Spatial and seasonal variation of arsenic speciation in Pantanal soda lakes.

The occurrence of high arsenic concentrations (up to 3000 µg L-1) in water of soda lakes of the Pantanal wetland is a remarkable case of natural arsenic contamination in South America. However, little is known about arsenic speciation in this environment, particularly regarding speciation changes related to lake trophic status and seasonal variations. To fill this gap, arsenic speciation analysis was carried out in surface (SW) and subsurface (SSW) waters sampled in five soda lakes with different eutrophication status, in two dry and one wet season. As(V) was the dominant species in these waters, while As(III), DMA, MMA and likely complex organic species were present in lower amounts. The results allow to conclude that the arsenic speciation in SW and SSW varies seasonally according to the regional wet or dry periods and lake water levels. In eutrophic turbid and in oligotrophic vegetated soda lakes, arsenic speciation was also characterized by spatial differences between edge and center or between the SW and SSW. Cyanobacteria or macrophytes/algae are involved in arsenic biotransformation in soda lakes through its metabolic and detoxification processes. Significant variation in surface water arsenic speciation occurs as a result of seasonal primary production fluctuation or water arsenic concentration changes in the soda lakes, increasing organoarsenics in dry periods, whereas in flood periods, As(V) prevails. Spatial distribution of arsenic species is significantly impacted by biogeochemical conditions at the water/sediment interface in soda lakes.

Magnetic solid phase extraction as a nonchromatographic method for the quantification of ultratrace inorganic arsenic in rice by inductively coupled plasma-optical emission spectrometry (ICP OES).

An alternative analytical method was developed for the quantification of inorganic arsenic (iAs) in rice by ICP OES. Iron nanoparticles modified with an organophosphorus compound were used as the solid phase for MSPE of iAs from the plant matrix. The MSPE procedure was performed using 4 mL of a buffer solution with pH 4.0, 20 mg of the nanomaterial, and a 15-min extraction time. The total As (tAs) by ICP OES was also quantified using the same MSPE procedure after solubilization of the samples by a block digester. The accuracy of tAs and iAs quantification was verified using CRM NIST 1568b (97 % and 101 % recovery, respectively). The precision (RSD < 15 %) and LOD and LOQ (1.08 and 3.70 µg kg-1, respectively) of the proposed method were satisfactory. The rice samples had tAs contents between 0.090 and 0.295 mg kg-1 and iAs mass fractions between 0.055 and 0.109 mg kg-1.

The impact of artisanal gold mining, ore processing and mineralization on water quality in Marmato, Colombia.

Marmato, Colombia, has been an important centre of gold mining since before the first Spanish colonizers arrived in 1536. The Marmato deposit is hosted in a dacite and andesite porphyry stock as sheeted sulphide-rich veinlet systems. The district is currently experiencing a surge in both major mining projects and artisanal mining, driven by sustained high gold prices. Ore from small-scale and artisanal gold mining is processed in numerous small mills (entables) around Marmato, which impact surface water quality through the discharge of milled waste rock slurry, highly alkaline cyanide-treated effluent, and high dissolved metal loads. To investigate the impact of artisanal mining and ore processing, water samples were collected in January 2012 from streams around Marmato. The average dissolved metal concentrations in impacted streams were Zn, 78 mg L-1; Pb, 0.43 mg L-1; Cu, 403 µg L-1 Cd, 255 µg L-1; As, 235 µg L-1; Ni, 67 µg L-1; Co, 55 µg L-1; Sb, 7 µg L-1; and Hg, 42 ng L-1, exceeding World Health Organization drinking water guidelines. In addition, arsenic speciation was conducted in-situ and indicated that 91-95% of inorganic arsenic species is in the form of As(V). Spatial analysis of the data suggests that entables processing ore for artisanal miners are the main contributor to water pollution, with high sediment loads, alkalinity and elevated concentrations of dissolved arsenic, cadmium, mercury and lead, caused by the processing of gold-bearing sulphides in the entables. Geochemical data from surface water were compared to a comprehensive data set of whole rock analyses from drill core and channel samples from the deposit, indicating that the deposit is significantly enriched in gold, silver, lead, zinc, arsenic, antimony, and cadmium compared to crustal averages, which is reflected in the surface water geochemistry. However, elevated mercury levels in surface water cannot be explained by enrichment of mercury in the deposit and strongly suggest that mercury is being added to concentrates during ore processing to amalgamate fine gold.

On-line speciation analysis of arsenic compounds in commercial edible seaweed by HPLC-UV-thermo-oxidation-HG-AFS.

Arsenic speciation analysis in dried seaweeds was carried out using an on-line HPLC-UV-thermo-oxidation-HG-AFS system. Species separated and quantified were: arsenite [As(III)], arsenate [As(V)], monomethylarsonic acid (MMA), dimethylarsinic acid (DMA) and different arsenosugars. Extraction efficiency ranged between 38 and 83%. Chromatographic separation was achieved in gradient elution mode using (NH4)2CO3 as mobile phase in the pH range 9-10.3. Total As concentration was quantified by ICP-MS after microwave digestion. Limits of detection were in the range 3.0 to 6.0 ng g-1 for the species under study based on peak height and the relative standard deviation was <8% at 10 µg L-1 As. The accuracy of the procedure was verified by analyzing the CRM BCR-279 Ulva lactuca. Results for total As were in agreement with the certified values. The HPLC-(UV)-HG-AFS system resulted suitable for quantification of eight As compounds. Results showed that arsenosugars are the most abundant compounds in the investigated seaweeds.

Non-chromatographic arsenic speciation analyses in wild shrimp (Farfantepenaeus brasiliensis) using functionalized magnetic iron-nanoparticles.

A new iron-magnetic nanomaterial functionalized with organophosphorus compound was used as solid-phase for arsenic speciation analysis in seafood samples by ICP-MS. The procedure was optimized using chemometric tools and the variables pH = 4.0, 15 min extraction time, and 20 mg of mass of material were obtained as the optimum point. The inorganic arsenic (iAs) extracted using nanoparticles presented concentrations between 20 and 100 µg kg-1 in the evaluated samples. The method was validated for accuracy using CRMs DOLT-5 and DORM-4. It was possible to reuse the same magnetic nanomaterial for 6 successive cycles, and we obtained a detection limit of 16.4 ng kg-1. The proposed method is suitable for the use of inorganic speciation of As, presenting good accuracy, precision, relatively low cost, and acquittance to green chemistry principles.

As3MT and GST Polymorphisms Influencing Arsenic Metabolism in Human Exposure to Drinking Groundwater.

The urinary arsenic metabolites may vary among individuals and the genetic factors have been reported to explain part of the variation. We assessed the influence of polymorphic variants of Arsenic-3-methyl-transferase and Glutathione-S-transferase on urinary arsenic metabolites. Twenty-two groundwater wells for human consumption from municipalities of Colombia were analyzed for assessed the exposure by lifetime average daily dose (LADD) (µg/kg bw/day). Surveys on 151 participants aged between 18 and 81 years old were applied to collect demographic information and other factors. In addition, genetic polymorphisms (GSTO2-rs156697, GSTP1-rs1695, As3MT-rs3740400, GSTT1 and GSTM1) were evaluated by real time and/or conventional PCR. Arsenic metabolites: AsIII, AsV, monomethylarsonic acid (MMA), and dimethylarsinic acid (DMA) were measured using HPLC-HG-AFS. The influence of polymorphic variants, LADD and other factors were tested using multivariate analyses. The median of total arsenic concentration in groundwater was of 33.3 µg/L and the median of LADD for the high exposure dose was 0.33 µg/kg bw/day. Univariate analyses among arsenic metabolites and genetic polymorphisms showed MMA concentrations higher in heterozygous and/or homozygous genotypes of As3MT compared to the wild-type genotype. Besides, DMA concentrations were lower in heterozygous and/or homozygous genotypes of GSTP1 compared to the wild-type genotype. Both DMA and MMA concentrations were higher in GSTM1-null genotypes compared to the active genotype. Multivariate analyses showed statistically significant association among interactions gene-gene and gene-covariates to modify the MMA and DMA excretion. Interactions between polymorphic variants As3MT*GSTM1 and GSTO2*GSTP1 could be potential modifiers of urinary excretion of arsenic and covariates as age, LADD, and alcohol consumption contribute to largely vary the arsenic individual metabolic capacity in exposed people.

Occupational exposure of foundry workers assessed by the urinary concentrations of 18 elements and arsenic species.

BACKGROUND: Some raw materials applied in Fe foundry industries may contain potentially toxic elements. Thus, foundry worker's occupational exposure is a constant health concern. METHOD: In this study, 194 urine samples from foundry workers were analyzed by inductively coupled plasma mass spectrometry for biomonitoring of Al, As, Ba, Cd, Co, Cr, Cs, Cu, Fe, I, Mn, Ni, Pb, Sb, Sn, Se, U and Zn. Moreover, arsenic speciation was performed in representative samples of production sector workers (group A) and administration sector workers (group B). RESULTS: Concentrations of As, Pb, Cd, Cu, Cs, I, Sb in urines from group A were higher than those found for group B. Samples of group A presented Cs, Ni, Mn, Pb, U and Zn concentrations higher than values reported for exposed workers assessed by other studies. Forty-four samples from group A exceed As-reference limits. Group A had approximately seven times more inorganic As (as arsenite) and 14 times more organic As (as dimethyl As) than group B. A statistically significant difference was observed in the elemental concentration in the workers' urine by the time in the function. Moreover, alcohol consumption is probably influencing the urine concentration of As, Ba, Cd, Co, Cu, Fe, I, Se and Zn. CONCLUSION: The monitored foundry workers are exposed to potentially toxic elements and more attention must be given to their health. Therefore, workplace safety conditions must be improved, and constant biomonitoring is necessary to ensure workers' health.

Geographical variations in arsenic contents in rice plants from Latin America and the Iberian Peninsula in relation to soil conditions.

Arsenic is a ubiquitous, toxic element that is efficiently accumulated by rice plants. This study assessed the spatial variability in the total As (tAs) contents and organic and inorganic forms in different types of rice, plant parts (husk, stem, leaves and phytoliths) and residues. Samples were collected in different countries in Latin America (Ecuador, Brazil and Peru) and the Iberian Peninsula (Spain and Portugal). The tAs content in commercial polished rice from the Latin American countries was similar (0.130-0.166 mg kg-1) and significantly lower than in the rice from the Iberian countries (0.191 ± 0.066 mg kg-1), and together, the tAs concentration in brown rice (236 ± 0.093 mg kg-1) was significantly higher than in polished and parboiled rice. The inorganic As (iAs) content in rice was similar in both geographical regions, and the aforementioned difference was attributed to dimethylarsinic acid (DMA). The relative abundance of organic species increased as the tAs content in rice grain increased. A meta-analysis of our and previously reported data confirmed the negative correlation between iAs/tAs and tAs. At low tAs concentrations, inorganic forms are dominant, while at higher values (tAs > 0.300 mg kg-1) the concentration of organic As increases substantially and DMA becomes the dominant form in rice grain. On the contrary, inorganic arsenic was always the dominant form, mainly as arsenate [As(V)], in leaves and stems. The presence in soils of high concentrations of amorphous Fe and Al oxides and hydroxides, which are capable of strongly adsorbing oxyanions (i.e. arsenate), was associated with low concentrations of As in rice plants. In addition, the presence of high concentrations of As(V) in stems and leaves, low concentration of As in phytoliths, and the As associated with organic matter in stems and husk, together suggest that rice plants take up more As(V) than As(III).

Arsenic in edible macroalgae: an integrated approach.

Arsenic is a metalloid naturally present in marine environments. Various toxic elements including arsenic (As) are bioaccumulated by macroalgae. This metalloid is subsequently incorporated as arsenate into the organism due to similarity to phosphate. In recent decades, the use of macroalgae in food has increased as a result of their numerous benefits; however, As consumption may exert potential consequences for human health. The objective of this review was to discuss the articles published up to 2019 on As in seaweed, including key topics such as speciation, toxicity of the most common species in marine macroalgae, and their effects on human health. Further, this review will emphasize the extraction methods and analysis techniques most frequently used in seaweed and the need to develop certified reference materials (CRMs) in order to support the validation of analytical methodologies for As speciation in macroalgae. Finally, this review will discuss current legislation in relation to the risk associated with consumption. The number of articles found and the different approaches, biological, analytical and toxicological, show the growing interest there has been in this field in the last few years. In addition, this review reveals aspects of As chemistry that need further study, such as transformation of organic metalloid species during digestion and cooking, which necessitates analytical improvement and toxicological experiments. Taken together our findings may contribute to revision of current legislation on As content in edible seaweed relating to human health in a growing market.

Arsenic speciation analysis in rice milk using LC-ICP-MS.

The consumption of rice milk has increased, mainly by individuals intolerant to lactose or allergic to cow milk. However, rice milk contains As. In this sense, the concentration of As in rice milk should be controlled. In the present study it is proposed a methodology for determination of As(III), dimethylarsenic (DMA), monomethylarsenic (MMA) and As(V) species in rice milk using LC-ICP-MS. The main features of the methodology are fast analysis, easy and simple sample preparation, where the sample is 3-fold diluted in the mobile phase and then filtered. The four arsenic species investigated were detected in the analysed samples, being As(V) the main species. The limit of quantification of the method ranges from 0.25 to 0.43 µg L-1 As. The analyte recovery ranged from 81 to 116% for samples spiked to 1.00 µg L-1 or 5.00 µg L-1 As and the relative standard deviation was better than 5%.

Total arsenic and inorganic arsenic speciation in groundwater intended for human consumption in Uruguay: Correlation with fluoride, iron, manganese and sulfate.

Medical Geology is a growing field in Uruguay and the groundwater quality has been the focus of multiple studies, being As levels one of its main concerns. The aim of this study was the application of analytical methodologies for the assessment of total arsenic and inorganic arsenic species, fluoride, iron, manganese and sulfate in groundwater samples from private wells, used for human consumption, and to evaluate the possible correlations among these parameters. The accuracy of the methods was ensured by using certified reference materials. A total of 48 groundwater samples from Uruguay were analyzed. The concentration ranges found were: tAs (1.72-120.48) µg L-1, F- (0.024-1.528) mg L-1, Fe (0.62-211.38) µg L-1 and Mn (0.11-8.705) µg L-1. Almost half of the samples presented tAs concentration levels above those recommended by WHO for drinking water (10 µg L-1), with the corresponding risks for human health. Results showed higher As(V) levels in the samples, which is in agreement with the oxidant conditions of the wells. Pearson correlations were performed, resulting in strong positive correlations for As/F-, As(V)/F- and As(V)/SO42-. As levels in groundwater and its relationship with other inorganic parameters, should be deeply studied to prevent long-term health effects.

Health risk apportionment of arsenic from multiple exposure pathways in Paracatu, a gold mining town in Brazil.

This study assessed various exposure pathways of arsenic and their health risk apportionment to the residents of Paracatu, a gold mining town in Brazil. We measured arsenic concentrations in 50 groundwater and surface town water samples from nearby residences, 38 surface soil dust from residential/commercial dwellings and roadside of Paracatu, and 600 airborne dust samples including PM10 and total suspended particulates (TSP), in additional to a previous reported food survey containing 90 samples from 15 major food categories. For the surface soil dust, bioaccessibility of arsenic as a surrogate of bioavailability was determined using an in vitro physiologically based extraction test (PBET). Rice and bean were found to contain the highest levels of arsenic in which the arsenic speciation was measured whereas the percentages of inorganic arsenic of other food items were taken from the literature for the risk apportionment calculation. The results show that the contribution of inhaled arsenic is ≤3% of the total daily intake, even assuming 100% BAC. The average bioaccessibility of arsenic in the surface soil dust was 3.4 ±â€¯2.0% (n = 17) with a bioaccessible concentration of 4.1 ±â€¯3.7 mg/kg. Food was the main contributor of the daily total intake of arsenic with rice and beans being the most significant ones. The total arsenic intake (ingestion + inhalation) is about 10% of the JECFA BMDL0.5 of 3 µg/kg b.w. per day, and the combined risk based on the cancer slope calculation is similar to the arsenic intake from the consumption of 2 L of water containing 10 µg/L of arsenic, a maximum concentration recommended by WHO. The holistic approach by addressing multiple pathways of exposure is considered a useful tool for health risk assessment throughout the life of mine including mine closure, and can be applied at legacy sites.

Arsenic and cadmium contents in Brazilian rice from different origins can vary more than two orders of magnitude.

Brazil is a major producer of rice, but there is not enough information about As and Cd in rice grown under different conditions in this country. Here, As and Cd were determined by ICP-MS and species of As by HPLC-ICP-MS in Brazilian husked rice, covering diverse cultivars and regions, as well as upland and flooded production systems. Significant differences were observed for contents of both elements according to the origin of rice. All samples were below the maximum limit for Cd (400 µg/kg) set by national legislation, while nine samples presented total As above the legislation limit (300 µg/kg). From 24 samples analyzed for As species, 42% showed iAs above the European limit for production of food to infants (100 µg/kg). The total As content in samples from Mato Grosso state presented a maximum value of 6 µg/kg, which combined with low Cd content make interesting further studies.

Interspecific differences in the bioaccumulation of arsenic of three Patagonian top predator fish: Organ distribution and arsenic speciation.

Interspecific differences in arsenic bioaccumulation and organ distribution (muscle, liver, kidney and gills) in three predator fish (creole perch, rainbow trout and brown trout) from a Patagonian lake impacted by volcanic eruptions were studied. Arsenic in fish organs were compared analyzing: 1) temporal (before and after volcanic eruption) and spatial (near and far from the volcano) influence of Puyehue-Cordón Caulle volcanic complex activity on arsenic concentrations; 2) the influence of growth (as total length), organ type and their interactions over arsenic accumulation; and 3) arsenic speciation and total arsenic relationship with carbon to nitrogen ratios (C:N), as a proxy of lipid presence, in fish muscle. In general, total arsenic concentrations in creole perch organs were 2-7 times higher than those recorded in the corresponding organs of salmonids. Arsenic was preferentially accumulated in liver and kidney in the three fish species. The influence of the volcanic activity over arsenic concentrations was more evident in creole perch: organs from creole perch captured closest to the volcano exhibited higher arsenic concentrations. Temporal variations were not so consistent. No clear relationship between arsenic and fish length was observed. Positive and linear relationship between arsenic in all pair of organs was found in creole perch, while rainbow trout showed a quadratic relationship between muscle and the remaining organs, indicating different arsenic assimilation-elimination relationships between organs and fish. The arsenic liver:muscle ratio in the three fish species was greater than 1, suggesting some level of arsenic stress. Arsenobetaine (AB) and dimethylarsinic acid (DMA) were the dominant arsenic species in muscle of these fish, having creole perch 3-4 times higher AB than rainbow trout. A positive relationship between C:N ratio and total arsenic concentrations was found, with higher C:N in creole perchs near the volcano. In terms of food safety, no inorganic arsenic compound were detected, therefore arsenic levels in fish from Lake Nahuel Huapi does not represent any health risk to consumers.

A feasible method for As speciation in several types of seafood by LC-ICP-MS/MS.

A method for arsenic speciation in shark, shrimp, squid, oyster and scallop using liquid chromatography coupled to inductively coupled plasma triple quadrupole mass spectrometry (LC-ICP-MS/MS) was proposed. Suitable sensitivity and selectivity by LC-ICP-MS/MS were obtained using 10 mmol L-1 (NH4)2HPO4 diluted in 1% methanol (pH 8.65) as mobile phase. Recoveries from 90 to 104% for arsenobetaine (AsB), arsenite [As(III)], dimethylarsinic acid (DMA), monomethylarsonic acid (MMA) and arsenate [As(V)] were obtained for all samples. A certificated reference material was also analyzed and the sum of As species was in agreement with the total As concentration. Limits of quantification (LOQ) for AsB, As(III), DMA, MMA, and As(V) were 6, 30, 6, 12 and 26 ng g-1, respectively. Higher concentration of AsB was found in all seafood, while As(III) and DMA were found only in oyster. Arsenate was found in squid and scallops, and MMA was below the LOQ in all samples.

Arsenic speciation in fish and shellfish from the North Sea (Southern bight) and Açu Port area (Brazil) and health risks related to seafood consumption.

In North Sea and Port Açu (Brazil) coastal areas, high arsenic (As) concentrations were observed in water, soil and sediments. Therefore, the impact of this contamination on fish and shellfish species bought from local fishermen was studied. Total As was assessed with ICP-OES (Brazil) and ICP-MS (North Sea) after microwave digestion. Toxic As was assessed with liquid chromatography-ICP-MS (Brazil) and hydride generation-atomic fluorescence spectrometry (North Sea). All analytical methods comply with Quality Assurance/Quality Control procedures. Several fish species have average Total As concentrations above 1 µg g-1 wet weight (ww), but the highest concentrations are found in less spotted dogfish, lemon sole and whelks from the North Sea, with respectively 50, 49 and 50 µg g-1 ww. High Total As concentrations correspond to high Toxic As concentrations, except for scallops having increased Toxic As concentrations. Toxic As fractions are highest in scallops (almost 10%) but rarely exceeds 2% in all other species. Liver samples were only analyzed in ray, dogfish and catfish and their Toxic As fractions are between 2 and 4 times higher than in muscle. For a consumption of 150 g of seafood, only 3 samples exceed the provisional total daily intake of 2 µg kg-1 bw, however, cancer risks are non-negligible. Using mean Toxic As concentrations for each of the different fish and shellfish species studied, Lifetime Cancer Risk values at the actual global seafood consumption rate of 54 g day-1 are above 10-4 for whelks, scallops, dogfish, ray and lemon sole.

Speciation of As in environmental samples using the nano-TiO2/PCHG-FAAS online system.

This work presents an alternative method for arsenic speciation using the nano-TiO2 hydride generation photocatalytic hydride generation (PCHG) system, which is easily separated from the medium. Nano-TiO2 was studied as photocatalyst to reduction of arsenic species by UV-induced with formic acid and atomic absorption detection of different forms of arsenic [As (III), As (V), dimethylarsinic acid (DMA)] in environmental samples (water, sediment and plant). The effect of the average pH, the organic acid concentration, the ultraviolet irradiation time and their amount were investigated. With the presence of formic acid, the process was more effective in the reduction of arsenic when compared to other organic acids, mainly acetic acid. In addition, the photocatalytic hydride generation and flame atomic absorption spectrometry (nano-TiO2/PCHG-FAAS) increased the identification and quantification of different arsenic species. The ultrasound extraction procedure was used as a method to prepare samples with solutions of 1.0 mol L-1 phosphoric acid. The accuracy of the measurements (n = 12), calculated as relative standard deviation, was less than 8.6%. The detection limits for As (III) and As (total) in samples were 0.418 and 0.574 µg g-1, respectively.

Arsenic in rice agrosystems (water, soil and rice plants) in Guayas and Los Ríos provinces, Ecuador.

Geogenic arsenic (As) can accumulate and reach high concentrations in rice grains, thus representing a potential threat to human health. Ecuador is one of the main consumers of rice in South America. However, there is no information available about the concentrations of As in rice agrosystems, although some water bodies are known to contain high levels of the element. We carried out extensive sampling of water, soil, rice plants and commercial rice (obtained from local markets). Water samples were analysed to determine physico-chemical properties and concentrations of dissolved arsenic. Soil samples were analysed to determine total organic C, texture, total Fe and amorphous Fe oxyhydroxides (FeOx), total arsenic (tAs) and the bioavailable fraction (AsMe). The different plant parts were analysed separately to determine total (tAs), inorganic (iAs) and organic arsenic (oAs). Low concentrations of arsenic were found in samples of water (generally <10µgl-1) and soil (4.48±3mgkg-1). The tAs in the rice grains was within the usual range (0.042-0.125mgkg-1 dry weight, d.w.) and was significantly lower than in leaves (0.123-0.286mgkg-1 d.w.) and stems (0.091-0.201mgkg-1 d.w.). The FeOx and tAs and also AsMe in flood water were negatively correlated with tAs in the plants. However, the concentrations of As in stems and leaves were linearly correlated with tAs in the soil and flood water. The relationship between tAs and arsenic in the grain fitted a logarithmic function, as did that between tAs in the grain and the stem. The findings seem to indicate that high concentrations of arsenic in the environment (soil or water) or in the rice stem do not necessarily imply accumulation of the element in the grain. The iAs form was dominant (>80%) in all parts of the rice plants.

A comparative evaluation of different ionic liquids for arsenic species separation and determination in wine varietals by liquid chromatography - hydride generation atomic fluorescence spectrometry.

The application of different ionic liquids (ILs) as modifiers for chromatographic separation and determination of arsenite [As(III)], arsenate [As(V)], dimethylarsonic acid (DMA) and monomethylarsonic acid (MMA) species in wine samples, by reversed-phase high performance liquid chromatography coupled to hydride generation atomic fluorescence spectrometry detection (RP-HPLC-HG-AFS) was studied in this work. Several factors influencing the chromatographic separation of the As species, such as pH of the mobile phase, buffer solution concentration, buffer type, IL concentration and length of alkyl groups in ILs were evaluated. The complete separation of As species was achieved using a C18 column in isocratic mode with a mobile phase composed of 0.5% (v/v) 1-octyl-3-methylimidazolium chloride ([C8mim]Cl) and 5% (v/v) methanol at pH 8.5. A multivariate methodology was used to optimize the variables involved in AFS detection of As species after they were separated by HPLC. The ILs showed remarkable performance for the separation of As species, which was obtained within 18min with a resolution higher than 0.83. The limits of detection for As(III), As(V), MMA and DMA were 0.81, 0.89, 0.62 and 1.00µg As L(-1). The proposed method was applied for As speciation analysis in white and red wine samples originated from different grape varieties.

Investigation of arsenic species in tailings and windblown dust from a gold mining area.

Research has shown the presence of high levels of arsenic (up to 2666 mg As kg(-1)) in tailings from a gold mining area of Brazil. This is an important point of attention, generating concerns about impacts on human health. Yet, a recent study showed that As bioaccessibility in the same area was very low (<4.4%). Thus, determination of the direct solid-phase speciation of As in the mine tailings and windblown dust is needed to explain this low bioaccessibility. Mine samples were collected from four subareas and windblown dust from eight sites. Synchrotron-based bulk-X-ray absorption near-edge structure (bulk-XANES) spectroscopy, micro-X-ray absorption near-edge structure (µ-XANES), and µ-X-ray fluorescence (µ-SXRF) spectroscopy were applied to determine As speciation. Bulk-XANES spectra indicated that As occurs as the As(V) oxidation state. Micro-XANES and µ-SXRF analyses revealed that As was also present as arsenopyrite (FeAsS) and its weathering products, but mostly it was As(V) as poorly crystalline ferric arsenate. This supports the findings of low bioaccessible As and highlights the importance of Fe oxides in immobilizing As in the terrestrial environment. All air particulate samples exhibited As-rich particles (up to 313 mg As kg(-1)). The air particulates exhibited solid-phase As species very similar to those found in the mine samples, which indicates that As in the windblown dust is not easily available.