were investigated relating to the determination of redox processes of the study area. Groundwater and sediment core samples were analyzed. Nitric acid digestion and sequential leaching experiment of sediment core samples revealed that the source of As in the groundwater is geogenic and leached primarily due to the sediment–water interactions. Unlikely, similar relations of total As with total Fe, Mn, and Al in acid extracts, leaching experiments showed a positive relation of Astotal with Fetotal and Altotal indicated that Fe and Al oxides/hydroxides are abundant and may be the major adsorbent of As in low pH condition. Arsenic concentrations in groundwater ranges from 0.1 to 60.6 μg/l. High As concentrations occurred in anaerobic stagnant groundwaters from Kumamoto plain area with high dissolved Fetotal, Mntotal, and Altotal, moderately dissolved HCO3 −, PO4 3−, SO4 2−, and low concentrations of NO3 − and DOC suggesting the reducing condition of subsurface aquifer. There is a range of As(III)/As(T) ratios from mostly arsenate to mostly arsenite. Groundwater pH was relatively high, and high As occurred at higher pH range. It is assumed that desorption of As from metal oxide surfaces was facilitated by the elevated pH, which is considered as an important process for As mobilization. In addition to this, a wide range of δ34SSO4 values (8.3–57.6 ‰) indicates that sulfur is undergoing redox cycling mediated by microbial activities. Following δ34SSO4 results, it is anticipated that dissolved As is coprecipitated as sulfides in the presence of dissolved Fe(II) in some places, though at this moment, there is no direct evidence of coprecipitation or sequester of As with Fe and sulfide ion. Finally, a combination of the following three variables are considered potentially important causes for the high dissolved As concentrations in groundwater of Kumamoto area—(1) high groundwater pH, (2) anoxic redox conditions, and (3) stagnant groundwater in younger age sediments, which have not been well flushed since burial.

Oxalate-based remediation of arsenic bound to amorphous Fe and Al hydrous oxides in soil

In this study, oxalate-based washing process was designed to remediate the arsenic (As)-contaminated soil, where As was mainly associated with amorphous iron–aluminum (Fe/Al) hydrous oxides. Oxalate is a naturally present organic acid and has been commonly used to extract Fe from amorphous oxides due to its reducing and chelating capacities. In the oxalate-based washing process, reductive and ligand-promoted dissolution of iron oxides occurred by oxalate and concurrently As bound to the iron oxides was released from the soil. In addition, desorption of As from the surface of soil could enhance the As removal when As(V) was reduced to As(III) by oxalate. As extraction by oxalate was effective for As bound to amorphous Fe/Al hydrous oxides, but was not effective for As combined with crystalline Fe/Al oxides and residual fraction. The germination test using the residual soil after soil washing showed that germination rate and growth of wheat (Triticumaestivum L.) and sunflower (Helianthus annus L.) were improved on the soil after oxalate washing compared to those on the initial and HCl washed soils. Consequently, oxalate was effective to extract As bound to amorphous Fe/Al hydrous oxides and had positive influence on the soil quality for plant growth.

Natural Occurrence of Arsenic in Groundwater from Lesvos Island, Greece

A geochemical analysis and modelling was carried out to investigate the As occurrence and release in groundwater from two different geological environments on Lesvos Island: (i) the volcanic area of Mandamados (ignimbrite of rhyolithic to rhyodacitic composition) and (ii) the metamorphic area of Tarti (schists and marbles) that comprises the geologic basement under ignimbrite. Seven sampling campaigns were conducted between October 2010 and October 2011, including 65 groundwater samples from 11 wells and springs. Chemical analyses showed As concentrations exceeding the 10-μg/L national drinking water limit in 46 % of the samples from Mandamados. Groundwater composition in Mandamados evolved from Ca-HCO3 type, to mixed type and finally to Na-Cl type along the groundwater flow direction, indicating the contribution of ion exchange in groundwater chemical composition, while Ca-HCO3 type waters were observed in the Tarti area. Arsenic speciation analysis showed that As(V) was the main species in all samples, indicating that As was released under oxidizing conditions. Statistical analysis suggested silicate weathering as the prime mechanism of As release in groundwater in both cases, while, in the Tarti area, carbonate dissolution may represent a secondary mechanism which could be related to the observed relatively low As concentrations in the region. In both areas, pH-related desorption of As, primarily from Fe mineral phases, was found to be the most important factor controlling the mobilisation of As, while the contribution of the redox control to As release in groundwater was generally found to be less significant.

Effect of reductive dissolution of iron (hydr)oxides on arsenic behavior in a water–sediment system: First release, then adsorption

Abstract Whether the reductive dissolution of iron (hydr)oxides promotes absorption or desorption of arsenic (As) is still in controversy. Here, we used laboratory simulation experiments to examine the absorption/desorption behavior of As when it is affected by microbial activity. Sediment from Yangzonghai Lake, which is known to be contaminated by As, was used in this experiment, and pollution abatement was performed using ferric salt flocculants (FeCl 3 ). In the presence of sulfides, the reductive dissolution of iron (hydr)oxides affects the behavior of As in sediment in two ways. First, the reductive dissolution of iron (hydr)oxide accelerates the desorption of As, thus releasing As(III) from the sediment, increasing the environmental risk of As. Secondly, reductive dissolution causes the system’s redox conditions to continually change. When the oxidation–reduction potential (Eh) of the system exceeds 80 mV, As is precipitated rather than desorpting. As is co-precipitated with sulfur released previously via microbially induced reductive dissolution, where sulfur precipitation is more important than reductive dissolution of iron (hydr)oxide in controlling the adsorption/desorption of As.

Arsenic concentration variability, health risk assessment, and source identification using multivariate analysis in selected villages of public water system, Lahore, Pakistan

This paper reports high levels and variability in arsenic (As) levels at locations identified as one of the highest As-contaminated locations in Pakistan. Groundwater pollution related to arsenic has been reported since many years in the areas lying in outskirts of District Lahore, Pakistan. A comparative study is done to determine temporal variations of As from three villages, i.e., Kalalanwala (KLW), Manga Mandi (MM), and Shamki Bhattian (SKB). Seventy-three percent of the 30 investigated samples ranging in depth from 20 to 200 m, show an increasing trend in variations of As concentration over a time span of 4 years and 87% of samples exceeded the WHO standard of 10 μg/L for As while 77% of samples have As concentration >50 μg/L (national standard). Further results indicate that high levels of As is accompanied with increase pH (r = 0.8) favoring desorption of As from minerals at higher pH under oxidizing conditions. For health risk assessment of arsenic, the average daily dose, hazard quotient (HQ), and cancer risk were calculated. The residents of the studied areas had toxic risk index in the order of SKB>KLW>MM, with 87% of samples exceeding the typical toxic risk index 1.00 (ranging from 2.3-48.6) which was 83% (ranging from 0.3-41) 4 years before. The results of the present study therefore indicate that arsenic concentrations are increasing in the area, which needs an immediate attention to provide alternate sources of water to save people at risk.

Phosphorus–arsenic interactions in variable-charge soils in relation to arsenic mobility and bioavailability

Phosphorus (P) influences arsenic (As) mobility and bioavailability which depends on the charge components of soil. The objective of this study was to examine P–As interaction in variable-charge allophanic soils in relation to P-induced As mobilization and bioavailability. In this work, the effect of P on arsenate [As(V)] adsorption and desorption was examined using a number of allophanic and non-allophanic soils which vary in their anion adsorption capacity. The effect of P on As uptake by Indian mustard (Brassica juncea L.) plants was examined using a solution culture, and a soil plant growth experiment involving two As-spiked allophanic and non-allophanic soils which vary in their anion adsorption capacity, and a field As-contaminated sheep dip soil. Arsenate adsorption increased with an increase in the anion adsorption capacity of soils. The addition of P resulted in an increase in As desorption, and the effect was more pronounced in the case of allophanic soil. In the case of both As-spiked soils and field contaminated sheep-dip soil, application of P increased the desorption of As, thereby increasing its bioavailability. The effect of P on As uptake was more pronounced in the high anion adsorbing allophanic than low adsorbing non-allophanic soil. In the case of solution culture, As phytoavailability decreased with increasing concentration of P which is attributed to the competition of P for As uptake by roots. While increasing P concentration in solution decreased the uptake of As, it facilitated the translocation of As from root to shoot. The net effect of P on As phytoavailability in soils depends on the extent of P-induced As mobilization in soils and P-induced competition for As uptake by roots. The P-induced mobilization of As could be employed in the phytoremediation of As-contaminated sites. However, care must be taken to minimize the leaching of As mobilized through the P-induced desorption, thereby resulting in groundwater and off site contamination.

Calcium–phosphate treatment of contaminated soil for arsenic immobilization

Abstract The application of As-based herbicides at several industrial sites has resulted in numerous localized areas of As-contaminated soil. In this study, an As-contaminated soil (As = 278 mg/kg) collected from an industrial site located in the southeastern USA was subjected to inorganic phosphate (Pi) treatments. Although Pi treatments have been previously used for flushing As from contaminated soils, in this study, contaminated soil was amended with Pi to study the possible immobilization of As through a co-precipitation mechanism. Specifically, the Pi amendment was aimed at simultaneous flushing of As from the soil with orthophosphoric acid and co-precipitating it as Ca–phosphate–arsenate phases. Bench-scale Pi treatment experiments were performed at different pH conditions, with and without the addition of Ca. Sorption of Pi on BH soil in the presence or absence of additional Ca was determined, along with the associated mobilization of As from the soil. A significant amount of the HNO3-digestible As (up to 55% at pH 4, 10–15% at pH 8, and ∼30% at pH 11) was released from the contaminated soil during the Pi sorption experiments. This increased mobility of As after the addition of Pi resulted from the competitive desorption of As from the soil. Although Pi sorption at high pH (>8) was largely controlled by precipitation, As did not co-precipitate with Pi. Aqueous geochemical modeling indicated that the lack of As co-precipitation during Pi-only treatment primarily resulted from the deficiency of Ca in the system. When additional Ca (16.9 mmol) was supplied along with Pi (3.38 mmol), the mobility of As decreased significantly at circum-neutral to high solution pH. Geochemical modeling suggested that the leachable As in the soil was potentially precipitated as As-bearing Ca–Pi phases. X-ray diffraction analysis of precipitates separated from the treated soil and from the synthetic leachate confirmed that the formation of a poorly crystalline carbonate apatite phase occurred as a consequence of the treatment. The results of this study support the potential application of Ca–Pi treatment for remediation of As-contaminated soil at environmentally relevant pH conditions.

Mobility of arsenic in aquifer sediments at Datong Basin, northern China: Effect of bicarbonate and phosphate

Effects of phosphate and bicarbonate concentration on mobilization of arsenic in aquifer sediments have not been extensively studied in flow-through experiments, where the dynamic-release behavior of elements can be monitored. In this work, these effects were investigated both through batch and column experiments, using a high-arsenic sediment sample from the Datong Basin, northern China. A solution of 1.0mM Ca(NO3)2 was first applied to a water-saturated column packed with the sediment; this was followed by leaching with either 0.10mM Na2HPO4 or 8.2mM NaHCO3 solutions. When the sediment was initially leached with 1.0mM Ca(NO3)2 solution, a rapid spike of As, Fe, Mn, and major cations was observed in the first 20 column pore volumes, reflecting the initial equilibration of the sediment to the influent Ca(NO3)2 in response to cation exchange (for cations) and sorption equilibrium (for Mn, Fe, As).After the Ca(NO3)2 solution was replaced with either the Na2HPO4 or NaHCO3 solution, a rapid increase in As concentration in the effluent was observed, consistent with the batch test results. Induced desorption of As from oxyhydroxide sorbents by Na2HPO4 suggests that phosphate competition was the major factor responsible for the observed increase of As, as indicated by a coinciding increase of K+ replaced in the exchange process. In the column leached with 8.2mM NaHCO3, high concentrations of sodium result in greater clay dispersion, and the transport of Fe/Mn oxyhydroxides with adsorbed arsenic may account for the enhanced arsenic concentration in the effluent, as suggested by the concurrently observed increase in Fe and Mn concentrations in the effluent.

Effect of seepage conditions on chemical attenuation of arsenic by soils across an abandoned mine site

The effect of seepage velocity on the As leaching/adsorption by soils collected from abandoned mine sites was evaluated under batch equilibrium and different seepage settings. The breakthrough curves (BTCs) of As leaching from the mine soil column initially displayed the peak export and gradually leveled off over the leaching experiment. A similar As peak was observed after a flow interruption period. Adsorption by downgradient soils was clearly nonlinear, as Freundlich N was <1. In the BTCs of the layered columns, where downgradient soils were overloaded above the mine soil, the extended lag period of As appearance and lower steady-state As concentration observed for slow seepage velocity supported the idea of kinetically limited As attenuation driven by soil adsorption. The perturbation of As concentration was insignificant when the intra-column As concentration gradient was higher. The As concentration drop and time to recovery were greater for less adsorptive soil and fast seepage velocity. Desorption of As from soils retrieved from both batch adsorption and column experiment demonstrate hysteric behavior. The results of this work demonstrated that the risk of As leaching from an abandoned mine site can be greatly attenuated by intermediate downgradient soils via chemical adsorption, which tends to be kinetically limited and energetically hysteric (i.e., non-identical energy pathway).

Field, Experimental, and Modeling Study of Arsenic Partitioning across a Redox Transition in a Bangladesh Aquifer

To understand redox-dependent arsenic partitioning, we performed batch sorption and desorption experiments using aquifer sands subjected to chemical and mineralogical characterization. Sands collected from the redox transition zone between reducing groundwater and oxic river water at the Meghna riverbank with HCl extractable Fe(III)/Fe ratio ranging from 0.32 to 0.74 are representative of the redox conditions of aquifers common in nature. One brown suboxic sediment displayed a partitioning coefficient (K(d)) of 7-8 L kg(-1) at equilibrium with 100 μg L(-1) As(III), while two gray reducing sediments showed K(d) of 1-2 L kg(-1). Lactate amendment to aquifer sands containing 91 mg kg(-1) P-extractable As resulted in the reduction of As and Fe with sediment Fe(III)/Fe decreasing from 0.54 to 0.44, and mobilized an equivalent of 64 mg kg(-1) As over a month. Desorption of As from nonlactate-amended sediment was negligible with little change in sediment Fe(III)/Fe. This release of As is consistent with microbial reduction of Fe(III) oxyhydroxides and the resulting decrease in the number of surface sites on Fe(III) oxyhydroxides. Arsenic partitioning (K(d)) in iron-rich, sulfur-poor aquifers with circumneutral pH is redox-dependent and can be estimated by HCl leachable sediment Fe(III)/Fe ratio with typical Fe concentrations.

Pilot Scale Ex-Situ Electrokinetic Remediation of Arsenic-Contaminated Soil

In this study, the effectiveness of ex situ electrokinetic remediation (EKR) in treating actual As-contaminated soil was evaluated at a pilot scale (1 m [W] × 1 m [L] × 1.5 m [H]). Ethylenediamine tetraacetic acid (EDTA) and sodium hydroxide as the catholyte and anolyte, respectively, were circulated to enhance the desorption of As. Two types of soil were collected from a real contaminated agricultural area: silty loam from a rice paddy and sandy clay loam from dry land. An average of 78% of the As was removed from the two types of soil after 8 weeks, and the residual As concentration met the level set by Korean legal regulations. The average removal rates were 1.06 and 1.55 mg/kg/day, respectively, for the paddy and dry field soil samples. In addition, fractionation analysis showed that most other fractions and even a large portion of the residual fraction were removed after EKR. The ex situ application provided electrolyte more uniformly to the entire soil sample; therefore, there was no significant variation in As removal depending on the depth of the soil. These results indicated that ex situ EKR is an effective technique for the remediation of As-contaminated sites.