Arsenic Speciation Analysis in Water Samples: A Review of The Hyphenated Techniques

Interests in the determination of different arsenic species in natural waters is caused by the fact that toxic effects of arsenic are connected with its chemical forms and oxidation states. In determinations of water samples inorganic arsenate (As(III), As(V)), methylated metabolities (MMAA, DMAA) and other organic forms such as AsB, AsC, arsenosugars or arsenic containing lipids have the most importance. This article provides information about occurrence of the dominant arsenic forms in various water environments. The main factors controlling arsenic speciation in water are described. The quantification of species is difficult because the concentrations of different forms in water samples are relatively lowcompared to the detection limits of the available analytical techniques. Several hyphenated methods used in arsenic speciation analysis are described. Specific advantages and disadvantages of methods can define their application for a particular sample analysis. Insufficient selectivity and sensitivity of arsenic speciation methods cause searching for a new or modifications already existing techniques. Some aspects of improvement and modifications of the methods are highlighted.     

Arsenic-speciation in arsenate-resistant and non-resistant populations of the earthworm,Lumbricus rubellus

Arsenic speciation was determined in Lumbricus rubellus Hoffmeister from arsenic-contaminated mine spoil sites and an uncontaminated site using HPLC-MS, HPLC-ICP-MS and XAS. It was previously demonstrated that L. rubellus from mine soils were more arsenate resistant than from the uncontaminated site and we wished to investigate if arsenic speciation had a role in this resistance. Earthworms from contaminated sites had considerably higher arsenic body burdens (maximum 1,358 mg As kg-1) compared to the uncontaminated site (maximum 13 mg As kg-1). The only organo-arsenic species found in methanol/water extracts for all earthworm populations was arsenobetaine, quantified using both HPLC-MS and HPLC-ICP-MS. Arsenobetaine concentrations were high in L. rubellus from the uncontaminated site when concentrations were expressed as a percentage of the total arsenic burden (23% mean), but earthworms from the contaminated sites with relatively low arsenic burdens also had these high levels of arsenobetaine (17% mean). As arsenic body burden increased, the percentage of arsenobetaine present decreased in a dose dependent manner, although its absolute concentration rose with increasing arsenic burden. The origin of this arsenobetaine is discussed. XAS analysis of arsenic mine L. rubellus showed that arsenic was primarily present as As(III) co-ordinated with sulfur (30% approx.), with some As(v) with oxygen (5%). Spectra for As(III) complexed with glutathione gave a very good fit to the spectra obtained for the earthworms, suggesting a role for sulfur co-ordination in arsenic metabolism at higher earthworm arsenic burdens. It is also possible that the disintegration of As(III)-S complexes may have taken place due to (a) processing of the sample, (b) storage of the extract or (c) HPLC anion exchange. HPLC-ICP-MS analysis of methanol extracts showed the presence of arsenite and arsenate, suggesting that these sulfur complexes disintegrate on extraction. The role of arsenic speciation in the resistance of L. rubellus to arsenate is considered.     

Speciation of arsenic using solid phase extraction cartridges

Various solid phase extraction (SPE) cartridges were investigated for speciation of arsenite [As(III)], arsenate [As(v)], monomethylarsonic acid (MMA) and dimethylarsinic acid (DMA). Cartridges containing different types of sorbent materials were tested for arsenic retention and elution characteristics. Alumina cartridges were found to completely retain all the four target arsenic species, and are suitable for removal and preconcentration purposes. For speciation analysis, different arsenic species were separated on the basis of their selective retention on and elution from specific cartridges. DMA was retained on a resin-based strong cation exchange cartridge and eluted with 1.0 M HCl. MMA and As(v) were both retained on a silica-based strong anion exchange cartridge and sequentially eluted with 60 mM acetic acid (for MMA) and 1.0 M HCl [for As(v)]. As(III) was not retained on either cartridge and remained in solution. Arsenic species in solution and those eluted from the cartridges were subsequently quantified by using flow injection with hydride generation atomic fluorescence spectrometry (FI-HGAFS) and hydride generation atomic absorption spectrometry (FI-HGAAS). A detection limit of 0.05 microg L(-1) arsenic in water sample was achieved using HGAFS. An application of the method was demonstrated at a drinking water treatment facility. As(III) and As(v) species were determined in water at various stages of treatment. The method is suitable for routine determination of trace levels of arsenic in drinking water to comply with more stringent environmental regulations.     

Antimony speciation in terrestrial plants. Comparative studies on extraction methods

A suitable method for the extraction of antimony species from plant materials prior to IC-HG-AFS analysis is presented. The extraction efficiency with different extraction systems using various aqueous and aqueous/solvent mixtures was initially evaluated by analysing the Virginia Tobacco Leaves Certified Reference Material. The concentration of antimony extracted was compared with the total antimony content in the plant material measured by HG-AFS after focused microwave-acidic digestion using HNO3 and H2O2. The proposed extraction procedures were applied to antimony speciation in several plants from a natural terrestrial environment impacted by mining activities. End-over-end agitation (4 h) followed by sonication (1 h) extraction using 0.1 mol l(-1) citric acid was found to provide the best extraction efficiency while also giving reliable speciation information. Both inorganic and methylantimony species were found in the extractable portion of some terrestrial plants.     

Monitoring the species of arsenic, chromium and nickel in milled coal, bottom ash and fly ash from a pulverized coal-fired power plant in western Canada

The concentration of As, Cr and Ni and their speciation (As3+;5+, Cr3+;6+ and Ni0;2+) in milled coal, bottom ash and ash collected by electrostatic precipitator (ESP) from a coal fired-power plant in western Canada were determined using HGAAS, ICP-AES and XANES. The chemical fractionation of these elements was also determined by a sequential leaching procedure, using deionized water, NH4OAC and HCI as extracting agents. The leachate was analyzed by ICP-AES. Arsenic in the milled coal is mostly associated with organic matter, and 67% of this arsenic is removed by ammonium acetate. This element is totally removed from milled coal after extraction with HCI. Arsenic occurs in both the As3+ and the As5+ oxidation states in the milled coal, while virtually all (>90%) of the arsenic in bottom ash and fly ash appears to be in the less toxic arsenate (As5+) form. Both Ni and Cr in the milled coal are extracted by HCI, indicating that water can mobilize Ni and Cr in an acidic environment. The chromium is leached by water from fly ash as a result of the high pH of the water, which is induced during the leaching. Ammonium acetate removes Ni from bottom ash through an ion exchange process. Chromium in milled coal is present entirely as Cr3+, which is an essential human trace nutrient. The Cr speciation in bottom ash is a more accentuated version of the milled coal and consists mostly of the Cr3+ species. Chromium in fly ash is mostly Cr3+, with significant contamination by stainless-steel from the installation itself.     

Arsenic speciation in human hair: a new perspective for epidemiological assessment in chronic arsenicism

The analysis for arsenic in hair is commonly used in epidemiological studies to assess exposure to this toxic element. However, poor correlation between total arsenic concentration in hair and water sources have been found in previous studies. Exclusive determination of endogenous arsenic in the hair, excluding external contamination has become an analytical challenge. Arsenic speciation in hair appears as a new possibility for analytical assessing in As-exposure studies. This study applied a relative simple method for arsenic speciation in human hair based on water extraction and HPLC-HG-ICP-MS. The concentration of arsenic species in human hair was assessed in chronically As(V)-exposed populations from two villages (Esqui?a and Illapata) of the Atacama Desert, Chile. The arsenic concentrations in drinking water are 0.075 and 1.25 mg L(-1), respectively, where As(V) represented between 92 and 99.5% of the total arsenic of the consumed waters. On average, the total arsenic concentrations in hair from individuals of Esqui?a and Illapata were 0.7 and 6.1 microg g(-1), respectively. Four arsenic species, As(III), DMA(V), MMA(V) and As(V), were detected and quantified in the hair extracts. Assuming the found species in extracts represent the species in hair, more than 98% of the total arsenic in hair corresponded to inorganic As. On average, As(III) concentrations in hair were 0.25 and 3.75 microg g(-1) in Esqui?a and Illapata, respectively; while, the As(V) average concentrations were 0.15 and 0.45 microg g(-1) in Esqui?a and Illapata, respectively. Methylated species represent less than 2% of the extracted As (DMA(V)+ MMA(V)) in both populations. As(III) in hair shows the best correlation with chronic exposure to As(V) in comparison to other species and total arsenic. In fact, concentrations of As(total), As(III) and As(V) in hair samples are correlated with the age of the exposed individuals from Illapata (R= 0.65, 0.69, 0.57, respectively) and with the time of residence in this village (R= 0.54, 0.71 and 0.58, respectively).     

Uptake of arsenic by alkaline soils near alkaline coal fly ash disposal facilities

The attenuation of arsenic in groundwater near alkaline coal fly ash disposal facilities was evaluated by determining the uptake of arsenic from ash leachates by surrounding alkaline soils. Ten different alkaline soils near a retired coal fly ash impoundment were used in this study with pH ranging from 7.6 to 9.0, while representative coal fly ash samples from two different locations in the coal fly ash impoundment were used to produce two alkaline ash leachates with pH 7.4 and 8.2. The arsenic found in the ash leachates was present as arsenate [As(V)]. Adsorption isotherm experiments were carried out to determine the adsorption parameters required for predicting the uptake of arsenic from the ash leachates. For all soils and leachates, the adsorption of arsenic followed the Langmuir and Freundlich equations, indicative of the favorable adsorption of arsenic from leachates onto all soils. The uptake of arsenic was evaluated as a function of ash leachate characteristics and the soil components. The uptake of arsenic from alkaline ash leachates, which occurred mainly as calcium hydrogen arsenate, increased with increasing clay fraction of soil and with increasing soil organic matter of the alkaline soils. Appreciable uptake of arsenic from alkaline ash leachates with different pH and arsenic concentration was observed for the alkaline soils, thus attenuating the contamination of groundwater downstream of the retired coal fly ash impoundment.     

Phytoremediation assessment of <Emphasis Type="Italic">Gomphrena globosa</Emphasis> and <Emphasis Type="Italic">Zinnia elegans</Emphasis> grown in arsenic-contaminated hydroponic conditions as a safe and feasible alternative to be applied in arsenic-contaminated soils of the Bengal Delta

Several agricultural fields show high contents of arsenic because of irrigation with arsenic-contaminated groundwater. Vegetables accumulate arsenic in their edible parts when grown in contaminated soils. Polluted vegetables are one of the main sources of arsenic in the food chain, especially for people living in rural arsenic endemic villages of India and Bangladesh. The aim of this study was to assess the feasibility of floriculture in the crop rotation system of arsenic endemic areas of the Bengal Delta. The effects of different arsenic concentrations (0, 0.5, 1.0, and 2.0 mg As L^?1) and types of flowering plant (Gomphrena globosa and Zinnia elegans) on plant growth and arsenic accumulation were studied under hydroponic conditions. Total arsenic was quantified using atomic absorption spectrometer with hydride generation (HG-AAS). Arsenic was mainly accumulated in the roots (72 %), followed by leaves (12 %), stems (10 %), and flowers (<1 %). The flowering plants studied did not show as high phytoremediation capacities as other wild species, such as ferns. However, they behaved as arsenic tolerant plants and grew and bloomed well, without showing any phytotoxic signs. This study proves that floriculture could be included within the crop rotation system in arsenic-contaminated agricultural soils, in order to improve food safety and also food security by increasing farmer’s revenue.     

Determination of arsenic species in fish, crustacean and sediment samples from Thailand using high performance liquid chromatography (HPLC) coupled with inductively coupled plasma mass spectrometry (ICP-MS)

Suitable techniques have been developed for the extraction of arsenic species in a variety of biological and environmental samples from the Pak Pa-Nang Estuary and catchment, located in Southern Thailand, and for their determination using HPLC directly coupled with ICP-MS. The estuary catchment comprises a tin mining area and inhabitants of the region can suffer from various stages of arsenic poisoning. The important arsenic species, AsB, DMA, MMA, and inorganic arsenic (As III and V) have been determined in fish and crustacean samples to provide toxicological information on those fauna which contribute to the local diet. A Hamilton PRP-X100 anion-exchange HPLC system employing a step elution has been used successfully to achieve separation of the arsenic species. A nitric acid microwave digestion procedure, followed by carrier gas nitrogen addition- (N2)-ICP-MS analysis was used to measure total arsenic in sample digests and extracts. The arsenic speciation of the biological samples was preserved using a Trypsin enzymatic extraction procedure. Extraction efficiencies were high, with values of 82-102%(As) for fish and crustacean samples. Validation for these procedures was carried out using certified reference materials. Fish and crustacean samples from the Pak Pa-Nang Estuary showed a range for total arsenic concentration, up to 17 microg g(-1) dry mass. The major species of arsenic in all fauna samples taken was AsB, together with smaller quantities of DMA and, more importantly, inorganic As. For sediment samples, arsenic species were determined following phosphoric acid (1 M H3PO4) extraction in an open focused microwave system. A phosphate-based eluant, pH 6-7.5, with anion exchange HPLC coupled with ICP-MS was used for separation and detection of AsIII, AsV, MMA and DMA. The optimum conditions, identified using an estuarine sediment reference material (LGC), were achieved using 45 W power and a 20 minute heating period for extraction of 0.5 g sediment. The stability and recovery of arsenic species under the extraction conditions were also determined by a spiking procedure which included the estuarine sediment reference material. The results show good stability for all species after extraction with a variability of less than 10%. Total concentrations of arsenic in the sediments from the Pak Pa-Nang river catchment and the estuary covered the ranges 7-269 microg g(-1)and 4-20 [micro sign]g g(-1)(dry weight), respectively. AsV was the major species found in all the sediment samples with smaller quantities of AsIII. The presence of the more toxic inorganic forms of arsenic in both sediments and biota samples has implications for human health, particularly as they are readily 'available'.     

A biomaterial based approach for arsenic removal from water

We demonstrate that the non-living, dried roots of the water hyacinth plant [Eichhornia crassipes(Mart.) Solms] can rapidly remove arsenic from water. Atomic absorption spectrometry was used to demonstrate that more than 93% of arsenite (As(iii)) and 95% of arsenate (As(v)) were removed from a solution containing 200 microg As l(-1) within 60 minutes of exposure to a powder produced from dried roots. No difference in removal efficiency was observed between the two oxidation states of As studied. The amount of arsenic remaining in solution was found to be less than 10 microg l(-1) which is the WHO guideline limit value for As in drinking water. The presence of arsenic in drinking water in a number of countries in the developing world has been found to be much higher than the WHO level, affecting the health of millions of people. In this paper, we show that a biomaterial produced from dried water hyacinth roots, a plant that is found in abundant supply in many parts of the world, can provide a simple, effective and yet cheap method for removing arsenic from contaminated water.     

Investigation of arsenic speciation on drinking water treatment media utilizing automated sequential continuous flow extraction with IC-ICP-MS detection

Three treatment media, used for the removal of arsenic from drinking water, were sequentially extracted using 10 mM MgCl2(pH 8), 10 mM NaH2PO4(pH 7) followed by 10 mM (NH4)2C2O4(pH 3). The media were extracted using an on-line automated continuous extraction system which allowed the arsenic in each of the extraction fluids to be speciated on-line using IC-ICP-MS. The 10 mM MgCl2 preferentially extracted As(III) from each of the media. The percentage of the arsenic extracted by the MgCl2, relative to a HNO3/H2O2 digestion of the media, ranged from 0.1-2.3% for the three solids. The next sequential extraction fluid, 10 mM NaH2PO4, extracted some of the residual As(III) remaining on each of the media but the predominant species extracted was As(V). The 10 mM NaH2PO4 extracted 15.3 to 42.8% of the total arsenic relative to a total digested concentration for each of the media. The As(III) and As(V) stability studies conducted in these two extraction fluids indicated that conversion between As(III) and As(V) was not significant for the short extraction fluid sample contact time associated with the on-line continuous flow extraction cell. Finally, the 10 mM (NH4)2C2O4 extraction fluid was utilized in an off-line analysis mode because the Fe and As concentrations extracted from the media were not compatible with direct ICP-MS detection. The (NH4)2C2O4 extracted 2.9-29% As(III) for all three media and caused an oxidation of As(III) to As(V) during the extraction period for one of the three media. The sum of the arsenic from each of the three extraction fluids represented 92%, 44% and 53% of the available total arsenic for the three media, respectively. The speciation results for each media were obtained by adding all the speciation results from all three extraction fluids together and the resulting distribution of As(III)/As(V) compared well with the speciation results obtained via XANES.     

Quantitative arsenic speciation in two species of earthworms from a former mine site

The relationship between the total arsenic concentration and the chemical speciation of arsenic in two species of earthworm (Lumbricus rubellus and Dendrodrilus rubidus) in relation to the host soil, was investigated for 13 sites of varying arsenic content, including a background level garden soil and a former mine site at the Devon Great Consols, UK. Earthworms were collected with the host soil (As soil concentration range 16-12, 466 mg kg(-1) dry weight) and measured for their total arsenic (concentration range 7-595 mg kg(-1) dry weight) using inductively coupled plasma mass spectrometry (ICP-MS). A methanol-water mixture was used to extract arsenic species from the earthworms prior to determination of the individual arsenic species by a combination of anion and cation exchange high performance liquid chromatography coupled to inductively coupled plasma mass spectrometry (HPLC-ICP-MS). A gradient elution anion exchange method is presented whereby nine arsenic species could be measured in one sample injection. Arsenic species were identified by comparison of retention times and sample spiking with known standards and a fully characterised seaweed extract. Arsenic was generally present in the earthworm as arsenate (As(V)) or arsenite (As(III)) and arsenobetaine (AB). Methylarsonate (MA), dimethylarsinate (DMA) and three arsenosugars (glycerol, phosphate, sulfate) were present as minor constituents. These results are discussed in relation to the mechanisms for coping with exposure to soil bound arsenic.     

Effect of fasting on the pattern of urinary arsenic excretion

Millions of people in some of the poorest regions of the world are exposed to high levels of arsenic through drinking contaminated water. It has been reported that development of cancer caused by arsenic exposure in such populations is dependent on dietary and nutritional factors which can modulate arsenic metabolism. Many people in arsenic exposed regions of Bangladesh and India practice fasting for at least one month every year when they refrain from consumption of food and fluid during daylight hours. How such practices may modulate arsenic metabolism has not been previously investigated. This study investigated this issue by determining total arsenic and its species in urine samples from a group of 29 unexposed volunteers at the beginning of the fasting and at the end of approximately 12 h of fasting period. Inductively coupled plasma mass spectrometry (ICP-MS) and high performance liquid chromatography (HPLC) coupled with ICP-MS was used to measure the total arsenic and arsenic speciation in the urine samples, respectively. The mean total levels of arsenic at the beginning of fasting (18.3 microg g(-1) creatinine) and at the end of approximately 12 h of fasting (17.7 microg g(-1) creatinine) did not differ significantly (p > 0.05). However, the percentages of urinary arsenic as the methylated arsenic species methylarsonate (MA) were found to be significantly different (p < 0.05) and this species was observed more frequently at the end of fasting, although its overall concentration was similar. There were no significant differences (p > 0.05) in both the concentrations and percentages of other urinary arsenic species detected, namely arsenobetaine (AB) and dimethylarsinate (DMA). Arsenite (As(III)) and arsenate (As(V)) were also analyzed, but were not detected. We conclude that fasting for a period of 12 h results in a significant increase in the percentage of urinary arsenic as MA, and its frequency of detection in the volunteers at the end of the fasting period is almost nine fold higher. This suggests that metabolism of arsenic is altered by fasting.     

An investigation of arsenic contamination in Peninsular Malaysia based on Centella asiatica and soil samples

The first objective of this study was to provide data of arsenic (As) levels in Peninsular Malaysia based on soil samples and accumulation of As in Centella asiatica collected from 12 sampling sites in Peninsular Malaysia. The second objective was to assess the accumulation of As in transplanted C. asiatica between control and semi-polluted or polluted sites. Four sites were selected which were UPM (clean site), Balakong (semi-polluted site), Seri Kembangan (semi-polluted site) and Juru (polluted site). The As concentrations of plant and soil samples were determined by Instrumental Neutron Activation Analysis. The As levels ranged from 9.38 to 57.05 μg/g dw in soils, 0.21 to 4.33 μg/g dw in leaves, 0.18 to 1.83 μg/g dw in stems and 1.32–20.76 μg/g dw in roots. All sampling sites had As levels exceeding the CCME guideline (12 μg/g dw) except for Kelantan, P. Pauh, and Senawang with P. Klang having the highest As in soil (57.05 μg/g dw). In C. asiatica, As accumulation was highest in roots followed by leaves and stems. When the As level in soils were higher, the uptake of As in plants would also be increased. After the transplantation of plants to semi-polluted and polluted sites for 3 weeks, all concentration factors were greater than 50 % of the initial As level. The elimination factor was around 39 % when the plants were transplanted back to the clean sites for 3 weeks. The findings of the present study indicated that the leaves, stems and roots of C. asiatica are ideal biomonitors of As contamination. The present data results the most comprehensive data obtained on As levels in Malaysia.     

Arsenic speciation in freshwater snails and its life cycle variation

Terrestrial snails are consumed by humans occasionally and they are an important food source for many creatures including fish and birds. Little is known about arsenic speciation in these gastropods, let alone life cycle variations. Here we report on the arsenic speciation in freshwater snails from Pender Island and Vancouver Island, B.C., Canada, which was determined on methanol/water extracts (43-59% extraction efficiency) by using high performance liquid chromatography-inductively coupled plasma-mass spectrometry (HPLC-ICP-MS) and HPLC-electrospray tandem mass spectrometry. The tetramethylarsonium ion, oxo-arsenosugars and thio-arsenosugars are the main arsenic species encountered. Arsenobetaine, which is commonly found in the marine environment, is minor. Live bearing snails Viviparidae sp. from Pender Island were maintained in aquaria and the arsenic speciation in the unborn, newly born, and adult animals was monitored. Oxo-arsenosugars predominate in the adults, whereas thio-arsenosugars seem to predominate in juveniles, suggesting that these arsenicals are snail metabolites.     

Comparison of arsenic uptake ability of barnyard grass and rice species for arsenic phytoremediation

In this research, the relative performance in arsenic (As) remediation was evaluated among some barnyard grass and rice species under hydroponic conditions. To this end, four barnyard grass varieties and two rice species were selected and tested for their remediation potential of arsenic. The plants were grown for 2 weeks in As-rich solutions up to 10 mg As L^?1 to measure their tolerance to As and their uptake capabilities. Among the varieties of plants tested in all treatment types, BR-29 rice absorbed the highest amount of As in the root, while Nipponbare translocated the maximum amount of As in the shoot. Himetainubie barnyard grass produced the highest biomass, irrespective of the quantity of As in the solution. In all As-treated solutions, the maximum uptake of As was found in BR-29 followed by Choto shama and Himetainubie. In contrast, while the bioaccumulation factor was found to be the highest in Nipponbare followed by BR-29 and Himetainubie. The results suggest that both Choto shama and Himetainubie barnyard grass varieties should exhibit a great potential for As removal, while BR-29 and Nipponbare rice species are the best option for arsenic phytoremediation.     

Modeling Phosphate Influence on Arsenate Reduction Kinetics by a Freshwater Cyanobacterium

Arsenic speciation in natural surface-water systems can be highly impacted through biological processes that result in non-thermodynamically predicted species to dominate the system. In laboratory experiments, arsenate reduction by a freshwater cyanobacterium exhibited saturation kinetics increasingly inhibited by elevating solution phosphate concentrations. Approximately 100% arsenate reduction occurred by days 4, 7, and 10 in the low (0.35 μm), middle (3.5 μm), and high (35 μm) phosphate treatments, respectively, with maximum arsenate reduction rates ranged from 0.013 μmol As g C⁻¹ day⁻¹ in the high-phosphate treatment to 0.398 μmol As g C⁻¹ day⁻¹ in the low-phosphate treatment. Saturation kinetic models were utilized to evaluate the impact of cell growth and arsenate-phosphate uptake competition on arsenate reduction rates by the cyanobacterium. Results showed reduced arsenicals dominate arsenic speciation once growth reached steady state, indicating reduced arsenicals may dominate natural systems, even when considering conservatively high, abiotic arsenic reoxidation.     

Extractable copper, arsenic and antimony by EDTA solution from agricultural Chilean soils and its transfer to alfalfa plants (Medicago sativa L.)

Following our research on copper, arsenic and antimony in Chilean ecosystems, a study to understand the mobility and transport of these elements from soil to plants was carried out. So, the aim of this study, which follows on from the previous work, was to demonstrate if the total concentrations of these elements or their fractions extracted by 0.05 M EDTA pH 7 from different Chilean soils correlate with the respective total concentrations in the edible tissue of alfalfa plants collected simultaneously from 20 different sites affected or unaffected by mining activities. The highest copper fractions extracted by EDTA solutions were obtained in contaminated soils from the central region (41-69%); however the northern soils presented the highest extractable fractions of arsenic (9-34%). The antimony fraction was low in all soils (0.4-8.0%). Alfalfa plants from all contaminated sites presented high copper, arsenic and antimony concentrations (19-126 mg kg(-1), 5.7-16.3 mg kg(-1) and 0.16-1.7 mg kg(-1), respectively). Statistically significant correlations were obtained between the total contents of copper and arsenic and their respective extractable fractions in soils. Good correlations were found between elements in alfalfa plants. Correlations were also obtained between the total concentrations of three elements in soils and in alfalfa plants. However, excepting for antimony in the northern samples, higher correlation coefficients were evaluated when the extractable fractions were considered. Samples from the north region presented the highest copper transfer factor and the lowest for arsenic, in spite of the high concentration of this metalloid extracted by EDTA solution in these soils. There was not a clear trend on the transfer factor for antimony, probably due to the low content of this element in alfalfa plants and/or the low recovery obtained for this element by EDTA.     

Development, validation, and uncertainty measurement of multi-residue analysis of organochlorine and organophosphorus pesticides using pressurized liquid extraction and dispersive-SPE techniques

Increased water use associated with rapid growth in the Las Vegas Valley has inadvertently led to the creation of unique wetland systems in Southern Nevada with an abundance of biological diversity. Constructed and naturally created wetlands in the Las Vegas Valley watershed were studied to characterize and understand their potential role for improving ecosystem services (i.e., water purification). Nutrient and metal removal was assessed at four sites including a natural urban runoff wetland, a constructed urban runoff wetland, a constructed wastewater wetland, and a natural urban runoff/wastewater wetland. Plant nutrient uptake was dependent on ambient nutrient concentrations in water and sediments of specific wetlands, irrespective of the type of plants present. Phosphorus was mostly concentrated in below-ground plant parts whereas nitrogen was concentrated in above-ground parts. As for metalloids, bulrushes were more efficient than cattails at taking up arsenic and selenium. Averaging all the wetland sites and plant species, total nitrogen, phosphorus, arsenic and selenium removal was 924.2, 61.5, 0.30, and 0.38 kg/ha/year, respectively. Our findings suggest that natural and created wetland systems can improve water quality in the Las Vegas Valley watershed for some common pollutants, however, other measures are still needed to improve water quality below regulatory thresholds.     

Monitoring of copper,arsenic and antimony levels in agricultural soils impacted and non-impacted by mining activities,from three regions in Chile

This paper reports a comparative study of the concentration of three important environmental elements that are often found together in mineral deposits and then associated with mining activities; copper, arsenic and antimony. These elements were determined in 26 different agricultural soils from regions I, II and V in Chile, zones where the most important and biggest copper industries of this country are located. As background levels of these elements in soils have not been well established, in this study, both, impacted and non-impacted agricultural soils from different regions were considered. The relationships between the concentrations of these elements in soils were also examined. The concentration ranges for copper, arsenic and antimony were 11-530; 2.7-202 and 0.42-11 mg kg(-1) respectively. The copper concentrations in non-polluted soils from the north and central zone of Chile were similar. However, three sites from the north region have copper concentration as higher as 100 mg kg(-1), values that exceed the critical concentration for copper in soils. The concentration of arsenic and antimony in the north soils were higher than in non-impacted ones and, in the case of arsenic, greatly exceeded the world average concentration reported for this element in soils. The highest arsenic and antimony concentrations were found in Calama and Quillagua soils, two different sites in the Loa valley. The arsenic/antimony concentration ratio was higher in Quillagua soil. The high concentrations of three elements determined in impacted soils from region V (Puchuncaví and Catemu valleys) clearly shows the impact produced in this zone by the industrial and mining activities developed in their proximities. At Puchuncaví valley a clear decrease was observed in copper, arsenic and antimony concentrations in soils on the function of the distance from the industrial complex "Las Ventanas", and all concentrations exceeded the reported critical values for this matrix. Instead at Catemu valley, only the copper concentration was higher than this value. Statistically significant correlation was found for Cu-Sb in all soils; more significant Cu-As, Cu-Sb and Sb-As correlations were evaluated for soils from Puchuncaví and Catemu valleys, corroborating that high concentrations of copper, arsenic and antimony in these soils coming from the same pollution sources, the copper industry and the thermoelectric power plant.