Arsenic speciation in the freshwater crayfish, Cherax destructor Clark

Arsenic is a proven carcinogen that is found in the soil in gold mining regions at concentrations that can be thousands of times greater than gold. During mining arsenic is released into the environment, easily entering surrounding water bodies.The yabby (Cherax destructor) is a common freshwater crustacean native to Australia's central and eastern regions. Increasing aquaculture and export of these animals has led us to question the effects of mine contamination on the yabbies themselves and to assess any potential risks to consumers.This study determined the species of arsenic present in a number of organs from the yabby. Several arsenic contaminated dam sites in the goldfields of western Victoria were sampled for yabby populations. Yabbies from these sites were collected and analysed for arsenic speciation using high performance liquid chromatography-inductively coupled plasma-mass spectrometry (HPLC-ICP-MS). Results showed that type of exposure influenced which arsenic species was present in each organ, and that as arsenic exposure increased the prevalence of inorganic arsenic species, mostly As(V), within the tissues increased.The bioaccessibility of the arsenic present in the abdominal muscle (the edible portion for humans) of the yabbies was assessed. It was found that the majority of the bioaccessible arsenic was present as inorganic As(III) and As(V).     

Arsenic sorption on TiO2 nanoparticles: Size and crystallinity effects

Single solute As (III) and As (V) sorption on nano-sized amorphous and crystalline TiO₂ was investigated to determine: size and crystallinity effects on arsenic sorption capacities, possible As (III) oxidation, and the nature of surface complexes. Amorphous and crystalline nanoparticles were prepared using sol-gel synthesis techniques. For amorphous TiO₂, solute pH in the range of 4-9 had a profound impact on only As (V) sorption. As (III) and As (V) sorption isotherms indicated that sorption capacities of the different TiO₂ polymorphs were dependent on the sorption site density, surface area (particle size) and crystalline structure. When normalized to surface area, As (III) surface coverage on the TiO₂ surface remained almost constant for particles between 5 and 20 nm. However, As (V) surface coverage increased with the degree of crystallinity. X-ray absorption spectroscopic analysis provided evidence of partial As (III) oxidation on amorphous TiO₂ rather than crystalline TiO₂. The data also indicated that As (III) and As (V) form binuclear bidentate inner-sphere complexes with amorphous TiO₂ at neutral pH.     

Field and laboratory arsenic speciation methods and their application to natural-water analysis

The toxic and carcinogenic properties of inorganic and organic arsenic species make their determination in natural water vitally important. Determination of individual inorganic and organic arsenic species is critical because the toxicology, mobility, and adsorptivity vary substantially. Several methods for the speciation of arsenic in groundwater, surface-water, and acid mine drainage sample matrices using field and laboratory techniques are presented. The methods provide quantitative determination of arsenite [As(III)], arsenate [As(V)], monomethylarsonate (MMA), dimethylarsinate (DMA), and roxarsone in 2-8 min at detection limits of less than 1 microg arsenic per liter (microg As L(-1)). All the methods use anion exchange chromatography to separate the arsenic species and inductively coupled plasma-mass spectrometry as an arsenic-specific detector. Different methods were needed because some sample matrices did not have all arsenic species present or were incompatible with particular high-performance liquid chromatography (HPLC) mobile phases. The bias and variability of the methods were evaluated using total arsenic, As(III), As(V), DMA, and MMA results from more than 100 surface-water, groundwater, and acid mine drainage samples, and reference materials. Concentrations in test samples were as much as 13,000 microg As L(-1) for As(III) and 3700 microg As L(-1) for As(V). Methylated arsenic species were less than 100 microg As L(-1) and were found only in certain surface-water samples, and roxarsone was not detected in any of the water samples tested. The distribution of inorganic arsenic species in the test samples ranged from 0% to 90% As(III). Laboratory-speciation method variability for As(III), As(V), MMA, and DMA in reagent water at 0.5 microg As L(-1) was 8-13% (n=7). Field-speciation method variability for As(III) and As(V) at 1 microg As L(-1) in reagent water was 3-4% (n=3).     

An investigation of arsenic compounds in fur and feathers using X-ray absorption spectroscopy speciation and imaging

The accumulation of arsenic in fur and feathers has been used as an indicator of environmental quality and animal health. However, difficulties remain in distinguishing between arsenic present from external sources versus ingestion. In addition, low extraction efficiencies limit the complete characterization of arsenic compounds in such tissues by conventional analytical techniques (e.g. high performance liquid chromatography inductively coupled plasma mass spectrometry, HPLC-ICP-MS). X-ray absorption spectroscopy (XAS) provides an alternative method for determining the speciation of arsenic compounds directly. Inorganic arsenic is hypothesized to bind to thiol groups present in keratin-rich fur and feathers; however, arsenic-sulphur compounds are rarely reported in extracts of these tissues. Here we report that 5-58% of the total detected arsenic in rodent fur (vole, deer mouse, red squirrel) and bird feathers (gray jay, American tree sparrow, dark-eyed junco) from animals living in areas of elevated arsenic best resembled an arsenic(III)-sulphur compound as determined using XAS. In addition, fur and feathers with non-detectable levels of arsenic by XAS, were able to reduce pentavalent arsenic applied as either contaminated soil or an arsenate solution. XAS-imaging was used to localize dominant trivalent (AsIII) and pentavalent (AsV) arsenic compounds, and results were used to produce a "map" of arsenic in the sample. It is believed that the some of the reduced arsenic was absorbed, while external AsV compounds associated with soil/dust particles were easily distinguished on goose feathers. However, distinguishing whether internal arsenic arose from exogenous (from the environment) or endogenous (from the body) sources proved difficult with this technique.     

Arsenic association and stability in long-term disposed arsenic residues

Long-term stability of arsenic residues is investigated by determining arsenic phases remaining in gold mining residues after two decades of impoundment. The residues, generated by arsenic coprecipitation with iron and lime, were disposed of in-lined sites for 9-16 years (pit C) and 16-23 years (pits A and B). Arsenic is present in the residues as As(V) species, predominantly in the form of amorphous iron arsenate (55-75% As_total, pits A and B; 55-70% As_total, pit C) and sorbed onto amorphous iron-oxyhydroxides (20-33% As_total, pits A and B; 22-37% As_total, pit C). The presence of minor Ca-arsenate phases (undefined composition) and Al-arsenate coprecipitates is also indicated. The passive enrichment of iron in pits A and B, and the relative low concentration of calcium, sulfur and arsenic if compared to those of pit C, suggest that a soluble Ca-arsenate phase (e.g. CaHAsO₄.H₂O), a fraction of gypsum and As(III) were dissolved along 16-23 years of residue disposal. The presence of As(V) only and excess iron demonstrates the importance of the oxidation state and high Fe/As ratio on long-term stability of arsenic residues.     

Arsenic removal from an aqueous solution by a modified fungal biomass

Non-viable fungal biomass of Aspergillus niger, coated with iron oxide was investigated for its potential to remove arsenic from an aqueous solution. A. niger biomass coated with iron oxide showed maximum removal (approximately 95% of As(V) and 75% of As(III)) at a pH of 6. No strong relationship was observed between the surface charge of the biomass and arsenic removal.     

Urinary arsenic concentrations and speciation in residents living in an area with naturally contaminated soils

A cross sectional study was carried out to evaluate arsenic exposure of residents living in an area with a soil naturally rich in arsenic (As), through urinary measurements. During the summer of 2007, 322 people aged over 7 years and resident in the study area for at least 4 days prior to the investigation were recruited. The sum of urinary inorganic arsenic and metabolites (iAs + MMA + DMA) and speciation were determined by graphite furnace atomic absorption spectrometry and high performance liquid chromatography coupled to inductively coupled plasma mass spectrometry, respectively. Geometric means levels of iAs + MMA + DMA were 3.6 µg/L or 4.4 µg/g creatinine. The percent of DMA, As(III) and MMA contribution to urinary arsenic concentrations was respectively 84.2%, 12% and 3.7%. We found significant associations between urinary arsenic concentrations and the consumption of seafood (p = 0.03), the consumption of wine (p = 0.03) and beer (p = 0.001), respectively 3 and 4 days before the investigation. When we focus on the various species, As(V) was rarely detected and DMA is the predominant metabolite composing the majority of measurable inorganic-related As in the urine. Considering the percent of DMA contribution to iAs + MMA + DMA urinary concentrations, almost half of the subjects had 100% of DMA contribution whatever the concentration of urinary As whereas the others had a lower DMA contribution, between 39 and 90%.Arsenic levels reported in this original study in France were between 2 and 4 times lower than in other studies dealing with iAs + MMA + DMA levels associated with soil arsenic exposure. Arsenic levels were similar to those observed in unexposed individuals in European countries, although 10% were above the French guideline values for the general population.     

Bioaccessibility of lead and arsenic in traditional Indian medicines

Arsenic and lead have been found in a number of traditional Ayurvedic medicines, and the practice of Rasa Shastra (combining herbs with metals, minerals and gems), or plant ingredients that contain these elements, may be possible sources. To obtain an estimate of arsenic and lead solubility in the human gastrointestinal tract, bioaccessibility of the two elements was measured in 42 medicines, using a physiologically-based extraction test. The test consisted of a gastric phase at pH 1.8 containing organic acids, pepsin and salt, followed by an intestinal phase, at pH 7 and containing bile and pancreatin. Arsenic speciation was measured in a subset of samples that had sufficiently high arsenic concentrations for the X-ray absorption near edge structure analysis used. Bioaccessible lead was found in 76% of samples, with a large range of bioaccessibility results, but only 29% of samples had bioaccessible arsenic. Lead bioaccessibility was high (close to 100%) in a medicine (Mahayograj Guggulu) that had been compounded with bhasmas (calcined minerals), including naga (lead) bhasma. For the samples in which arsenic speciation was measured, bioaccessible arsenic was correlated with the sum of As(V)-O and As(III)-O and negatively correlated with As-S. These results suggest that the bioaccessible species in the samples had been oxidized from assumed As-S raw medicinal ingredients (realgar, As₄S₄, added to naga (lead) bhasma and As(III)-S species in plants). Consumption at recommended doses of all medicines with bioaccessibile lead or arsenic would lead to the exceedance of at least one standard for acceptable daily intake of toxic elements.     

Arsenic bioaccessibility in CCA-contaminated soils: Influence of soil properties, arsenic fractionation, and particle-size fraction

Arsenic bioaccessibility in soils near chromated copper arsenate (CCA)-treated structures has recently been reported, and results have shown that soil properties and arsenic fractionation can influence bioaccessibility. Because of the limited data set of published results, additional soil samples and a wider range of soil properties are tested in the present work. The objectives are: (1) to confirm previous results regarding the influence of soil properties on arsenic bioaccessibility in CCA-contaminated soils, (2) to investigate additional soil properties influencing arsenic bioaccessibility, and to identify chemical extractants which can estimate in vitro gastrointestinal (IVG) bioaccessibility, (3) to determine arsenic speciation in the intestinal phase of the IVG method and, (4) to assess the influence of two particle-size fractions on arsenic bioaccessibility. Bioaccessible arsenic in eight soils collected near CCA-treated utility poles was assessed using the IVG method. Five out of the eight soils were selected for a detailed characterization. Moreover, these five soils and two certified reference materials were tested by three different metal oxide extraction methods (citrate dithionite (CD), ammonium oxalate (OX), and hydroxylamine hydrochloride (HH)). Additionally, VMINTEQ was used to determine arsenic speciation in the intestinal phase. Finally, two particle-size fractions (< 250 μm, < 90 μm) were tested to determine their influence on arsenic bioaccessibility. First, arsenic bioaccessibility in the eight study-soils ranged between 17.0 ± 0.4% and 46.9 ± 1.1% (mean value 30.5 ± 3.6%). Using data from 20 CCA-contaminated soil samples, total organic carbon (r = 0.50, p < 0.05), clay content (r = − 0.57, p < 0.01), sand content (r = 0.48, p < 0.05), and water-soluble arsenic (r = 0.66, p < 0.01) were correlated with arsenic bioaccessibility. The mean percentage of total arsenic extracted from five selected soils was: HH (71.9 ± 4.1%) > OX (58.0 ± 3.1%) > water-soluble arsenic (2.2 ± 0.5%), while the mean value for arsenic bioaccessibility was 27.3 ± 2.8% (n = 5). Arsenic extracted by HH (r = 0.85, p < 0.01, n = 8) and OX (r = 0.93, p < 0.05, n = 5), showed a strong correlation with arsenic bioaccessibility. Moreover, dissolved arsenic in the intestinal phase was exclusively under the form of arsenate As(V). Finally, arsenic bioaccessibility (in mg/kg) increased when soil particles < 90 μm were used.     

Mineralogical and geochemical controls of arsenic speciation and mobility under different redox conditions in soil, sediment and water at the Mokrsko-West gold deposit, Czech Republic

Naturally contaminated soil, sediment and water at the Mokrsko-West gold deposit, Central Bohemia, have been studied in order to determine the processes that lead to release of As into water and to control its speciation under various redox conditions. In soils, As is bonded mainly to secondary arseniosiderite, pharmacosiderite and Fe oxyhydroxides and, rarely, to scorodite; in sediments, As is bonded mainly to Fe oxyhydroxides and rarely to arsenate minerals.The highest concentrations of dissolved As were found in groundwater (up to 1141 μg L^− 1), which mostly represented a redox transition zone where neither sulphide minerals nor Fe oxyhydroxide are stable. The main processes releasing dissolved As in this zone are attributed to the reductive dissolution of Fe oxyhydroxides and arsenate minerals, resulting in a substantial decrease in their amounts below the groundwater level. Some shallow subsurface environments with high organic matter contents were characterized by reducing conditions that indicated a relatively high amount of S^− 2,0 in the solid phase and a lower dissolved As concentration (70-80 μg L^− 1) in the pore water. These findings are attributed to the formation of Fe(II) sulphides with the sorbed As. Under oxidizing conditions, surface waters were undersaturated with respect to arsenate minerals and this promoted the dissolution of secondary arsenates and increased the As concentrations in the water to characteristic values from 300 to 450 μg L^− 1 in the stream and fishpond waters. The levels of dissolved As(III) often predominate over As(V) levels, both in groundwaters and in surface waters. The As(III)/As(V) ratio is closely related to the DOC concentration and this could support the assumption of a key role of microbial processes in transformations of aqueous As species as well as in the mobility of As.     

Enhanced recovery of arsenite sorbed onto synthetic oxides by L-ascorbic acid addition to phosphate solution: calibrating a sequential leaching method for the speciation analysis of arsenic in natural samples

Stripping voltammetry capable of detecting 0.3microg/L arsenate and arsenite was applied for speciation analysis of arsenic sorbed onto synthetic ferrihydrite, goethite at As/Fe ratio of approximately 1.5mg/g with or without birnessite after sequential extraction using 1M phosphate (24 and 16 h) and 1.2M HCl (1h). Precautions to avoid oxygen were undertaken by extracting under anaerobic conditions and by adding 0.1M l-ascorbic acid to 1M NaH(2)PO(4) (pH 5). Addition of l-ascorbic acid did not reduce As(V) to As(III). The recovery rate for As(III) using l-ascorbic acid for extraction (pH 5) but not for adsorption was 81% and 74% of total sorbed As, and was 99% and 97% of extracted As for ferrihydrite and goethite, respectively. Birnessite oxidized most As(III) during the adsorption procedure. l-ascorbic acid used both in adsorption and extraction procedures improved the recovery of As(III) to 79-94% for ferrihydrite-birnessite and 57-94% for goethite-birnessite systems with Fe/Mn ratios of 7, 70, 140 and 280g/g.     

Remediation of arsenic contaminated soils by iron-oxide application, evaluated in terms of plant productivity, arsenic and phytotoxic metal uptake

Four iron-bearing additives, selected for known or potential ability to adsorb anions, were evaluated for their effectiveness in attenuation of arsenic (As) in three soils with different sources of contamination (canal dredgings, coal fly ash deposits, and low-level alkali waste). Amendments used were lime, goethite (alpha-FeOOH) (crystallised iron oxide) and three iron-bearing additives, iron grit and iron (II) and (III) sulphates plus lime, which result in 'de novo' iron oxide formation in soils. Each was applied to the test soils at a rate of 1% w/w. A series of plant growth trials were conducted on the equilibrated, amended soils using spinach (Spinacia oleracea) and tomato (Lycopersicon esculentum) as test crops. These were grown in the contaminated soils for a period of three months in controlled glasshouse conditions. Evaluation of the potential of the amendments as immobilising agents was determined by plant growth (biomass) and elemental accumulation in plant tissues, indicating the bioavailability of As and other heavy metals following amendment. Goethite produced the most promising results in terms of reduction of plant shoot As content. It was concluded that, whilst Fe-oxides may be used as effective in situ amendments to attenuate As in soils by reducing its bioavailability, their effects on plant growth require careful consideration. In addition, soil-plant transfer of As was not completely halted by any amendment.     

Influence of metals and metal speciation on the growth of filamentous bacteria

Calcium, copper, nickel and zinc were examined for their effect on the growth of axenic filamentous bacteria which included strains of Thiothrix, type 021N and type 1701. All organisms grew best at the upper range of calcium concentrations tested. Heavy metals were also less toxic to Thiothrix strain A1 at higher calcium concentrations. Copper was more inhibitory than either nickel or zinc and copper-nickel and copper-zinc mixtures appeared to act synergistically in suppressing the development of Thiothrix strain A1. In contrast, nickel toxicity could be reduced by the addition of zinc to the medium. Metal toxicity could also be diminished by the chelating agent, EDTA; therefore, free metal ions were most likely responsible for the observed toxic effects. A computer model, MINEQL, was used to predict metal speciation and to determine the potential for various media components to control speciation of the metals. The suitability of the computer model was determined by comparison of predicted and analyzed free metal ion concentrations.     

Assessment of the solubility and bioaccessibility of arsenic in realgar wine using a simulated gastrointestinal system

Consumption of arsenic (As) wine is a traditional activity during the classic Chinese festival of Duanwu, colloquially known worldwide as the Dragon Boat Day. Arsenic wine is drunk on the morning of the fifth day of the fifth lunar calendar month to commemorate the death of Qu Yuan, a famed Chinese poet who drowned himself in protest of a corrupt government, and to protect against ill fortune. Although realgar minerals are characteristically composed of sparingly soluble tetra-arsenic tetra-sulfides (As₄S₄), purity does vary with up to 10% of As being present as non-sulfur bound species, such as arsenate (As^V) and arsenite (As^III). Despite, the renewed interest in As speciation and the bioaccessibility of the active As components in realgar based Chinese medicines, little is known about the safety surrounding the cultural practice of drinking As wine. In a series of experiments the speciation and solubility of As in a range of wines were investigated. Furthermore, a simulated gastrointestinal system was employed to predict the impact of digestive processes on As bioavailability. The predominant soluble As species found in all the wines were As^III and As^V. Based on typical As wine recipes employing 0.1 g realgar mL^− 1 wine, the concentration of dissolved As ranged from ca. 100 to 400 mg L^− 1 depending on the ethanol content of the preparation: with the As solubility found to be higher in wines with a lower proportion of ethanol. Based on a common 100 mL measure of wine with a concentration of 400 mg As L^− 1, the amount of soluble As would equate to around half of the acute minimal lethal dose for adults. This is likely an underestimate of the bioaccessible concentration, as a three-fold increase in bioaccessibility could be observed in the intestinal phase based on the results from the stimulated gastrointestinal system.     

Enhanced arsenic removal using mixed metal oxide impregnated chitosan beads

Mixed metal oxide impregnated chitosan beads (MICB) containing nanocrystalline Al₂O₃ and nanocrystalline TiO₂ were successfully developed. This adsorbent exploits the high capacity of Al₂O₃ for arsenate and the photocatalytic activity of TiO₂ to oxidize arsenite to arsenate, resulting in a removal capacity higher than that of either metal oxide alone. The composition of the beads was optimized for maximum arsenite removal in the presence of UV light. The mechanism of removal was investigated and a mode of action was proposed wherein TiO₂ oxidizes arsenite to arsenate which is then removed from solution by Al₂O₃. Pseudo-second order kinetics were used to validate the proposed mechanism. MICB is a more efficient and effective adsorbent for arsenic than TiO₂-impregnated chitosan beads (TICB), previously reported on, yet maintains a desirable life cycle, free of complex synthesis processes, toxic materials, and energy inputs.     

Aquatic microbial activity and macrofaunal profiles of an Oklahoma stream

A toxicity assessment was conducted on Skeleton Creek, near Enid, Okla. This creek received effluents from an oil refinery, municipal waste treatment facility, and a fertilizer processing plant. Microbial activity assays, which focused on sediments, included: dehydrogenase, alkaline phosphatase, glucosidase, amylase and protease activity. Microbial electron transport system activity was also measured in overlying waters and sediments. Results were compared to a study conducted at the same time by the U.S. Environmental Protection Agency (EPA) which measured in-stream fish, plankton and benthic communities. In addition, EPA conducted 7-day Ceriodaphnia reproductive toxicity tests and 7-day larval fathead minnow growth tests. Effects occurred below the 3 discharges and similar response patterns were noted between surrogate microbial assays and stream communities. These results highlight the importance and feasibility of multi-tiered test schemes in aquatic toxicity assessments.     

Arsenic microdistribution and speciation in toenail clippings of children living in a historic gold mining area

Arsenic is naturally associated with gold mineralisation and elevated in some soils and mine waste around historical gold mining activity in Victoria, Australia. To explore uptake, arsenic concentrations in children's toenail clippings and household soils were measured, and the microdistribution and speciation of arsenic in situ in toenail clipping thin sections investigated using synchrotron-based X-ray microprobe techniques. The ability to differentiate exogenous arsenic was explored by investigating surface contamination on cleaned clippings using depth profiling, and direct diffusion of arsenic into incubated clippings. Total arsenic concentrations ranged from 0.15 to 2.1 µg/g (n = 29) in clipping samples and from 3.3 to 130 µg/g (n = 22) in household soils, with significant correlation between transformed arsenic concentrations (Pearson's r = 0.42, P = 0.023) when household soil was treated as independent. In clipping thin sections (n = 2), X-ray fluorescence (XRF) mapping showed discrete layering of arsenic consistent with nail structure, and irregular arsenic incorporation along the nail growth axis. Arsenic concentrations were heterogeneous at 10 × 10 µm microprobe spot locations investigated (< 0.1 to 13.3 µg/g). X-ray absorption near-edge structure (XANES) spectra suggested the presence of two distinct arsenic species: a lower oxidation state species, possibly with mixed sulphur and methyl coordination (denoted As^≈ III_{(-S, -CH3)}); and a higher oxidation state species (denoted As^≈ V_(-O)). Depth profiling suggested that surface contamination was unlikely (n = 4), and XRF and XANES analyses of thin sections of clippings incubated in dry or wet mine waste, or untreated, suggested direct diffusion of arsenic occurred under moist conditions. These findings suggest that arsenic in soil contributes to some systemic absorption associated with periodic exposures among children resident in areas of historic gold mining activity in Victoria, Australia. Future studies are required to ascertain if adverse health effects are associated with current levels of arsenic uptake.     

Identification and characterization of metabolic properties of bacterial populations recovered from arsenic contaminated ground water of North East India (Assam)

Diversity of culturable bacterial populations within the Arsenic (As) contaminated groundwater of North Eastern state (Assam) of India is studied. From nine As contaminated samples 89 bacterial strains are isolated. 16S rRNA gene sequence analysis reveals predominance of Brevundimonas (35%) and Acidovorax (23%) along with Acinetobacter (10%), Pseudomonas (9%) and relatively less abundant (<5%) Undibacterium, Herbaspirillum, Rhodococcus, Staphylococcus, Bosea, Bacillus, Ralstonia, Caulobacter and Rhizobiales members. High As(III) resistance (MTC 10–50 mM) is observed for the isolates obtained from As(III) enrichment, particularly for 3 isolates of genus Brevundimonas   (MTC 50 mM). In contrast, high resistance to As(V) (MTC as high as 550 mM) is present as a ubiquitous property, irrespective of isolates' enrichment condition. Bacterial genera affiliated to other groups showed relatively lower degree of As resistance [MTCs of 15–20 mM As(III) and 250–350 mM As(V)]. As(V) reductase activity is detected in strains with high As(V) as well as As(III) resistance. A strong correlation could be established among isolates capable of reductase activity and siderophore production as well as As(III) tolerance. A large number of isolates (nearly 50%) is capable of anaerobic respiration using alternate inorganic electron acceptors [As(V), Se(VI), Fe(III), ₃NO²⁻${{\text{NO}}_3}^{2\mathrm{-}}$, ₄SO²⁻${{\text{SO}}_4}^{2\mathrm{-}}$, S₂O₃²⁻${{\text{S}}_2{\text{O}}_3}^{2\mathrm{-}}$]. Ability to utilize different carbon sources ranging from C2–C6 compounds along with some complex sugars is also observed. Particularly, a number of strains is found to possess ability to grow chemolithotrophically using As(III) as the electron donor. The study reports for the first time the identity and metabolic abilities of bacteria in As contaminated ground water of North East India, useful to elucidate the microbial role in influencing mobilization of As in the region.     

Arsenic solubility and distribution in poultry waste and long-term amended soil

The purpose of this study was to quantify the solubility and distribution of As among solid-phase components in poultry wastes and soils receiving long-term poultry waste applications. Arsenic in the water-soluble, NaOCl-extractable (organically bound), NH(2)OH x HCl-extractable (oxide bound) and residual fractions were quantified in an Upper Coastal Plain soil (Neshoba County, MS) that received annual waste applications. After 25 years, As in the amended soil had a mean of 8.4 mg kg(-1) compared to 2.68 mg kg(-1) for a non-amended soil. Arsenic in the amended soil was mainly in the residual fraction (72% of total), which is generally considered the least bioavailable fraction. Arsenic in poultry waste samples was primarily water-soluble (5.3-25.1 mg kg(-1)), representing 36-75% of the total As. To assess the extent of spatial heterogeneity, total As in a 0.5-ha area within the long-term waste-amended field was quantified. Soil surface samples were taken on 10-m grid points and results for total As appeared negatively skewed and approximated a bimodal distribution. Total As in the amended soil was strongly correlated with Fe oxides, clay and hydroxy interlayered vermiculite concentrations, and negatively correlated with Mehlich III-P, mica and quartz contents.     

Optimization of capacity and kinetics for a novel bio-based arsenic sorbent, TiO2-impregnated chitosan bead

The optimization of TiO₂-impregnated chitosan beads (TICB) as an arsenic adsorbent is investigated to maximize the capacity and kinetics of arsenic removal. It has been previously reported that TICB can 1) remove arsenite, 2) remove arsenate, and 3) oxidize arsenite to arsenate in the presence of UV light and oxygen. Herein, it is reported that adsorption capacity for TICB is controlled by solution pH and TiO₂ loading within the bead and enhanced with exposure to UV light. Solution pH is found to be a critical parameter, whereby arsenate is effectively removed below pH 7.25 and arsenite is effectively removed below pH 9.2. A model to predict TICB capacity, based on TiO₂ loading and solution pH, is presented for arsenite, arsenate, and total arsenic in the presence of UV light. The rate of removal is increased with reductions in bead size and with exposure to UV light. Phosphate is found to be a direct competitor with arsenate for adsorption sites on TICB, but other relevant common background groundwater ions do not compete with arsenate for adsorption sites. TICB can be regenerated with weak NaOH and maintain full adsorption capacity for at least three adsorption/desorption cycles.