Evaluation and standardisation of a simple HG-AAS method for rapid speciation of As(III) and As(V) in some contaminated groundwater samples of West Bengal, India

A simple HG-AAS technique has been evaluated and standardised for rapid speciation of As(III) and As(V) in a number of contaminated groundwater samples of West Bengal, India. Citric acid has been used for selective hydride formation of As(III). The sensitivity of the evaluated HG-AAS method is 7.91 mg(-1)l, standard deviation, 0.001 and detection limit, 0.4 microg l(-1). As(III) sensitivity remains constant in the sample pH range of 2.3-10.6. Concomitant mineral matrix of the water samples did not interfere with arsenic determination. Eight out of ten groundwater samples analysed for As(IlI)and As(V) contain more As(III), which lies in the range of 54-350 ppb. As(III) estimation in drinking water along with total arsenic should be invoked as a policy for a realistic risk assessment of the contaminated water.     

Speciation of inorganic arsenic in alimentary and environmental aqueous samples by using derivative anodic stripping chronopotentiometry (dASCP)

The purpose of this research was to develop a sensitive and accurate chronopotentiometric method at a gold film electrode, to determine trace and ultra trace levels of As(III) and As(V) in alimentary and environmental water systems. As(III) was directly determined in the aqueous matrix at a deposition potential of -300 mV for 180 s and at a constant anodic current of 2.5 microA, without any sample pre-treatment; moreover the chronopotentiometric method did not require a time-consuming de-oxygenation step prior to the analysis. A 3M HCl solution was chosen as the best stripping medium. The direct analysis of As(V) required the application of a high negative over-potential and, thus, measurements were characterized by poor reproducibility; therefore As(V) was determined after reduction to As(III) with KI in a strong hydrochloric acid solution. Under the optimised electrochemical conditions, detection limits of 0.08 microg As(III) l(-1) were achieved and no significant interferences from Cd, Cu, Pb, Zn and organic substances were observed. As(V) was the most abundant species in all the studied environmental and alimentary aqueous matrices. Amongst the beverages, tea and coffee presented the As(V) highest concentration ranges (934-1740 microg l(-1) and 850-1290 microg l(-1), respectively) while bottled mineral water the lowest (<1.61 microg l(-1)); whereas As(III) levels lower than 5.0 microg l(-1) were detected only in wine samples.     

Speciated arsenic in air: measurement methodology and risk assessment considerations

Accurate measurement of arsenic (As) in air is critical to providing a more robust understanding of arsenic exposures and associated human health risks. Although there is extensive information available on total arsenic in air, less is known on the relative contribution of each arsenic species. To address this data gap, the authors conducted an in-depth review of available information on speciated arsenic in air. The evaluation included the type of species measured and the relative abundance, as well as an analysis of the limitations of current analytical methods. Despite inherent differences in the procedures, most techniques effectively separated arsenic species in the air samples. Common analytical techniques such as inductively coupled plasma mass spectrometry (ICP-MS) and/or hydride generation (HG)- or quartz furnace (GF)-atomic absorption spectrometry (AAS) were used for arsenic measurement in the extracts, and provided some of the most sensitive detection limits. The current analysis demonstrated that, despite limited comparability among studies due to differences in seasonal factors, study duration, sample collection methods, and analytical methods, research conducted to date is adequate to show that arsenic in air is mainly in the inorganic form. Reported average concentrations of As(III) and As(V) ranged up to 7.4 and 10.4 ng/m3, respectively, with As(V) being more prevalent than As(III) in most studies. Concentrations of the organic methylated arsenic compounds are negligible (in the pg/m3 range). However because of the variability in study methods and measurement methodology, the authors were unable to determine the variation in arsenic composition as a function of source or particulate matter (PM) fraction. In this work, the authors include the implications of arsenic speciation in air on potential exposure and risks. The authors conclude that it is important to synchronize sample collection, preparation, and analytical techniques in order to generate data more useful for arsenic inhalation risk assessment, and a more robust documentation of quality assurance/quality control (QA/QC) protocols is necessary to ensure accuracy, precision, representativeness, and comparability.     

Arsenic speciation of atmospheric particulate matter (PM10) in an industrialised urban site in southwestern Spain

An arsenic speciation study has been performed in PM10 samples collected on a fortnight basis in the city of Huelva (SW Spain) during 2001 and 2002. The arsenic species were extracted from the PM10 filters using a NH2OH x HCl solution and sonication, and determined by HPLC-HG-AFS. The mean bulk As concentration of the samples analyzed during 2001 and 2002 slightly exceed the mean annual 6 ng m(-3) target value proposed by the European Commission for 2013, arsenate [As(V)] being responsible for the high level of arsenic. The speciation analyses showed that As(V) was the main arsenic species found, followed by arsenite [As(III)] (mean 6.5 and 7.8 ng m(-3) for As(V), mean 1.2 and 2.1 ng m(-3) for As(III), in 2001 and 2002, respectively). The high levels of arsenic species found in PM10 in Huelva have a predominant industrial origin, such as the one from a nearby copper smelter, and do not present a seasonal pattern. The highest daily levels of arsenic species correspond to synoptic conditions in which the winds with S and SW components transport the contaminants from the main emission source. The frequent African dust outbreaks over Huelva may result in an increment of mass levels of PM10, but do not represent a significant input of arsenic in comparison to the anthropogenic source. The rural background levels of arsenic around Huelva are rather high, in comparison to other rural or urban areas in Spain, showing a relatively high atmosphere residence time of arsenic. This work shows the importance of arsenic speciation in studies of aerosol chemistry, due to the presence of arsenic species [As(III) and As(V)] with distinct toxicity.     

Influence of sulfide (S2-) on preservation and speciation of inorganic arsenic in drinking water

Generally, H2SO4, HNO3, HCl or the combination of ethylenediaminetetraacetate with acetic acid (EDTA-HAc) have been used to preserve arsenite and arsenate species prior to analysis. When these acidic preservatives are added in sulfidic water, instantaneous precipitation of poorly crystalline orpiment, As2S3(am), occurs, thereby lowering the total arsenic, As(Tot), analysis. A new method for the determination of As(Tot) was developed in which acid-preserved sulfidic water samples were oxidized with NaOCl, converting As2S3(am) and thioarsenic species to arsenate. A new method was also developed for the separation of uncharged arsenite and charged thioarsenic species in fresh, unpreserved sulfidic water by adsorbing the charged thioarsenic species while allowing uncharged arsenite to pass through a strong-base resin unhindered. The adsorbed thioarsenic species could be eluted efficiently with 0.16 M NaOCl solution.     

Arsenic(III) and iron(II) co-oxidation by oxygen and hydrogen peroxide: Divergent reactions in the presence of organic ligands

Iron-catalyzed oxidation of As(III) to As(V) can be highly effective for toxic arsenic removal via Fenton reaction and Fe(II) oxygenation. However, the contribution of ubiquitous organic ligands is poorly understood, despite its significant role in redox chemistry of arsenic in natural and engineered systems. In this work, selected naturally occurring organic ligands and synthetic ligands in co-oxidation of Fe(II) and As(III) were examined as a function of pH, Fe(II), H₂O₂, and radical scavengers (methanol and 2-propanol) concentration. As(III) was not measurably oxidised in the presence of excess ethylenediaminetetraacetic acid (EDTA) (i.e. Fe(II):EDTA < 1:1), contrasting with the rapid oxidation of Fe(II) by O₂ and H₂O₂ at neutral pH under the same conditions. However, partial oxidation of As(III) was observed at a 2:1 ratio of Fe(II):EDTA. Rapid Fe(II) oxidation in the presence of organic ligands did not necessarily result in the coupled As(III) oxidation. Organic ligands act as both iron speciation regulators and radicals scavengers. Further quenching experiments suggested both hydroxyl radicals and high-valent Fe species contributed to As(III) oxidation. The present findings are significant for the better understanding of aquatic redox chemistry of iron and arsenic in the environment and for optimization of iron-catalyzed arsenic remediation technology.     

Arsenic uptake and speciation and the effects of phosphate nutrition in hydroponically grown kikuyu grass (Pennisetum clandestinum Hochst)

Background

This work focuses on the accumulation and mobility properties of arsenic (As) and the effects of phosphate (P) on its movement in Pennisetum clandestinum Hochst (kikuyu grass), grown hydroponically under increasing arsenate (As(V)) concentrations. The uptake of both ions and the relative kinetics show that phosphate is an efficient competitive inhibitor of As(V) uptake. The P/As uptake rate ratios in roots indicate that P is taken up preferentially by P/As transporters. An arsenite (As(III)) efflux from roots was also found, but this decreased when the arsenate concentration in the solution exceeded 5???M.

Methods

Increases in both arsenite and arsenate concentrations in roots were observed when the arsenate concentration in the solution was increased, and the highest accumulation of As(III) in roots was found when plants were grown at 5???M As(V). The low ratios of As accumulated in shoots compared to roots suggest limited mobility of the metalloid within Kikuyu plants.

Results

The results indicate that arsenic resistance in kikuyu grass in conditions of moderate exposure is mainly dependent on the following factors: 1) phosphate nutrition: P is an efficient competitive inhibitor of As(V) uptake because of the higher selectivity of membrane transporters with respect to phosphate rather than arsenate; and 2) a detoxification mechanism including a reduction in both arsenate and arsenite root efflux.

Conclusions

The As tolerance strategy of Kikuyu limits arsenate uptake and As translocation from roots to shoots; therefore, this plant cannot be considered a viable candidate for use in the phytoextraction of arsenic from contaminated soils or water.     

Speciation of arsenic and chromium metal ions by reversed phase high performance liquid chromatography

The speciation of arsenic [As(III) and As(V)] and chromium [Cr(III) and Cr(VI)] was carried out by high performance liquid chromatography. The column used was Econosil C18 (250 x 4.6 mm i.d., particle size 10 microm). The mobile phases consisted of water-acetonitrile (80:20, v/v) for arsenic and 10 mM ammonium acetate buffer (6.0 pH)-acetonitrile (10:90, v/v) for chromium speciation separately and respectively. The detection was carried out by UV-Vis at 410 nm and atomic absorption spectrometer (AAS) respectively and separately. The values of alpha and Rs of As(III) and As(V) species were 1.4 and 1.5 respectively while the values of alpha and Rs for Cr(III) and Cr(VI) were 1.35 and 0.2 respectively. The effect of the acetonitrile percentages was also carried out on the speciation of arsenic only. The relative standard deviation and limit of detection were in the range of 0.01-0.02 and 0.4-1.0 microg/ml respectively.     

Simultaneous reduction of Cr(VI) and oxidation of As(III) by Bacillus firmus TE7 isolated from tannery effluent

Hexavalent chromium [Cr(VI)] and arsenite [As(III)] are the most toxic forms of chromium and arsenic respectively, and reduction of Cr(VI) to Cr(III) and oxidation of As(III) to As(V) has great environmental implications as they affect toxicity and mobility of these toxic species. Bacillus firmus strain TE7, resistant to chromium and arsenic was isolated from tannery effluent. The strain exhibited ability to reduce Cr(VI) and oxidize As(III). It reduced 100 mg L^?1 Cr(VI) within 60 h in nutrient broth and oxidized 150 mg L^?1 As(III) within 10 h in minimal medium. It also completely reduced 15 mg L^?1 Cr(VI) and oxidized 50 mg L^?1 of As(III) simultaneously in minimal medium. To the best of our knowledge, this is the first bacterial strain showing simultaneous reduction of Cr(VI) and oxidation of As(III) and is a potential candidate for bioremediation of environments contaminated with these toxic metal species.     

Characterizing As(III,V) adsorption by soils surrounding ash disposal facilities

Leachate derived from unlined coal ash disposal facilities is a potential anthropogenic source of arsenic to the environment. To establish a theoretical framework for predicting attenuation of arsenic by soils subject to ash landfill leachate, which is typically enriched in calcium and sulfate, the adsorption of As(V) and As(III) was characterized from 1 mM CaSO₄ for 18 soils obtained down-gradient from three ash landfill sites and representing a wide range in soil properties. As(V) consistently exhibited an order of magnitude greater adsorption than As(III). As(V) adsorption was best described by coupling pH with 15 s DCB-Fe (R² = 0.851,  = 0.001), although pH coupled to clay, DCB-Fe, or DCB-Al also generated strong correlations. For As(III), pH coupled to Ox–Fe (R² = 0.725,  = 0.001) or Ox–Fe/Al (R² = 0.771,  = 0.001) provided the best predictive relationships. Ca²⁺ induced increases in As(V) adsorption whereas sulfate suppressed both As(V) and As(III) adsorption. Attenuation of arsenic from ash leachate agreed well with adsorption measured from 1 mM CaSO₄ suggesting that the use of 1 mM CaSO₄ in laboratory adsorption tests is a reasonable approach for estimating arsenic behavior in soils surrounding ash landfills. We also showed that the impact of leachate-induced changes in soil pH over time may not be significant for As(V) adsorption at pH < 7; however, As(III) adsorption may be impacted over a wider pH range especially if phyllosilicate clays contribute significantly to adsorption. The benefits and limitations of predicting arsenic mobility using linearized adsorption coefficients estimated from nonlinear adsorption isotherms or from the relationships generated in this study are also discussed.     

Diel cycles of arsenic speciation due to photooxidation in acid mine drainage from the Iberian Pyrite Belt (Sw Spain)

Twenty four hours diel cycles of arsenic speciation in Acid Mine Drainage (AMD) due to photooxidation have been reported for the first time. AMD samples were taken during 48 h (31st March and 1st April, 2005) at 6 h intervals from the effluent of a massive abandoned polymetallic sulphide mine of the Iberian Pyrite Belt (Sw Spain). Samples were preserved in situ using cationic exchange prior to analysis by coupled high performance liquid chromatography, hydride generation and atomic fluorescence spectrometry (HPLC-HG-AFS) for arsenic speciation. The results indicated the presence of inorganic arsenic species with daily means of 262mugl(-1) for As(V) and 107 microg l(-1) for As(III). No marked diel trend was observed for As(V). However, a marked diel trend was observed for As(III) in the two studied days, with maximum concentrations during nighttime (141-143 microg l(-1)) and minimum concentrations at daytime (72-77 microg l(-1)). This difference in concentration during daytime and nighttime is ca. 100%. A similar diel cycle was observed for iron. An explanation for the arsenic diel cycles observed is the light induced photooxidation of As(III) and the elimination of As(V) due to its adsorption onto Fe precipitates during the daytime. Furthermore, the diel changes in arsenic speciation emphasize the importance of designing suitable sampling strategies in AMD systems.     

模拟酸雨对氧化锰吸附砷(Ⅲ)的解吸行为研究

以合成的氧化锰为吸附剂研究了酸雨pH值、酸雨离子强度、解吸时间和解吸次数等因素对模拟酸雨解吸砷(Ⅲ)的影响。实验结果表明:氧化锰对砷(Ⅲ)吸附容量较大,等温平衡吸附量为:48.38 mg/g。模拟酸雨的pH值与离子强度对砷(Ⅲ)的解吸影响不大;解吸反应在90 min后基本达到平衡,平衡解吸量为2.69×10-2mg/g;随解吸次数的增加解吸量变化不大。氧化锰对砷(Ⅲ)的吸附主要是专性的配位吸附,吸附砷(Ⅲ)后难以被模拟酸雨解吸。     

Evaluating of arsenic(V) removal from water by weak-base anion exchange adsorbents

Arsenic contamination of groundwater has been called the largest mass poisoning calamity in human history and creates severe health problems. The effective adsorbents are imperative in response to the widespread removal of toxic arsenic exposure through drinking water. Evaluation of arsenic(V) removal from water by weak-base anion exchange adsorbents was studied in this paper, aiming at the determination of the effects of pH, competing anions, and feed flow rates to improvement on remediation. Two types of weak-base adsorbents were used to evaluate arsenic(V) removal efficiency both in batch and column approaches. Anion selectivity was determined by both adsorbents in batch method as equilibrium As(V) adsorption capacities. Column studies were performed in fixed-bed experiments using both adsorbent packed columns, and kinetic performance was dependent on the feed flow rate and competing anions. The weak-base adsorbents clarified that these are selective to arsenic(V) over competition of chloride, nitrate, and sulfate anions. The solution pH played an important role in arsenic(V) removal, and a higher pH can cause lower adsorption capacities. A low concentration level of arsenic(V) was also removed by these adsorbents even at a high flow rate of 250–350 h^?1. Adsorbed arsenic(V) was quantitatively eluted with 1 M HCl acid and regenerated into hydrochloride form simultaneously for the next adsorption operation after rinsing with water. The weak-base anion exchange adsorbents are to be an effective means to remove arsenic(V) from drinking water. The fast adsorption rate and the excellent adsorption capacity in the neutral pH range will render this removal technique attractive in practical use in chemical industry.     

Sequential soil washing techniques using hydrochloric acid and sodium hydroxide for remediating arsenic-contaminated soils in abandoned iron-ore mines

Sequential washing techniques using single or dual agents [sodium hydroxide (NaOH) and hydrochloric acid (HCl) solutions] were applied to arsenic-contaminated soils in an abandoned iron-ore mine area. We investigated the best remediation strategies to maximize arsenic removal efficiency for both soils and arsenic-containing washing solution through conducting a series of batch experiments. Based on the results of a sequential extraction procedure, most arsenic prevails in Fe-As precipitates or coprecipitates, and iron exists mostly in the crystalline forms of iron oxide. Soil washing by use of a single agent was not effective in remediating arsenic-contaminated soils because arsenic extractions determined by the Korean standard test (KST) methods for washed soils were not lower than 6mg kg(-1) in all experimental conditions. The results of X-ray diffraction (XRD) indicated that iron-ore fines produced mobile colloids through coagulation and flocculation in water contacting the soils, containing dissolved arsenic and fine particles of ferric arsenate-coprecipitated silicate. The first washing step using 0.2M HCl was mostly effective in increasing the cationic hydrolysis of amorphous ferrihydrite, inducing high removal of arsenic. Thus, the removal step of arsenic-containing flocs can lower arsenic extractions (KST methods) of washed soils. Among several washing trials, alternative sequential washing using 0.2M HCl followed by 1M HCl (second step) and 1M NaOH solution (third step) showed reliable and lower values of arsenic extractions (KST methods) of washed soils. This washing method can satisfy the arsenic regulation of washed soil for reuse or safe disposal application. The kinetic data of washing tests revealed that dissolved arsenic was easily readsorbed into remaining soils at a low pH. This result might have occurred due to dominant species of positively charged crystalline iron oxides characterized through the sequential extraction procedure. However, alkaline extraction using NaOH was effective in removing arsenic readsorbed onto the surface of crystalline minerals. This is because of the ligand displacement reaction of hydroxyl ions with arsenic species and high pH conditions that can prevent readsorption of arsenic.     

Adsorption of As(III) versus As(V) from aqueous solutions by cerium-loaded volcanic rocks

Environmental Science and Pollution Research - Contamination of drinking water with arsenic causes severe health problems in various world regions. Arsenic exists predominantly as As(III) and As(V)...     

Arsenic speciation in arsenic-rich Brazilian soils from gold mining sites under anaerobic incubation

BACKGROUND: Arsenic speciation in environmental samples is essential for studying toxicity, mobility and bio-transformation of As in aquatic and terrestrial environments. Although the inorganic species As(III) and As(V) have been considered dominant in soils and sediments, organisms are able to metabolize inorganic forms of arsenic into organo-arsenic compounds. Arsenosugars and methylated As compounds can be found in terrestrial organisms, but they generally occur only as minor constituents. We investigated the dynamics of arsenic species under anaerobic conditions in soils surrounding gold mining areas from Minas Gerais State, Brazil to elucidate the arsenic biogeochemical cycle and water contamination mechanisms. METHODS: Surface soil samples were collected at those sites, namely Paracatu Formation, Banded Iron Formation and Riacho dos Machados Sequence, and incubated in CaCl2 2.5 mmol L(-1) suspensions under anaerobic conditions for 1, 28, 56 and 112 days. After that, suspensions were centrifuged and supernatants analyzed for soluble As species by IC-ICPMS and HPLC-ICPMS. RESULTS: Easily exchangeable As was mainly arsenite, except when reducible manganese was present. Arsenate was mainly responsible for the increase in soluble arsenic due to the reductive dissolution of either iron or manganese in samples from the Paracatu Formation and Riacho dos Machados Sequence. On the other hand, organic species of As dominated in samples from the Banded Iron Formation during anaerobic incubation. DISCUSSION: Results are contrary to the expectation that, in anaerobic environments, As release due to the reductive dissolution of Fe is followed by As(V) reduction to As(III). The occurrence of organo-arsenic species was also found to be significant to the dynamics of soluble arsenic, mainly in soils from the Banded Iron Formation (BIF), under our experimental conditions. CONCLUSIONS: In general, As(V) and organic As were the dominant species in solution, which is surprising under anaerobic conditions in terrestrial environments. The unexpected occurrence of organic species of As was attributed to enrollment of ternary organic complexes or living organisms such as algae or cyanobacteria. PERSPECTIVES: These findings are believed to be useful for remediation strategies in mine-affected regions, as the organic As species are in general considered to be less toxic than inorganic ones and even As(V) is considered less mobile and toxic than As(III).     

Investigation of arsenic removal in batch wise water treatments by means of sequential hydride generation flow injection analysis

Arsenic water pollution is a big issue worldwide. Determination of inorganic arsenic in each oxidation state is important because As(III) is much more toxic than As(V). An automated arsenic measurement system was developed based on complete vaporization of As by a sequential procedure and collection/preconcentration of the vaporized AsH(3), which was subsequently measured by a flow analysis. The automated sensitive method was applied to monitoring As(III) and As(V) concentrations in contaminated water standing overnight. Behaviors of arsenics were investigated in different conditions, and unique time dependence profiles were obtained. For example, in the standing of anaerobic water samples, the As(III) concentration immediately began decreasing whereas dead time was observed in the removal of As(V). In normal groundwater conditions, most arsenic was removed from the water simply by standing overnight. To obtain more effective removal, the addition of oxidants and use of steel wools were investigated. Simple batch wise treatments of arsenic contaminated water were demonstrated, and detail of the transitional changes in As(III) and As(V) were investigated.     

Organo-modified sericite in the remediation of an aquatic environment contaminated with As(III) or As(V)

The aim of this investigation was to obtain the hybrid material precursor to the naturally and abundantly available sericite, a mica-based clay; the materials were further employed in the remediation of arsenic from aqueous solutions. The study was intended to provide a cost-effective and environmentally benign treatment technology. The hybrid organo-modified sericite was obtained using hexadecyltrimethylammonium bromide (HDTMA) and alkyldimethylbenzylammonium chloride (AMBA) organic surfactants by introducing regulated doses of HDTMA or AMBA. The materials were characterized using infrared and X-ray diffraction analytical data, whereas the surface morphology was discussed by taking its SEM images. These materials were employed to assess the pre-concentration and speciation of As(III) and As(V) from aqueous solutions. The batch reactor data showed that increasing the sorptive concentration (from 1.0 to 15.0 mg/L) and pH (i.e., pH 2.0 to 10.0) caused the percent uptake of As(III) and As(V) to decrease significantly. The kinetic data showed that a sharp initial uptake of arsenic reached its equilibrium state within about 50 min of contact time, and the sorption kinetics followed a pseudo-second-order rate law both for As(III) and As(V) sorption. A 1,000 times increase in the background electrolyte concentration, i.e., NaNO₃, caused a significant decrease in As(III) removal, whereas As(V) was almost unaffected, which inferred that As(III) was adsorbed, mainly by the van der Waals or even by the electrostatic attraction, whereas As(V) was adsorbed chemically and formed “inner-sphere” complexes at the solid/solution interface. The equilibrium state modeling studies indicated that the sorption data fitted well the Freundlich and Langmuir adsorption isotherms. Henceforth, the removal capacity was calculated under these equilibrium conditions. It was noted that organo-modified sericite possessed a significantly higher removal capacity compared to its virgin sericite. Between these two organo-modified sericite, the HDTMA-modified sericite possessed a higher removal capacity compared to the AMBA-modified sericite.     

Distribution of soil arsenic species, lead and arsenic bound to humic acid molar mass fractions in a contaminated apple orchard

Excessive application of lead arsenate pesticides in apple orchards during the early 1900s has led to the accumulation of lead and arsenic in these soils. Lead and arsenic bound to soil humic acids (HA) and soil arsenic species in a western Massachusetts apple orchard was investigated. The metal-humate binding profiles of Pb and As were analyzed with size exclusion chromatography-inductively coupled plasma mass spectrometry (SEC-ICP-MS). It was observed that both Pb and As bind "tightly" to soil HA molar mass fractions. The surface soils of the apple orchard contained a ratio of about 14:1 of water soluble As (V) to As (III), while mono-methyl (MMA) and di-methyl arsenic (DMA) were not detectable. The control soil contained comparatively very low levels of As (III) and As (V). The analysis of soil core samples demonstrated that As (III) and As (V) species are confined to the top 20 cm of the soil.