Search

Background: Edible insects may contain arsenic. Analysis of arsenic species is necessary in order to accurately assess arsenic exposure., Objective: An analytical method was validated and used to determine and quantitate arsenic species in edible insects., Methods: Arsenic species were extracted from edible insects by heating at 100°C in 0.3 mol/L nitric acid. The concentration of arsenic species was then determined by LC-inductively coupled plasma-mass spectrometry (LC-ICP-MS) using an octadecylsilane (ODS) column with a mobile phase containing an ion-pair reagent., Results: The LOD (0.007-0.012 mg/kg), LOQ (0.021-0.038 mg/kg), repeatability (1.2-3.2%), intermediate precision (2.8-4.5%), and trueness (recoveries 97-102% based on spiked samples) of the proposed method were satisfactory for inorganic arsenic, dimethylarsinic acid (DMA), and arsenobetaine (AB) in edible insects. Total arsenic was detected in all samples obtained in Japan (Asian forest scorpion, diving beetles, giant water bug, grasshoppers, June beetles, mole crickets, male rhino beetle, female rhino beetle, sago worms, and silkworm pupae) and consisted of mostly inorganic arsenic. Beetles in particular showed relatively high levels., Conclusion: Arsenic content varies among edible insect species. Feed control is important, as arsenic concentrations in edible insects may be feed dependent., Highlights: Arsenic species in edible insects were analyzed by LC-ICP-MS using an ODS column with a mobile phase containing an ion-pair reagent. Inorganic arsenic was detected in most samples, with concentrations ranging from <0.04 to 29.3 mg/kg., (© The Author(s) 2023. Published by Oxford University Press on behalf of AOAC INTERNATIONAL. All rights reserved. For permissions, please email: journals.permissions@oup.com.)

Six arsenic species, namely arsenite (AsIII), arsenate (AsV), monomethylarsonic acid (MMA), dimethylarsinic acid (DMA), arsenobetaine (AsB) and arsenocholine (AsC) were speciated using a combination of high-performance liquid chromatography and inductively coupled plasma mass spectrometry (HPLC-ICP-MS). Under optimum chromatographic conditions, six arsenic species were well separated, and the performance of the combined system (HPLC-ICP-MS) for the species was determined. The limits of detection were calculated in the range of 0.14-0.29 ng/mL, and the corresponding quantification limits ranged between 0.45 and 0.97 ng mL -1 for the species. Spike recovery experiments performed on rice samples were used to validate the method's applicability to complex matrices. The recovery results calculated ranged between 93 and 109%, validating the method's applicability. Triplicate measurements for all spiked samples recorded percent relative standard deviation values below 10%., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

Dietary intake and urinary excretion of monomethylarsonic acid (MMA), dimethylarsinic acid (DMA) and arsenobetaine (AsB) were measured in 150 adult Japanese subjects. Duplicate diet (DD) samples and first void of urine on the next morning of DD sampling day were collected and analysed for arsenic species with liquid chromatography-ICP mass spectrometry. Median (min-max) intakes of MMA, DMA and AsB were <2.3 (<2.3-<2.3), 4.57 (<2.3-24.3), and 13.6 (<2.4-231) μg As/day, respectively, and median urinary concentrations were 1.90 (<0.37-26.), 21.9 (<0.27-141) and 19.6 (<0.37-1063) ng As/mg creatinine, respectively. Interrelationships between intake levels and urinary concentrations were mostly significant with positive coefficients indicating mutual association due to co-exposure, metabolism and/or dietary habit. Urinary concentrations and intake levels of AsB were also positively correlated confirming the applicability of urine analysis as biomarker of exposure. The present descriptive results provide with essential piece of information in assessing health risk of methylated arsenicals for population who consume marine products and rice.

Cadmium, inorganic arsenic and, potentially, dimethyl arsenic acid are carcinogens widely elevated in rice. Here it was identified that the food-safe and common cadmium chelator citric acid efficiently removed cadmium from intact grain via pre-soaking procedure, while also reducing arsenic species. A twostep pre-soaking stage was developed whereby rice was first incubated, at ambient temperature, in 1 M citric acid for 12 h, and then in 1 M calcium carbonate for another 12 h, the latter step to neutralize pH, followed by cooking. When 10 different individual types of rice were processed in such a way this resulted in removal rates of 79% for cadmium, 81% for inorganic arsenic and a 66% for DMA. The technology is particularly suitable for bulk food processing and could be deployed in the most cadmium and arsenic impacted regions where rice is a staple., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

Arsenic is a wildly distributed carcinogen in the environment. Arsenic-induced apoptosis has been extensively studied in therapeutics and toxicology. LncRNA MEG3 has been extensively studied as apoptosis regulatory gene in recent years. However, it stays unclear regarding how the mechanism of MEG3 regulates arsenic-induced apoptosis. Our focus was to explore the effects of MEG3 on arsenic-induced apoptosis. MTS assay was used to test cell viability, and qRT-PCR was for the examination of gene expressions. The effect of the apoptosis and necrosis after knockdown MEG3 was detected with double staining. Our results demonstrated that MEG3 expression was positively correlated with the concentration of three arsenic species (inorganic arsenic (iAs), monomethylarsonic acid (MMA) and dimethylarsinic acid (DMA)) (p < 0.05). The ability of iAs to induce MEG3 expression was much higher compared with that induced by MMA and DMA. In addition, our experiments confirmed that MEG3 knockdown increased cell viability and arsenic-induced apoptosis, but cell viability decreased after iAs treatment. Moreover, LncRNA MEG3 regulated apoptosis via down-regulate API5 while up-regulate CASP7, CCND3 and APAF1. It is further proved that arsenic-induced apoptosis increased after the knockdown of MEG3, which regulates these genes. These findings provide experimental evidence and possible mechanisms for subsequent research on the effects of arsenic on health.

This study assesses arsenic (As) fractionation in sediments and speciation in muscle tissues of Bagrid catfish, Chrysichthys nigrodigitatus from Lagos Lagoon, southwest Nigeria to determine risks to ecological receptors and humans. Residual As was the predominant geochemical fraction (86.2%) in sediments. Arsenite [As (III)] concentrations which ranged from 0.06 to 0.53 mg kg -1 in catfish muscle tissue, accounting for 25.9% of total As was the dominant species. Less toxic dimethylarsinic acid (DMA) which varied between 0.06 and 0.27 mg kg -1 made up to 10.8% of total As in catfish muscle tissue. Estimated human average daily intake (ADI) of As as As (III) and DMA were 1.35 × 10 -4 and 0.62 × 10 -4  mg kg -1 BW with corresponding hazard quotients (HQs) of 0.45 and 0.21, respectively, indicate no apparent health hazard to adult consumers. The incremental lifetime cancer risks (ILCR) of 0.78 × 10 -3 for total As, 0.20 × 10 -3 for As (III), and 0.93 × 10 -3 for DMA, for adults from the consumption of catfish is slightly higher than the US EPA threshold and indicates moderate carcinogenic risk. Furthermore, 12.5% bioavailable fraction of As in sediment and relatively higher levels of As (III) in fish tissues has ecological and public health implications., Competing Interests: Declaration of competing interest The authors declare that they have no known competing interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

Uptake, distribution and speciation of arsenic (As) were determined in the bracket fungus Fomitopsis betulina (previously Piptoporus betulinus), commonly known as the birch polypore, collected from a woodland adjacent to a highly contaminated former mine in the Southwest UK and at an uncontaminated site in Quebec, Canada, with no past or present mining activity. The fruiting body was divided into cap, centre and pores representing the top, middle and underside to identify trends in the distribution and transformation of As. Total As, determined by inductively coupled plasma-mass spectrometry (ICP-MS), was approximately tenfold higher in the mushroom from the contaminated compared to the uncontaminated site. Overall, accumulation of As was low relative to values reported for some soil-dwelling species, with maximum levels of 1.6 mg/kg at the contaminated site. Arsenic speciation was performed on aqueous extracts via both anion and cation high-performance liquid chromatography-ICP-MS (HPLC-ICP-MS) and on whole dried samples using X-ray absorption near edge structure (XANES) analysis. Seven As species were detected in F. betulina from the contaminated site by HPLC-ICP-MS: arsenite (As III ), arsenate (As V ), dimethylarsinate (DMA V ), methylarsonate (MA V ), trimethylarsine oxide (TMAO), tetramethylarsonium ion (Tetra) and trace levels of arsenobetaine (AB). The same As species were observed at the uncontaminated site with the exception of TMAO and Tetra. Arsenic species were localized throughout the fruiting body at the contaminated site, with the cap and pores containing a majority of As V , only the cap containing TMAO, and the pores containing higher concentrations of DMA V and MA V as well as tetra and a trace of AB. XANES analysis demonstrated that the predominant form of As at the contaminated site was inorganic As III coordinated with sulphur or oxygen and As V coordinated with oxygen. This is the first account of arsenic speciation in F. betulina or any fungi of the family Fomitopsidaceae.

Since arsenic (As) exposure is largely due to geochemical contamination, this study focused on the remediated area of Santana do Morro, a district of Santa Bárbara, Minas Gerais, Brazil, which was previously contaminated with As due to gold mining. Total As concentrations in sediment, soil and plants were determined, next to As species, anionic arsenic compounds As(III), As(V), monomethylarsonic acid (MMA) and dimethylarsinic acid (DMA), in plants samples. Total As concentrations in soil and sediments were slightly elevated (16-18 µg g-1) and most of the plants contained low levels of As (< 1 µg g-1). The exception was a native plant Eleocharis geniculata (L.) which contained elevated levels of As (4 µg g-1). The exposure of this plant to As under controlled conditions (hydroponics) indicated its possible tolerance to elevated As levels and suggesting its potential use in phytomonitoring of As-contaminated sites. This plant is able to metabolize arsenate to arsenite and contained MMA and DMA, both in its natural habitat and under controlled conditions.

With recently legislated maximum levels of inorganic arsenic (iAs) in white and brown rice in Canada, the regulatory bodies are evaluating the need for regulation of As levels in infant food products. Rice is a major part of infants' diet, and therefore, the presence of As in this staple food causes concerns. So far, the scientific community was lacking suitable certified reference material (CRM) which could be used to assess the accuracy of developed analytical methods for As speciation in infants' food products. As a result, we have developed BARI-1, a baby cereal coarse rice flour reference material which was certified for total arsenic (0.248 ± 0.018 mg kg -1 ), cadmium (0.0134 ± 0.0014 mg kg -1 ), mercury (0.0026 ± 0.0003 mg kg -1 ), lead (0.0064 ± 0.0016 mg kg -1 ), inorganic As (0.113 ± 0.016 mg kg -1 ) and dimethylarsinic acid (DMA) (0.115 ± 0.010 mg kg -1 ), and reference value for monomethylarsonic acid (MMA) (0.0045 ± 0.0008 mg kg -1 ) was reported. We also observed trace amounts of an unknown As compound, with chromatographic retention time close to DMA. Participating laboratories were allowed to use their in-house-validated extraction and/or digestion methods, and the detection of total metals was done by ICP-MS whereas HPLC-ICP-MS was used for As speciation. Despite the diversity in sample preparation and quantitation methods, reported values were in good agreement. For iAs measurement, the comparison between hydride generation ICP-MS and HPLC-ICP-MS found iAs overestimation with the former method, possibly due to interference from DMA. The certification was accomplished with a CRM rapid response approach in collaborative, focused effort completing the CRM development in few months instead of the typical multiyear project. This approach allowed to respond to measurement needs in a timely fashion. Graphical abstract.

The role of water and bottom sediment pollution of a river subjected to a strong industrial anthropo-pressure in coastal plants was investigated. The work presented the influence of polluted environment on accumulation of metal(loid)s (including arsenic and its species) in Stuckenia pectinata L., Galium aparine L., and Urtica dioica L. The study provided important information on the contents of organic and inorganic arsenic species in selected plants and their response to heavy metal and arsenic contamination. The As(III), As(V), AB (arsenobetaine), MMA (monomethylarsonic acid), and DMA (dimethylarsinic acid) ions were successfully separated on the Hamilton PRP-X100 column with high-performance liquid chromatography-inductively coupled plasma-mass spectrometry (HPLC-ICP-MS) techniques. The Pollution Load Index and geo-accumulation Index (I geo ) values clearly indicate significant pollution of the examined ecosystem with heavy metals. The chemometric analysis with the concepts of (Dis)similarity Analysis, Cluster Analysis, and Principal Component Analysis helped to visualize the variability of the As species concentrations and to analyse correlations between sampling point locations and analyte contents.

As stand-alone approaches, chromatographic separations of arsenic in lichen using HPLC-ICP-MS or the use of sequential extractions have historically been shown to have low analyte recoveries and poor analyte selectivity respectively. This study modifies the first step of a sequential extraction with a chromatographic separation of five arsenic species using HPLC-ICP-MS, followed by a three-step sequential extraction and analysis with ICP-MS. The method was applied to lichens from a rural and urban site to demonstrate the applicability thereof, and the sum of arsenic concentrations from the extraction steps were compared to the total arsenic concentrations. Short term species stability of the As species in the lichen matrix was also evaluated over 1 month in the water-extractable fraction, where As species concentrations changed week by week, providing insight into biotransformation mechanisms. In the modified extraction step, dimethylarsinic acid (DMA) and arsenobetaine and an unknown As species (AsB + U1) were statistically (p < 0.05) higher in the urban site than the rural site. Analyte recoveries using the combined method were higher than other studies reported in literature, with percentage recoveries of 104% and 111% of As in the urban and rural sites respectively. Arsenic concentrations were found in the following order of abundance at both sites: oxidizable > reducible > water-extractable > residual. Concentrations of total As in the oxidizable and non-bioavailable fraction were statistically lower (p < 0.05) in the rural site than in the urban site. Based upon the information gained from this study, we could draw concise conclusions regarding the source apportionment, timing and the magnitude of the pollution event., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

The bioaccessibility of total arsenic (tAs) and arsenic species in Bellamya aeruginosa collected from Xiangjiang River was evaluated using an in vitro digestion model, to assess the potential health risks to local residents. The tAs concentrations in gastropod samples ranged from 1.98 to 6.33 mg kg -1 (mean 3.79 ± 1.60 mg kg -1 ). Five arsenic species including arsenite [As(III)], arsenate [As(V)], dimethylarsinic acid (DMA), arsenobetaine (AsB), and arsenocholine (AsC) were detected. Inorganic arsenic (iAs) concentrations, which were about a half of organic arsenic (oAs), were higher than the maximum permissible limit (≤0.50 mg kg -1 in aquatic products). Bioaccessible concentrations of tAs in digestive juices were found to be decreased in the order: intestinal phase > gastric phase > salivary phase. As(III) and AsC were the predominant species, but AsB was not detectable in all digestive juices. Bioaccessible iAs concentrations, which were close to the level of bioaccessible oAs, were not significantly different among three digestive juices, but also above 0.50 mg kg -1 . Accordingly, bioaccessibility of tAs was highest in intestinal phase (48%), then in gastric phase (40%), and lowest in salivary phase (33%). Bioaccessibility of As(III) was close to 100%, and bioaccessibility of iAs was much higher than that of oAs. The mean values of target hazard quotient (THQ) and bioaccessible THQ were 0.80 and 0.70, respectively. The probability of experiencing non-carcinogenic effects was reduced to 18% down from 22% as considering iAs bioaccessibility. The mean values of carcinogenic risk (CR) and bioaccessible CR were higher than the acceptable value (1 × 10 -4 ). Gastropod consumption from sampling sites may cause a potential carcinogenic risk., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Inc. All rights reserved.)

To assess the two most toxicologically relevant species of As, namely arsenite (As(III)) and arsenate (As(V)), chromatographic separations often require two separate chromatographic columns to address the co-elution of arsenobetaine (AsB) with As(III). This issue is typically observed using conventional isocratic methods on anion exchange columns, increasing cost and analysis time. Here, we optimize the extraction of inorganic As from a lichen air biomonitor and develop an isocratic method for the chromatographic separation of five common As species on a PRP X-100 anion exchange column, resulting in the complete baseline separation of all species under study. This method was then applied to lichen biomonitors from an urban and rural site to demonstrate its use. In order of abundance, the various arsenic species in lichens from the urban site in South Africa were As(V) > As(III) > AsB > dimethylarsinic acid (DMA) > monomethylarsonic acid (MMA), and As(V) > AsB > As(III) > DMA > MMA for the rural site, where MMA was present in extremely low, non-quantifiable concentrations in lichens from both sites. Total concentrations of As were higher in samples from the urban site (6.43 ± 0.25 μg/g) than in those from the rural site (1.87 ± 0.05 μg/g), with an overall extraction efficiency of 19% and 40%, respectively. The optimized method utilized relatively inexpensive solvents and is therefore low-cost and eco-friendly in comparison with conventional chromatographic techniques. This is the first study which addresses the optimized extraction and characterization of As species in a South African lichen biomonitor of air pollution. Graphical abstract .

Arsenic and its inorganic species: As (III), As (V), dimethylarsenic acid (DMA) and monomethylarsenic acid (MMA) were determined in hypoallergenic formulas and grain porridges commercially available on Polish market, dedicated for infant 0-8 months. After quantitative extraction with 0.5% HNO 3 , separation of individual species was performed by high performance liquid chromatography (HPLC), and their determination by neutron activation analysis (NAA) and inductively coupled plasma mass spectrometry (ICP-MS). Due to relatively low content of As in the analysed samples, it was only possible to determine DMA using the HPLC-ICP-MS mode. HPLC separation coupled with off-line determination by NAA enabled the determination of more extracted As species (especially inorganic) with good accuracy. Certified reference material (CRM) Rice Flour SRM 1568b (NIST) was used for the validation of both procedures., (Copyright © 2019. Published by Elsevier Ltd.)

Roxarsone (ROX), an organoarsenic feed additive, occurs as itself and its metabolites including As(V), As(III), monomethylarsonic acid (MMA) and dimethylarsinic acid (DMA) in animal manure. Animal manure improves soil biological property, whereas As compounds impact microorganisms. The integral influence of animal manure bearing ROX metabolites on soil biological quality is not clear yet. Herein, the effect of four chicken manures excreted by chickens fed with four diets containing 0, 40, 80 and 120 mg ROX kg -1 , on soil biological attributes. ROX addition in chicken diets increased total As and ROX metabolites in manures, but decreased manure total N, ammonium and nitrate. The elevated ROX metabolites in manures increased soil total As, As species and total N, and increased first and then decreased soil nitrate and nitrite, but did not affect soil ammonium in manure-applied soils. The promoting role of both soil As(III) and ammonium on soil microbial biomass carbon and nitrogen, respiration and saccharase activity, were exceeded or balanced by the inhibiting effect of soil nitrate. The suppression of soil catalase activity by soil As(V) was surpassed by the enhancement caused by soil nitrate and nitrite. Soil urease, acid phosphatase and polyphenol oxidase activities were not suitable bioindicators in the four manure-amended soils. Soil DMA did not affect soil biological properties, and MMA was not detectable in all manure-amended soils. The above highlights the complexity of joint influence of soil As and N on biological attributes. Totally, when ROX is used at allowable dose in chicken diet, soil biological quality would be suppressed in manure-amended soil., (Copyright © 2019 Elsevier Inc. All rights reserved.)

Correlations between the concentrations of arsenic in scalp hair and in drinking water as well as in blood and/or urine have been reported. These correlations clearly show exposure⁻absorption⁻excretion relationships. In addition, arsenic metabolites such as monomethylarsonic acid and dimethylarsinic acid have been identified and quantified in these tissues and fluids, leaving little doubt that elevated levels of arsenic in the hair can reflect systemic arsenic intoxication. Consequently, hair analysis has potential merit as a screening procedure for poisoning by arsenic. However, questions regarding the exogenous versus the endogenous deposition of arsenic in the hair, and uncertainties about the normal level of arsenic in the hair remain unresolved. Pending their resolution, the determination of arsenic in hair should remain a screening tool, and clinical signs and symptoms should be employed to complete the diagnosis of arsenic poisoning.

Rice (Oryza sativa) is believed to be a major source of arsenic (As) exposure in humans, especially in Asia. In this study, As accumulation, distribution and source analysis of rice are investigated in five sites (SZ, QH, XZ, WS and JX) in the Nansi Lake area, an important rice-growing region in north China. Findings show that total As average concentrations were 6.3-13.6 mg kg -1 and 5.5-9.9 μg L -1 in paddy soil and irrigation water, respectively. Inorganic arsenic As(III) and dimethylarsinic acid DMAs(V) were the major speciation in polished rice, with a small proportion of As(V) evident. Notably, the percentage of As(III) increased by 63.9-68.5%. Based on survey data, the addition of total As to farm soil due to fertilizer application was 31.5-11,580 mg per hectare per year. According to the results of Spearman's rank correlation analysis and Principal Component Analysis (PCA), As levels in soil and irrigation water may be important factors influencing As concentration in rice., (Copyright © 2018 Elsevier Inc. All rights reserved.)

A rapid and sensitive method was established for arsenic (As) speciation based on high performance liquid chromatography coupled to inductively coupled plasma mass spectrometry (HPLC-ICP-MS). This method was validated for the quantification of four arsenic species, including arsenite (As III ), arsenate (As V ), monomethylarsonic acid (MMA V ) and dimethylarsinic acid (DMA V ) in cynomolgus macaque plasma. Separation was achieved in just 3.7 min with an alkyl reverse phase column and highly aqueous mobile phase containing 20 mM citric acid and 5 mM sodium hexanesulfonate (pH = 4.3). The calibration curves were linear over the range of 5⁻500 ng·mL -1 (measured as As), with r > 0.99. The above method was validated for selectivity, precision, accuracy, matrix effect, recovery, carryover effect and stability, and applied in a comparative pharmacokinetic study of arsenic species in cynomolgus macaque samples following intravenous and intragastrical administration of arsenic trioxide solution (0.80 mg·kg -1 ; 0.61 mg·kg -1 of arsenic); in addition, the absolute oral bioavailability of the active ingredient As III of arsenic trioxide in cynomolgus macaque samples was derived as 60.9 ± 16.1%.

High-performance liquid chromatography (HPLC) coupled with inductively coupled plasma mass spectrometry (ICP-MS) was applied to the speciation of arsenic [As(III), As(V), and AsB (arsenobetaine)], MMA (monomethylarsonic acid), DMA (dimethylarsinic acid), antimony [Sb(III) and Sb(V)], and chromium [Cr(III) and Cr(VI)] in water and bottom sediment samples collected from the urban Bytomka River (Poland). The main objective of the study was the research of As, Cr and Sb species in the Bytomka River, as well as the simplified three-stage sequential chemical extraction of bottom sediments according to the Institute for Reference Materials and Measurements (BCR). The contents of V, Mn, Co, Ni, Cu, Zn, Rb, Sr, Ag, Cd, Te, Ba, Tl, Pb, Fe, Ga, and U in the water and bottom sediments were tested using the ICP-MS technique. The risk assessment code (RAC) indicated a medium risk for As and a high risk for Sb to the environment. Sequential chemical extraction of bottom sediments showed that As and Cr were strongly demobilized. Sb was mainly bound with the ion-exchange fraction and posed a serious threat to the environment. Chemometric analysis with the (dis)similarity analysis and principal component analysis (PCA) allowed for visualization of the variability and correlations of the analyzed elements.

Total As and As speciation were measured in 147 red wines collected worldwide by ICP-MS and HPLC-ICP-MS, respectively. The samples included mid-priced to prestigious wines with vintages covering a period of almost 50 years. Total As concentration ranged from below 0.1 to 56 µg/L (average value: 4.0 ± 5.9 µg/L). None of the samples presented a concentration exceeding the limit set by the Office of Vine and Wine of 200 µg/L. Inorganic As was the most abundant form, representing from about half to all total As, mainly as As(III). Dimethylarsinic-acid (DMA) was detected in slightly less than half of the samples, accounting for a few to several dozens of percent. Monomethylarsonic-acid (MMA) was only detected in a few samples. In average, the DMA concentration seemed to be higher in the Bordeaux wines than in the other ones, irrespective of the total As concentration.

Arsenite (As(III)) has been considered as a human carcinogen associated with many human cancers especially skin cancer. Elucidation of the transformed species of As(III) during its metabolism in cells is beneficial for evaluation of its bioeffect. In this work, a hyphenated method of reversed phase ion pair high performance liquid chromatography - inductively coupled plasma mass spectrometry (RP-IP-HPLC-ICP-MS) equipped with collision/reaction cell technology (CCT) was developed for speciation of As(III) and its metabolites (arsenate [As(V)], monomethylarsonic acid [MMA(V)], and dimethylarsinic acid [DMA(V)]) in SCC-7 cells. The developed analytical method exhibits low limits of detection for interest arsenic species in the range of 14-27 ng/L and wide linear range up to four orders of magnitude, providing a sensitive tool for arsenic metabolites analysis and further understanding the metabolism of As(III) in SCC-7 cells. The effect of exposure time, exposure concentrations and elimination time on the arsenic species and total arsenic in SCC-7 cells incubated by As(III) were systematically studied. At low exposure concentrations (< 5 μM), large proportion of intracellular As(III) transformed to methylated metabolites, and the final methylated metabolite DMA(V), which could not be completely removed from the cells in the elimination process, is considered to play as the primary carcinogen. While at high exposure concentrations (> 5 μM), most of intracellular As(III) probably bound to biomacromolecules rather than followed biomethylation process, exhibiting different metabolism., (Copyright © 2018 Elsevier B.V. All rights reserved.)

The aim of the study was to estimate the significance of the role of arsenite (As(III)), arsenate (As(V)), and dimethylarsinic acid (DMA) presence in modified Knop medium in the efficiency of phytoextraction of arsenic (As) in Acer platanoides root, stem, and leaves. The addition of particular As forms in single, double, and triple experimental systems was associated with a lower increase of seedling biomass compared to control plants (system free of As forms addition). Depending on As forms and their concentration in solution, negative symptoms from slight visible changes (inorganic forms separately or jointly), through smaller and discolored leaves (after DMA addition), and finally to their withering (after high DMA addition) were observed. Changes of color and shape for root systems exposed to particular As forms separately or jointly were also observed, in spite of the fact that there were no significant changes in biomass of seedlings growing in all experimental systems. The highest mean concentrations of As in root, stem, and leaves (590, 70, and 140 mg kg -1 dry weight (DW), respectively) were observed in plants growing under different experimental systems. The highest bioconcentration factor values were 10.8 for plants exposed to 0.06 mM of As(III) and DMA, while the highest translocation factor (1.0) was recorded for plants growing under the same As forms (0.6 and 0.06 mM, respectively). The obtained results indicate that the presence of particular As forms not only determines As phytoextraction and transport of this metalloid form but also has a decisive influence on plant morphology and survivability. As regards the practical aspects of phytoremediation, the kind of As forms present in substrate are more important than their total concentration.

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 (NH 4 ) 2 HPO 4 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., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

The edible ink stain bolete (Cyanoboletus pulverulentus) was found to hyperaccumulate arsenic. We analyzed 39 individual collections determined as C. pulverulentus, mostly from the Czech Republic. According to our results, concentrations of arsenic in C. pulverulentus fruit-bodies may reach 1300mgkg -1 dry weight. In most collections, data for total and bioavailable arsenic in underlying soils were collected but no significant correlation between the soil arsenic content and arsenic concentrations in the associated fruit-bodies was found. Within the fruit-bodies, we found the majority of arsenic accumulated in the hymenium. Besides occasional traces of methylarsonic acid (MA), the arsenic speciation in all mushroom samples consisted solely of dimethylarsinic acid (DMA) and no inorganic arsenic was detected. Because of the carcinogenic potential of DMA, C. pulverulentus should not be recommended as an edible mushroom and its consumption should be restricted., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

Birds are at a higher level in the food chain; however, the potential bioaccumulation and biotransformation of arsenic (As) in birds in As mines has rarely been studied. In this study, four passerine bird species (tree sparrow [Passer montanus], light-vented bulbul [Pycnonotus sinensis], Garrulax canorus [Leucodioptron canorus], and magpie [Pica pica]) were collected from an abandoned As mine in China. The highest recorded As concentrations were 4.95 mg/kg and 51.65 mg/kg in muscles and feathers, respectively. Detection using high-performance liquid chromatography inductively coupled plasma mass spectrometry (HPLC-ICP-MS) revealed six As species, including arsenite (As(III)), arsenate (As(V)), dimethylarsinic acid (DMA), monomethylarsonic acid (MMA), arsenobetaine (AsB) and arsenocholine (AsC), with the former three species as the dominant (>92%) and the latter three as the minor As species (<6.17%). Further analysis of the selected bird samples using the X-ray absorption near edge structure (XANES) technique revealed the existence of As(III)-tris-glutathione (As(III)-GSH), which can be regarded as equivalent to the non-extractable and unidentified As form in the HPLC-ICP-MS data. Both methods revealed similar patterns of As species in the birds from the As mine, with muscles containing mainly inorganic As and DMA and feathers containing mainly inorganic As. The results of this study contribute to the knowledge regarding As accumulation and speciation in terrestrial organisms., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

A slurry sampling procedure for arsenic speciation analysis in baby food by arsane generation, cryogenic trapping and detection with atomic absorption spectrometry is presented. Several procedures were tested for slurry preparation, including different reagents (HNO 3 , HCl and tetramethylammonium hydroxide - TMAH) and their concentrations, water bath heating and ultrasound-assisted agitation. The best results for inorganic arsenic (iAs) and dimethylarsinate (DMA) were reached when using 3molL -1 HCl under heating and ultrasound-assisted agitation. The developed method was applied for the analysis of five porridge powder and six baby meal samples. The trueness of the method was checked with a certified reference material (CRM) of total arsenic (tAs), iAs and DMA in rice (ERM-BC211). Arsenic recoveries (mass balance) for all samples and CRM were performed by the determination of the tAs by inductively coupled plasma mass spectrometry (ICP-MS) after microwave-assisted digestion and its comparison against the sum of the results from the speciation analysis. The relative limits of detection were 0.44, 0.24 and 0.16µgkg -1 for iAs, methylarsonate and DMA, respectively. The concentrations of the most toxic arsenic species (iAs) in the analyzed baby food samples ranged between 4.2 and 99µgkg -1 which were below the limits of 300, 200 and 100µgkg -1 set by the Brazilian, Chinese and European legislation, respectively., (Copyright © 2017 Elsevier B.V. All rights reserved.)

Recent epidemiological studies have reported adverse health effects, including skin cancer, due to low concentrations of arsenic via drinking water. We conducted a study to assess whether low arsenic contaminated ground water affected health of the residents who consumed it. For precise biomonitoring results, the inorganic (trivalent arsenite (As III) and pentavalent arsenate (As V)) and organic forms (monomethylarsonate (MMA) and dimethylarsinate (DMA)) of arsenic were separately quantified by combining high-performance liquid chromatography and inductively coupled plasma mass spectroscopy from urine samples. In conclusion, urinary As III, As V, MMA, and hair arsenic concentrations were significantly higher in residents who consumed arsenic contaminated ground water than control participants who consumed tap water. But, most health screening results did not show a statistically significant difference between exposed and control subjects. We presume that the elevated arsenic concentrations may not be sufficient to cause detectable health effects. Consumption of arsenic contaminated ground water could result in elevated urinary organic and inorganic arsenic concentrations. We recommend immediate discontinuation of ground water supply in this area for the safety of the residents., Competing Interests: The authors disclose no conflicts of interest.

Paddy rice (Oryza sativa L.) as the staple food in China was found to be efficient in accumulating arsenic (As) due to cultivated in flooded paddy soil. Uptake and translocation of As in rice plant depended on the As species. In this work, rice plant samples including roots, straws and grains as well as rhizosphere soils were collected from paddy fields near Changsha, a mine impacted city in Southern China. The total As concentrations in the collected samples were observed in the descending order as root > soil > straw > grain. The predominant As species detected in rice plants were inorganic forms: arsenite [As(III)] and arsenate [As(V)]. Except monomethylarsonate (MMA) and dimethylarsinate (DMA), other two organoarsenicals, arsenobetaine (AsB) and arsenocholine (AsC), were also detected in rice plants. DMA and AsB were mainly formed in rice roots with the assistance of microorganisms. MMA and AsC detected in straws might be derived from methylation and oxidation of As(III). The results of multiple linear regressions indicated that the straw As species were remarkable predictors of the corresponding grain As species. Demethylation or degradation of MMA, DMA and AsC were predicted when translocated from straw to grain., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

Arsenic species and a possible source of methylated arsenic in a Panax Notoginseng (PN) medicinal plant were explored to further understand the change of inorganic arsenic to the less toxic methylated form to minimize the health risks associated with its medicinal use. Arsenic speciation in PN from major planting areas was determined using high-performance liquid chromatography coupled with hydride generator-atomic fluorescence (HPLC-HG-AFS). Pot experiments were performed to explore the source of methylated arsenic in PN, and the arsenite methyltransferase (arsM) gene abundance was determined using quantitative reverse transcription PCR (q-RTPCR). Methylated arsenic (monomethylarsonic acid (MMA) + dimethylarsinic acid (DMA)) accounted for 43% ± 30% of the total arsenic in PN from planting areas, while the primary species in soil was As(V) (94% ± 0.12%). In the pot experiments, methylated arsenic accounted for 37%-49% of the total arsenic in PN, and As (V) was the primary species in soil (>98%). The four detected arsenic species in PN increased as the amount of As added to soil increased. The methylated arsenic contents in the PN root were significantly positively correlated with the ArsM gene abundance in soil, suggesting that methylated arsenic in PN is likely from the planting soil., (Copyright © 2016. Published by Elsevier Ltd.)

Arsenic (As) speciation is essential in assessing health risks from As-contaminated soil. Release of soil-bound arsenic, As transformation by human gut microbiota, and the subsequent intestinal absorption of soil As metabolites were evaluated. A colon microbial community in a dynamic human gut model and the intestinal epithelial cell line Caco-2 were cultured. Arsenic speciation analysis and absorption of different As species were undertaken. In this study, soil As release (3.7-581.2 mg kg -1 ) was observed in the colon. Arsenic in the colon digests was transformed more quickly than that in the soil solid phase. X-ray absorption near-edge spectroscopy (XANES) analysis showed that 44.2-97.6% of arsenite [As(III)] generated due to arsenate [As(V)] reduction was in the soil solid phase after the colon phase. We observed a high degree of cellular absorption of soil As metabolites, exhibiting that the intestinal absorption of monomethylarsonic acid and As(III) (33.6% and 30.2% resp.) was slightly higher than that of dimethylarsinic acid and As(V) (25.1% and 21.7% resp.). Our findings demonstrate that human gut microbiota can directly release soil-bound arsenic, particularly As-bearing amorphous Fe/Al-oxides. Determining As transformation and intestinal absorption simultaneously will result in an accurate risk assessment of human health with soil As exposures., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

This study measured the elemental and species concentrations of arsenic (As) in the water, sediments and food webs of two shallow Chinese freshwater lakes. Organic As species were widely detected in various organisms from the two lakes (60%-100% of the total). Among these organisms, dimethylarsinic acid (DMA) was predominant in most of the samples. The average concentrations and corresponding proportions were 0.59 mg/kg, 81% in fish; 3.24 mg/kg, 70.63% in zoobenthos; and 1.34 mg/kg, 79% in plants. The average concentrations and corresponding proportions of monomethylarsonic acid (MMA) and inorganic As were much lower, ranging from n.d. (not detected) to 1.94 mg/kg and from n.d. to 1.54 mg/kg, with an average proportion of 14 and 7.4%, respectively. In Lake Taihu, the mean As concentrations in different fish tissues were generally low and in the following order: eggs (0.47) < skin (0.62) < muscles (0.91) < gills (1.65) < livers (5.47) mg/kg. DMA occupied 75%-100% of the total As species, while MMA and inorganic As were much less prevalent.

A method of high performance liquid chromatography with a Hamilton PRP-X100 ion-exchange column (250 × 4.1 mm id, 10 μm) coupled to inductively coupled plasma mass spectrometry was employed to generate a full concentration-time profile of arsenic speciation after oral administration. The results exhibited good linearity and revealed that, in the pills, the average arsenic concentration was 10105.4 ± 380.7 mg/kg, and in the water extraction solution, the inorganic As(III) and As(V) concentrations were 220.1 ± 12.6 and 45.5 ± 2.3 mg/kg, respectively. No trace of monomethyl arsenic acid was detected in any of the plasma samples. We then successfully applied the established methodology to examine the pharmacokinetics of arsenic speciation. The resulting data revealed that, after oral administration in rats, the plasma concentration of each arsenic species reached C max shortly after initial dosing, and that the distribution and elimination of As(V) was faster than that of As(III) and dimethyl arsenic acid. Additionally, the t 1/2 values of As(V), As(III), and dimethyl arsenic acid were 3.4 ± 1.6, 14.3 ± 4.0, and 19.9 ± 1.6 h, respectively. This study provides references for the determination of arsenic speciation in mineral-containing medicines and could serve as a useful tool in measuring the true toxicity in traditional medicines that contain them., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Arsenic (As) contamination in soil can lead to elevated transfer of As to the food chain. One potential mitigation strategy is to genetically engineer plants to enable them to transform inorganic As to methylated and volatile As species. In this study, we genetically engineered two ecotypes of Arabidopsis thaliana with the arsenite (As(III)) S-adenosylmethyltransferase (arsM) gene from the eukaryotic alga Chlamydomonas reinhardtii. The transgenic A. thaliana plants gained a strong ability to methylate As, converting most of the inorganic As into dimethylarsenate [DMA(V)] in the shoots. Small amounts of volatile As were detected from the transgenic plants. However, the transgenic plants became more sensitive to As(III) in the medium, suggesting that DMA(V) is more phytotoxic than inorganic As. The study demonstrates a negative consequence of engineered As methylation in plants and points to a need for arsM genes with a strong ability to methylate As to volatile species.

A novel analytical method has been developed for the determination of all five arsenic species known to exist in atmospheric particulate matter (PM), i.e., the inorganic arsenite iAs(III) and arsenate iAs(V), and the methylated methylarsonate (MA), dimethylarsinate (DMA) and trimethylarsine oxide (TMAO). Although the methylated species were first detected in PM in the late 1970s, most of the recent studies focus mainly on the two inorganic As species, ignoring TMAO in particular. In the present study, an HPLC (with an anion and cation exchange column connected in series)-arsine generation-ICP-MS system provided complete separation of all five As species and limits of detection from 10 to 25 pg As mL(-1). This method was applied to analyze water extracts of the inhalable fraction of atmospheric PM (PM10, PM2.5 and PM2.1). 81 samples were collected, most during Saharan dust events, from a semirural area, and analyzed. The total water extractable arsenic ranged from 0.03 to 0.7 ng of As m(-3), values that are representative for remote areas. iAs(V) was the most abundant species followed by TMAO, DMA, iAs(III) and MA. None of the As species showed any particular trend with the presence or intensity of dust events, or seasonality, except for TMAO, which showed higher concentrations during the colder months.

Response surface methodology was applied to optimize the parameters for microwave-assisted extraction of six major inorganic and organic arsenic species (As(III), As(V), dimethyl arsenic acid, monomethyl arsenic acid, p-arsanilic acid, and roxarsone) from chicken tissues, followed by detection using a high-performance liquid chromatography with inductively coupled mass spectrometry detection method, which allows the simultaneous analysis of both inorganic and organic arsenic species in the extract in a single run. Effects of extraction medium, solution pH, liquid-to-solid ratio, and the temperature and time of microwave-assisted extraction on the extraction of the targeted arsenic species were studied. The optimum microwave-assisted extraction conditions were: 100 mg of chicken tissue, extracted by 5 mL of 22% v/v methanol, 90 mmol/L (NH4 )2 HPO4 , and 0.07% v/v trifluoroacetic acid (with pH adjusted to 10.0 by ammonium hydroxide solution), ramping for 10 min to 71°C, and holding for 11 min. The method has good extraction performance for total arsenic in the spiked and nonspiked chicken tissues (104.0 ± 13.8% and 91.6 ± 7.8%, respectively), except for the ones with arsenic contents close to the quantitation limits. Limits of quantitation (S/N = 10) for As(III), As(V), dimethyl arsenic acid, monomethyl arsenic acid, p-arsanilic acid, and roxarsone in chicken tissues using this method were 0.012, 0.058, 0.039, 0.061, 0.102, and 0.240 mg/kg (dry weight), respectively., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The National Institute of Standards and Technology is developing a kelp powder standard reference material (SRM) in support of dietary supplement measurements. Edible seaweeds such as kelp and laver consumed as diet or dietary supplement contain tens of mg/kg arsenic. The speciation information of arsenic in the seaweed should be provided because the total arsenic alone does not fully address the safety issue of the dietary supplement as the value assignment is originally intended. The inability to avail all arsenic species for value assignment measurements prevented the certification of arsenic species in the candidate SRM; however, approximately 70 % of total arsenic extracted with a 1:1 volume fraction of methanol:water mixture allowed arsenic speciation values to be assigned to a procedure-defined extract, which may be used for method validation in research to improve upon current extraction and measurement practices. Arsenic species in kelp and laver were identified using electrospray ionization ion trap time of flight mass spectrometry (ESI-IT-TOF). Arsenosugars As(328), As(482), and As(392) were found in the kelp candidate SRM while As(328) and As(482) were found in GBW 08521, a certified reference material (CRM) of laver produced by the National Institute of Metrology of China (NIM). A discovery that the digests of kelp and laver contained only dimethylarsinic acid led to the conclusion that the seaweeds did not contain detectible levels of arsenobetaine, arsenocholine or trimethylarsine oxide that could overlap with the peaks of arsenosugars in the separation. The mean ± s of (5.68 ± 0.28) mg/kg and (13.43 ± 0.31) mg/kg found for As(482) and As(392) in kelp, respectively, using instrumental neutron activation analysis (INAA) demonstrated that value assignment measurement of arsenosugars was possible without arsenosugar calibration standards.

Background: Rice is a potentially important route of human exposure to arsenic, especially in populations with rice-based diets. However, arsenic toxicity varies greatly with species. The initial purpose of the present study was to evaluate arsenic speciation in rice., Results: It appeared very clear from the present study that inorganic arsenic shared maximum arsenic load in rice straw while in grains it is considerably low. As species recovered from rice grain and straw are principally As(III) and As(V) with a small amount of dimethylarsenic acid (DMA) and almost non-detectable monomethylarsonic acid (MMA) and arsenobetain (AsB). Discussion of the health risk of As in rice has largely been based on its inorganic arsenic content because these species have generally been considered to be more toxic than MMA and DMA and can be directly compared to As in drinking water, assuming equal bioavailability of inorganic As in the rice matrix and in water. The maximum dietary risk of exposure to inorganic arsenic through transplanted boro paddy in the present experiment was calculated to be almost 1706% of the provisional tolerable weekly intake for an adult of 60 kg body weight., Conclusion: As species recovered from boro rice grain and straw are principally As(III) and As(V) with a small amount of DMA and almost non-detectable MMA and AsB. Reductions in total As load through organic amendments in boro rice grain and straw samples were manifested predominately through reduced accumulations of inorganic As species [As(III) and As(V)], between which As(V) accounted for the larger share., (© 2014 Society of Chemical Industry.)

Rice consumption is a major route of As exposure to human for the population of worldwide. This study investigates the effect of phytotoxicity and rice genotypes on the content and speciation of As in rice grains grown in different levels of As-elevated paddy soils from Taiwan. Three levels of As-elevated soils and six rice genotypes commonly planted in Taiwan were used for this study. The results indicate that As contents in grains of rice is not proportional to soil As concentrations and they were equal or higher in indica genotypes than japonica genotypes used in this study. It was also found that the As phytotoxicity not only reducing the grain yields but also the As concentrations in grain of rice. The predominant As species found in rice grains were dimethylarsinic acid (DMA) and arsenite. The concentrations of DMA increased with total As concentrations, wherggeas the arsenite remained in a narrow range from 0.1 to 0.3 mg kg(-1). Because of the lower toxicity of DMA than inorganic As species, the health risks may not be increased through consumption of rice even when total As content in the grains is increased., (Copyright © 2014 Elsevier B.V. All rights reserved.)

Levels of arsenic in Australian and imported rice (n = 36) were evaluated using inductively coupled plasma mass spectrometry (ICP-MS) for total arsenic and a hyphenated high-performance liquid chromatography ICP-MS system for arsenic species. The study also assessed the daily intake of total As from diets of healthy children (n = 15), collected over three consecutive days. A wide variation of total As levels (range: <0.05-0.42 mg/kg) in Australian and imported rice was found. The mean level of total As (0.24 ± 0.09 mg/kg, n = 10) in the Australian rice was relatively higher than imported rice from other countries (0.09 ± 0.04 mg/kg, n = 26). The mean level (0.25 ± 0.08 mg/kg, n = 7) of dimethylarsenic acid was considerably higher than that of inorganic As (III) (0.07 ± 0.03 mg/kg, n = 7) in the Australian rice. Children's daily intakes of total As varied widely, ranging from 1.7 to 31.2 (11.5 ± 8.9 µg/day), which was comparable to other countries.

The extraction of arsenic (As) species present in rice flour samples was investigated using different extracting solvents, and the concentration of each species was determined by HPLC-ICP-MS after heat-assisted extraction. The extraction efficiencies for total arsenic species and especially for arsenite [As(III)] and arsenate [As(V)] were investigated. As(III), As(V) and dimethylarsinic acid (DMAA) were found in the samples, and the concentration of DMAA did not vary with treatment conditions. However, the concentrations of extracted total arsenic and those of As(III) and As(V) depended on the extracting solvents. When an extracting solvent was highly acidic, the concentrations of extracted total arsenic were in good agreement with the total arsenic concentration determined by ICP-MS after microwave-assisted digestion, though a part of the As(V) was reduced to As(III) during the highly acidic extraction process. Extraction under neutral conditions increased the extracted As(V), but extracted total arsenic was decreased because a part of the As(III) could not be extracted. Optimum conditions for the extraction of As(III) and As(V) from rice flour samples are discussed to allow the accurate determinations of As(III), As(V) and DMAA in the rice flour samples. Heat block extraction techniques using 0.05 mol L(-1) HClO4 and silver-containing 0.15 mol L(-1) HNO3 were also developed., (Copyright © 2014 Elsevier B.V. All rights reserved.)

A method was developed for the simultaneous determination of arsenic acid [As (V)], arsenious acid [As (III)], arsenobetaine (AsB), monomethylarsonic acid (MMA) and dimethylarsinic acid (DMA) in rice by liquid chromatography-inductively coupled plasma-mass spectrometry (LC-ICP-MS). The extraction reagent was 0.3 mol/L nitric acid with heat-assistant condition for 1.5 h at 95 degrees C. Then, the five arsenic species were separated by an anion exchange column (Dionex IonPac AS19, 250 mm x 4 mm) and detected by ICP-MS. Four kinds of extracted solutions were compared through the extraction efficiency. The concentration of nitric acid, the temperature and the extraction time were optimized. The recoveries of the five arsenic species spiked in rice at two levels ranged from 89.6% to 99.5% with the relative standard deviations (RSDs, n = 5) of 0.6% - 3.6%. The measured values of the arsenic species in standard rice materials were consistent with their standard values. The linear ranges were 0.05 - 200 microg/L for AsB and DMA, 0.10-400 microg/L for As (III) and MMA, 0.15-600 microg/L for As (V). The limits of detection for the five arsenic species were 0.15-0.45 microg/kg. The results showed that the method is much more precise for the risk assessment of the rice. This method is simple, accurate and durable for the determination of arsenic species in rice.

Saliva, an easily accessible biofluid, is validated as biomarker of arsenic (As) exposure in several villages of West Bengal, India. Pentavalent arsenic [As(V)] was found to be the predominant species in saliva, with the amount of inorganic As [As(V) and trivalent form, As(III)] being more than half of the total As in the samples. Significant association was found between total daily ingestion of As and As(V) (r = 0.59; p = 0.000), As(III) (r = 0.60; p = 0.000), dimethylarsinous acid (DMA(V)) (r = 0.40; p = 0.000), and monomethylarsonous acid (MMA(V)) (r = 0.44; p = 0.000), implying that these species have mainly been derived from the methylation of the inorganic As in the water that study participants drank and the food they ate. Analysis of confounding effects of age, sex, smoking, body mass index and the prevalence of skin lesion suggests that women and controls with no skin lesion had a higher capacity to methylate the ingested As compared to the rest of the population. Thus, our study demonstrates that As species in saliva can be an useful tool to predict the individual susceptibility where higher As exposure and a lower methylation capacity are implicated in the development of As-induced health effects.

A study was conducted to develop a microwave-enhanced extraction method for the determination of arsenic species in prenatal and children's dietary supplements prepared from plant materials. The method was optimized by evaluating the efficiency of various solutions previously used to extract arsenic from the types of plant materials used in the dietary supplement formulations. A multivitamin standard reference material (NIST SRM 3280) and a prenatal supplement sample were analyzed in the method optimization. The identified optimum conditions were 0.25 g of sample, 5 mL of 0.3 mol L(-1) orthophosphoric acid (H3PO4) and microwave heating at 90 °C for 30 min. The extracted arsenic was speciated by cation exchange ion chromatography-inductively coupled plasma mass spectrometry (IC-ICP-MS). The method detection limit (MDL) for the arsenic species was in the range 2-8 ng g(-1). Ten widely consumed prenatal and children's dietary supplements were analyzed using the optimized protocol. The supplements were found to have total arsenic in the concentration range 59-531 ng g(-1). The extraction procedure recovered 61-92% of the arsenic from the supplements. All the supplementary products were found to contain arsenite (As(3+)) and dimethylarsinic acid (DMA). Arsenate (As(5+)) was found in two of the supplements, and an unknown specie of arsenic was detected in one product. The results of the analysis were validated using mass balance by comparing the sum of the extracted and non-extracted arsenic with the total concentration of the element in the corresponding samples., (Copyright © 2014 Elsevier B.V. All rights reserved.)

Dimethylarsinic acid (DMA(V)) was pre-concentrated from water samples using a strong cation exchange (SCX) disk functionalized with sulfonic groups, before being analyzed by wavelength dispersive X-ray fluorescence spectrometry (WDXRF). The adsorption of DMA(V) occurred preferentially on the surface of the SCX disk, regardless of pH levels, probably due to interactions with the sulfonic functional groups. However, no other arsenic species, such as arsenate (iAs(V)), arsenite (iAs(III)), and monomethylarsonic acid (MMA(V)), were retained. The SCX-WDXRF method produced a strongly linear calibration curve (R(2)=0.9996) with its limit of detection at 0.218 μgL(-1) when a one-liter water sample was used for pre-concentration. The As intensity of the system was sensitive to the Pb content retained on the SCX disk owing to the proximity of the As-Kα and Pb-Lα lines. To compensate for this interference, a correction factor was developed by considering the calibration slope ratio between the X-ray intensity measured at a Bragg angle of 48.781° and the Pb content of the SCX disks. The results of spike tests for iAs(V), iAs(III), MMA(V), and DMA(V) with and without the addition of Pb in synthetic landfill leachate exhibited reasonable recoveries (i.e., 98-105%) after the spectral adjustment for the Pb interference., (Crown Copyright © 2013. Published by Elsevier B.V. All rights reserved.)

The measurement of As species in rice is normally accomplished by extraction followed by HPLC-ICPMS analysis. This method, however, has not been comprehensively validated by comparing these speciation results with XANES, which does not require sample extraction, due to the challenge of conducting XANES analysis at very low As concentrations. In this study As speciation data using nitric acid extraction/HPLC-ICPMS and XANES are compared to verify the efficacy of using 2% v/v nitric acid extraction and HPLC-ICPMS to measure inorganic As, DMA, and MA in reference rice materials and common rice varieties obtainable in Australia. Total As and As species (As(III), As(V), DMA, and MA) concentrations measured in 8 reference materials were in agreement with published values. XANES analysis was performed on 5 samples having total As concentrations ranging from 0.198 to 0.335 μg g(-1). XANES results gave similar proportions of total As(III), As(V), and DMA to HPLC-ICPMS. XANES was able to distinguish two forms of As(III): As(III) and As(III)GSH. Total As concentrations in rice samples varied from 0.006 to 0.45 μg g(-1) As (n = 47) with a mean ± std of 0.127 ± 0.112 μg g(-1) As with most As present as inorganic species (63 ± 26%). DMA was found in nearly all the rice samples with the majority of samples containing concentrations below 0.05 μg g(-1) As while MA concentrations were negligible (<0.003 μg g(-1) As). Six rice varieties produced in Australia, China, and Spain all had elevated DMA concentrations (0.170-0.399 μg g(-1) As) that were correlated with total As concentrations (r(2) = 0.7518). In conclusion, comparison of As speciation by HPLC-ICPMS and XANES showed that similar As species were detected indicating the appropriateness of using 2% v/v nitric acid for extraction of rice prior to speciation. Common rice varieties obtainable in Australia generally have low As concentrations with most As present as inorganic As.

Arsenic speciation and concentrations were determined in mollusks and crustaceans in the intertidal zone from twelve locations in Zhanjiang estuary, South China. Metal concentrations (Ag, As, Cd, Cu, Hg, Ni, Pb, and Zn) were also concurrently determined in these species. Arsenic speciation analysis showed that the less-toxic arsenobetaine (AsB) constituted 80.6-98.8 % of all As compounds, and dimethylarsinic acid (DMA) constituted 0.47-3.44 %. Monomethylarsonic acid (MMA) and As(V) were only detected in the whelk Drupa fiscella and the crab Heteropilumnus ciliatus, respectively. Arsenite [As(III)] was not detected in any of the sampled specimens, but there were also unidentified other As species. A strong spatial variation of metals in the oyster Saccostrea cucullata was found in the estuary, confirming that oysters can be used as a good biomonitor of metal contamination in the studied area. The concentrations of eight metals in the studied mollusks and crustaceans clearly revealed that these invertebrates accumulated different metals to different degrees. Furthermore, As, Cd, Cu, Hg, and Pb contents in mollusks and crustacean samples were below the Food and Agricultural Organization (FAO) safe concentrations, thus there was no obvious health risk from the intake of the metals through marine mollusks and crustaceans consumption.

Taking arsenic (As)-contaminated paddy soil as test object, and by using high performance liquid chromatography inductively coupled plasma-mass spectrometry (HPLC-ICP-MS), this paper studied the variations of As species in soil solution when the soil was sterilized or non-sterilized and incubated at different temperatures (5, 27, and 50 degrees C) under flooding. In the soil solution (pore water), only As(III) (arsenite), As(V) (arsenate), and DMA(V) ( dimethylarsinic acid) were detected, but no MMA(V)(mono methylarsinic acid) was found. With the increasing time of flooding and at the test temperatures, arsenite became the predominant species, averagely accounting for 64%, followed by As(V), with the proportion of 35%, and DMA(V), with the least proportion of 1%. Soil sterilization or non-sterilization had less effect on the concentrations of As(III) and DMA(V) in the soil solution, but remarkably affected the reduction of As(V) and the methylation of As(III). The promotion effect of soil sterilization decreased gradually with the increasing time of flooding and incubation. At 50 degrees C and after flooded for 23 days, the DMA(V) concentration in sterilized soil solution was the highest and up to 23.7 ng x mL(-1), indicating that some thermophilic microbes remained in sterilized soil became predominant species, and promoted the methylation of As(III) In sum, the total arsenic concentration in non-sterilized soil at incubation temperature 27 degrees C and flooded for 23 days was relatively low (501 ng x mL(-1)), and thus, in As-contaminated paddy rice planting areas, to adopt the water management mode of short cycle flooding-non-flooding could decrease the As level in soil solution as far as possible, and in the same time, save water resources and ensure yielding.

Arsenic trioxide has been successfully used as a therapeutic in the treatment of acute promyelocytic leukemia (APL). Detailed monitoring of the therapeutic arsenic and its metabolites in various accessible specimens of APL patients can contribute to improving treatment efficacy and minimizing arsenic-induced side effects. This article focuses on the determination of arsenic species in saliva samples from APL patients undergoing arsenic treatment. Saliva samples were collected from nine APL patients over three consecutive days. The patients received 10 mg arsenic trioxide each day via intravenous infusion. The saliva samples were analyzed using high-performance liquid chromatography coupled with inductively coupled plasma mass spectrometry. Monomethylarsonous acid and monomethylmonothioarsonic acid were identified along with arsenite, dimethylarsinic acid, monomethylarsonic acid, and arsenate. Arsenite was the predominant arsenic species, accounting for 71.8 % of total arsenic in the saliva. Following the arsenic infusion each day, the percentage of methylated arsenicals significantly decreased, possibly suggesting that the arsenic methylation process was saturated by the high doses immediately after the arsenic infusion. The temporal profiles of arsenic species in saliva following each arsenic infusion over 3 days have provided information on arsenic exposure, metabolism, and excretion. These results suggest that saliva can be used as an appropriate clinical biomarker for monitoring arsenic species in APL patients.

Roxarsone is an organoarsenic feed additive that can be metabolised to other higher toxic arsenic (As) species in animal manure such as arsenate, arsenite, monomethylarsonic acid, dimethylarsinic acid, 3-amino-4-hydroxyphenylarsonic acid and other unknown As species. The accumulation, transport and distribution of As species in turnip (Brassica rapa L.) and lettuce (Lactuca sativa L.) amended with roxarsone and its metabolites in chicken manure were investigated. Results showed arsenite was the predominant As form, followed by arsenate in turnip and lettuce plants, and a low content of dimethylarsinic acid was detected only in lettuce roots. Compared with the control plants treated with chicken manure without roxarsone and its metabolites, the treatments containing roxarsone and its metabolites increased arsenite content by 2.0-3.2% in turnip shoots, by 6.6-6.7% in lettuce shoots, by 11-44% in turnip tubers and by 18-20% in lettuce roots at two growth stages. The enhanced proportion of arsenate content in turnip shoots, turnip tubers and lettuce roots was 4.3-14%, 20-35% and 70%, respectively, while dimethylarsinic acid content in lettuce roots increased 2.4 times. Results showed that the occurrence of dimethylarsinic acid in lettuce roots might be converted from the inorganic As species and the uptake of both inorganic and organic As compounds in turnip and lettuce plants would be enhanced by roxarsone and its metabolites in chicken manure. The pathway of roxarsone metabolites introduced into the human body via roxarsone → animal → manure → soil → crop was indicated.

Total arsenic and four arsenic species; arsenite (iAs(III)), arsenate (iAs(V)), dimethylarsinic acid (DMA(V)) and monomethylarsonic acid (MA(V)), are reported in 28 geothermal features from the Taupo Volcanic Zone (TVZ) and Waikato region of New Zealand. Samples were collected for arsenic speciation analysis via a solid phase extraction (SPE) kit allowing the separation, stabilisation and pre-concentration of the species at the time of sample collection in the field. This is the first research to present data for arsenic species collected by this technique in geothermal waters from New Zealand. Total arsenic concentrations, determined by inductively coupled plasma mass spectrometry (ICP-MS), ranged from 0.008 to 9.08 mg l⁻¹ As. The highest levels were discovered in three features in Tokaanu (Taumatapuhipuhi, Takarea #5 and #6), with arsenic concentrations of 8.59, 8.70 and 9.08 mg l⁻¹ As, respectively. Inorganic arsenic species were predominant in the geothermal waters, with arsenite contributing to more than 70% of the total arsenic in the majority of samples. Organic species were also determined in all samples, indicating the presence of microbial activity. A potential risk to human health was highlighted due to the high levels of arsenic, mainly as arsenite, in geothermal features linked to bathing pools. Further research is needed into dermal absorption as a potential route of arsenic exposure whilst bathing in these hot pools, as it may contribute to an occurrence of acute arsenic-related health problems.