Predominant Arsenic Species Research Articles

Arsenosugar extracted from algae: Assessment of countercurrent chromatography for isolation

Arsenosugars are the predominant species of arsenic in most seaweed. The analysis of these compounds is hampered by the lack of calibration standards needed in their unambiguous identification and quantification. This affects the availability of reliable information on their potential toxicity, which is scarce and controversial.Knowing the potential of centrifugal partition chromatography (CPC) as a preparative separation technique applied to a number of natural compounds, the aim of this work is to investigate the feasibility of CPC in the case of isolation and purification of arsenosugars from algae extracts. Several biphasic solvents systems have been studied to evaluate the distribution of the As species. Given the physical characteristics of these compounds, the presence of strong acids, the formation of ionic pairs or the presence of salts at high ionic strength have been considered. System 1-BuOH/EtOH/sat.(NH4)2SO4/water at a volume ratio 0.2:1:1:1 originates adequate distribution constants of analytes that allows the required separation. The total arsenic content and the arsenic speciation of the eluted solutions from CPC were analyzed by ICP-MS and IC-ICP-MS, respectively.The developed CPC procedure allows us to obtain of the three arsenosugars with a purity of 98.7 % in PO4-Sug, 90.4 % in SO3-Sug and 96.1 % in SO4-Sug.

Survey of arsenic content in edible seaweeds and their health risk assessment

Since humans are especially sensitive to arsenic exposure, predominantly through diet, a strict control of the most widely consumed seaweeds is mandatory. Total arsenic contents and arsenic species in twenty-five different seaweeds from five different origins were studied. Seaweeds selected, included Phaeophyta (brown seaweed), Chlorophyta (green seaweed) and Rhodophyta (red seaweed) genera. The highest arsenic content appears in the Phaeophyta seaweed in the range from 11 to 162 mg kg−1 dried weight. Arsenosugars were found to be the predominant species of arsenic in most seaweeds, being up to 99.7% of total arsenic in some samples. The arsenic dietary intakes for seaweeds studied were assessed and the Target Hazard Quotients (THQ) and the Target Cancer Risk (TCR) were calculated, taking into account inorganic arsenic contents (iAs). iAs species in seaweeds showed low risk of arsenic intake except for Hizikia fusiforme samples.

Gut Microbiota Control the Bioavailability and Metabolism of Organoarsenicals of Seaweeds in Mice after Oral Ingestion.

Edible seaweed consumption is an essential route of human exposure to complex organoarsenicals, including arsenosugars and arsenosugar phospholipids. However, the effects of gut microbiota on the metabolism and bioavailability of arsenosugars in vivo are unknown. Herein, two nori and two kelp samples with phosphate arsenosugar and sulfonate arsenosugar, respectively, as the predominant arsenic species, were administered to normal mice and gut microbiota-disrupted mice treated with the broad-spectrum antibiotic cefoperazone for 4 weeks. Following exposure, the community structures of the gut microbiota, total arsenic concentrations, and arsenic species in excreta and tissues were analyzed. Total arsenic excreted in feces and urine did not differ significantly between normal and antibiotic-treated mice fed with kelp samples. However, the total urinary arsenic of normal mice fed with nori samples was significantly higher (p < 0.05) (urinary arsenic excretion factor, 34-38 vs 5-7%), and the fecal total arsenic was significantly lower than in antibiotic-treated mice. Arsenic speciation analysis revealed that most phosphate arsenosugars in nori were converted to arsenobetaine (53.5-74.5%) when passing through the gastrointestinal tract, whereas a large portion of sulfonate arsenosugar in kelp was resistant to speciation changes and was excreted in feces intact (64.1-64.5%). Normal mice exhibited greater oral bioavailability of phosphate arsenosugar from nori than sulfonate arsenosugar from kelp (34-38 vs 6-9%). Our work provides insights into organoarsenical metabolism and their bioavailability in the mammalian gut.

Arsenic and heavy metals at Japanese abandoned chemical weapons site in China: distribution characterization, source identification and contamination risk assessment.

As-containing chemical weapons (CWs) and their degraded products pose a great threat to the environment and to human health. In this study, concentration and distribution characteristics, source identification, and health risk assessments were determined for As, Cr, Ni, Cu, Zn, Cd and Pb in environmental samples from Lianhuapao (LHP), a typical site of Japanese abandoned chemical weapons (JACWs) in China. The results show that the concentration levels of As, Cr and Ni in the LHP soils are abnormally high, with 69.57%, 83.33% and 91.67%, respectively, of the total sample exceeding the risk screening values for soil contamination of agricultural land. As levels in water samples were generally within safety limits, with the exception of perched water in the core contamination area. In the study area, none of the dominant plant species were enriched with As, except for the Pteris vittata L. Pentavalent arsenic was found to be the predominant arsenic species in the topsoil and water samples. Source identification using statistical approaches indicated that the concentrations of As, Pb, Cu, Cd and Zn are likely influenced by JACWs, while Cr and Ni levels may be related to the natural weathering process. The total concentrations of As, Cr and Ni showed a significant degree of contamination, but only As displayed high potential ecological risk. The calculated indexes of health risk evaluation strongly indicate an unacceptable carcinogenic risk (1E-04) to children, and higher non-carcinogenic risk, relative to that of adults. Our data indicate that the health risk from the resulting As contamination is still a cause for concern, although the JACWs were excavated decades ago from these soils.

Aqueous Arsenic Speciation with Hydrogeochemical Modeling and Correlation with Fluorine in Groundwater in a Semiarid Region of Mexico

In arid and semiarid regions, groundwater becomes the main source to meet the drinking water needs of large cities, food production, and industrial activities. For this reason, necessary studies must be carried out to estimate its quantity and quality, always seeking sustainable management, thus avoiding social conflicts or a decrease in the productive activities of humanity. This research explains the behavior of groundwater quality concerning arsenic speciation and its relationship with fluoride. The average total arsenic concentration of 19.95 µg/L and 20.29 µg/L is reported for the study period from 2015 to 2020, respectively, according to the Mexican standard. If the population drinks water directly, it is exposed to possible damage to health. The predominant arsenic species is As (V), with 95% and As (III) with 5%, this finding will allow us to define in greater detail the type of remediation that is required to reduce the content of this element in the water. Regarding the relationship between arsenic and fluorine, very small Pearson correlation coefficients of the order of 0.3241 and 0.3186 were found. The estimation of the space–time variation made it possible to identify the areas with the highest concentration of arsenic and fluorine, allowing the definition of the operating policies of these wells, thereby protecting the health of the inhabitants who consume this water.

Evaluation of arsenic species in leukocytes and granulocytes of acute promyelocytic leukemia patients treated with arsenic trioxide

Concentrations of arsenic metabolites were important to clarify the sensitivity and resistance of APL (acute promyelocytic leukemia) patients to arsenic trioxide (As2O3). Our purpose was to evaluate levels and distributions of arsenic species in leukocytes and granulocytes of APL patients. Inorganic arsenic (iAs), monomethylarsonic acid (MMA), and dimethylarsinic acid (DMA) were measured by high performance liquid chromatography coupled inductively coupled plasma mass spectrometry (HPLC-ICP-MS). Leukocytes were collected from 21 patients treated with As2O3 during induction, consolidation, and drug-withdrawal period. The upregulation of granulocytes in induction period was closely related to the differentiation of promyelocytes. Therefore, granulocytes were collected during induction period from 4 APL patients and purified by flow cytometry sorting using a panel of monoclonal antibodies specific for CD45, CD3, CD14, and CD19. The developed HPLC-ICP-MS method was precise and accurate with the limit of quantification of 0.5 ng/mL. During induction, consolidation, and drug-withdrawal period, the general trend of arsenic species was iAs > MMA > DMA (P < 0.05) in leukocytes. iAs was predominant arsenic species with median concentration of 10.84 (6.03–14.62) ng/mL. MMA was major methylated metabolite with median concentration of 0.94 (0.60–2.50) ng/mL. Moreover, arsenicals were detected in leukocytes during drug-withdrawal. In granulocytes, iAs was found during induction period with median concentration of 1.08 ng/mL, while MMA and DMA were not detected. These results showed that iAs was the primary arsenic species in leukocytes and granulocytes from APL patients treated with As2O3. This study suggested that iAs might play a dominant therapeutic role during the whole treatment process of APL.

Pollution characteristics and health risk assessment of arsenic transformed from feed additive organoarsenicals around chicken farms on the North China Plain

Arsenic is frequently found in poultry waste, most of which is transformed from feed additive organoarsenicals, resulting in arsenic pollution of soils and water around poultry farms. The North China Plain, an important area for livestock breeding of China, was chosen to investigate the pollution characteristics and assess the health risk of arsenic around chicken farms. Among the 138 chicken farms sampled, almost no roxarsone, a common organoarsenical, was detected in chicken feeds, manure, and surface soils, while the detectable rate of other arsenic species was high. Because of long-term enrichment, the concentrations of arsenic species in manure were generally higher than that in feed. As(III) was the main inorganic arsenic species in the manure, where is reducing environment. In surface soils beneath the accumulated manure, As(V) was the predominant arsenic species with 100% detectable rate. The detectable rate and average concentrations at 0 cm were generally higher than those at 25 cm depth, indicating that arsenic accumulated in the surface soils. In addition, a typical conceptual diagram of arsenic was developed to clarify the pollution process from feed to soil. Through health risk assessment of inorganic arsenic, the carcinogenic risk (CR) and non-carcinogenic risk (non-CR) were both negligible. The city of Jiaozuo had the highest CR and non-CR, which was 11 times higher than that of the city with the lowest risks. This study presents a clear picture and evaluation of arsenic pollution on chicken farms, inspiring future studies assessing arsenic pollution after the ban of organoarsenicals.

Total arsenic and water-soluble arsenic species in foods of the first German total diet study (BfR MEAL Study)

Arsenic can occur in foods as inorganic and organic forms. Inorganic arsenic is more toxic than most water-soluble organic arsenic compounds such as arsenobetaine, which is presumed to be harmless for humans. Within the first German total diet study, total arsenic, inorganic arsenic, arsenobetaine, dimethylarsinic acid and monomethylarsonic acid were analyzed in various foods. Highest levels of total arsenic were found in fish, fish products and seafood (mean: 1.43 mg kg−1; n = 39; min–max: 0.01–6.15 mg kg−1), with arsenobetaine confirmed as the predominant arsenic species (1.233 mg kg−1; n = 39; min–max: 0.01–6.23 mg kg−1). In contrast, inorganic arsenic was determined as prevalent arsenic species in terrestrial foods (0.02 mg kg−1; n = 38; min–max: 0–0.11 mg kg−1). However, the toxicity of arsenic species varies and measurements are necessary to gain information about the composition and changes of arsenic species in foods due to household processing of foods.

Improved grain yield and lowered arsenic accumulation in rice plants by inoculation with arsenite-oxidizing Achromobacter xylosoxidans GD03

Arsenite is the predominant arsenic species in flooded paddy soil, and arsenite bioaccumulation in rice grains has been identified as a major problem in many Asian countries. Lowering arsenite level in rice plants and grain via accelerating arsenite oxidation is a potential strategy to help populations, who depended on rice consumption, to reduce the internal exposure level of arsenic. We herein isolated a strain, Achromobacter xylosoxidans GD03, with the high arsenite-oxidizing ability and plant growth-promoting traits. We observed that arsenite exposure could promote A. xylosoxidans GD03 to excrete indole-3-acetic acid and thus promoted rice growth. The pot culture experiments of Indica rice cultivar Guang You Ming 118 (GYM118) demonstrated that A. xylosoxidans GD03 inoculation of paddy soil (4.5–180 × 108 CFU GD03/kg soil) significantly accelerated arsenite oxidation in flooded soil. The daily arsenic oxidation rate with GD03 inoculation was 1.5–3.3 times as that without strain GD03 inoculation within the whole growth period of Indica GYM118 in the presence of the native microflora. It thus led to a 34–69%, 43–74%, 24–76% and 35–57% decrease in arsenite concentration of the stems, leaves, bran and grain of Indica GYM118 respectively and a 59–96% increase in rice grain yield. The paddy soil inoculated with 40.0 mL/kg of A. xylosoxidans GD03 resulted in a lowest As(III) concentrations in all rice organs of Indica GYM118, which equivalent to only 24–50% of the As(III) concentrations in the group without GD03 inoculation. The results highlight that a highly arsenite-oxidizing bacterium could accelerate arsenite oxidation of paddy soil when facing competition with the native microflora, thus decrease arsenic toxicity and bioavailable soil arsenic.

AuNPs-polyaniline nanosheet array on carbon nanofiber for the determination of As(III)

Abstract As(III) is a highly toxic and predominant arsenic species especially in anoxic groundwater. In this paper, the measurement of trace amount of As(III) was reported by using the Au-PANI-Fe-CNFs composite as sensing platform. The Au-PANI-Fe-CNFs composite was constructed by the formation of polyaniline (PANI) nanosheet array on the electrospun Fe-containing carbon nanofibers (Fe-CNFs) substrate followed by self-deposition of Au nanoparticle. PANI presents a uniform array structure on the fiber surface. Au nanoparticles were deposited uniformly on the PANI nanosheet surface by means of the reducing property of PANI, with the particle size of about 20 ± 6 nm. The presence of Fe in the CNFs accelerates the growth of PANI nanosheet and improves the As adsorption in the sensing process of As(III) thereafter. The obtained Au-PANI-Fe-CNFs exhibit excellent electrochemical performance for the detection of As(III) in water, because of the unique structure of PANI array and uniform distribution of AuNPs. The designed electrode displays wide linear range (5– 400 ppb) and high sensitivity with a detection limit of 0.5 ppb (S/N ≥ 3). This novel modified electrode shows a great opportunity for the electrochemical analysis of arsenic and its analogues in water.

Chronic arsenate exposure affects amphipod size distribution and reproduction.

Arsenate (As V) is the predominant inorganic species of arsenic in oxic aquatic environments. Chronic water quality criteria for arsenate have not been established due to the scarcity of relevant studies on its impact on aquatic biota. We examined the acute and chronic effects of arsenate on the benthic amphipod Leptocheirus plumulosus, an important test organism for ecotoxicological studies. We determined that a concentration of 1,971 µg/L arsenate induced 50% mortality (LC50) in juveniles in 96-hr water only exposure. Subsequently, we tested the efficacy of a 42-day sediment bioassay to determine chronic population-level effects. Specifically, we analyzed the survivorship, size distribution, reproduction and offspring sex ratio of this amphipod to a sublethal concentration of arsenate. The sublethal concentration was determined based on the results of the acute tests. Arsenate (500 µg/L) was added to seawater (20 psu) overlying natural sediments (particle sizes < 250 µm). Fifteen replicate chambers per treatment were employed, each stocked with 20 stage-sorted juvenile amphipods (500–600 µm). Five replicates per treatment were destructively sampled on week 3 and ten replicates were sampled on week 6. Arsenate exposure did not affect the survivorship of parental amphipods, as expected, but it decreased significantly the number of offspring in the largest size classes. By week 6, arsenate-exposed replicates had statistically fewer sexually mature offspring compared to controls, likely because the overall reproduction was suppressed. Arsenate exposed amphipods had significantly fewer offspring than controls by week 6 (9.3 vs. 19.1 per parent), but the sex ratio of the offspring was not altered. Our results indicate that size distribution and reproduction may be more sensitive endpoints than survivorship for the chronic effects of arsenate in oxic systems. The extended 42-day bioassay with Leptocheirus plumulosus is a very promising tool to study the effects of toxicants on population dynamics.

Arsenic concentrations, diversity and co-occurrence patterns of bacterial and fungal communities in the feces of mice under sub-chronic arsenic exposure through food

BackgroundArsenic, a global pollutant and a threshold-free primary carcinogen, can accumulate in rice. Previous studies have focused on arsenic poisoning in drinking water and the effects on gut microbes. The research on arseniasis through food, which involves the bio-transformation of arsenic, and the related changes in gut microbiome is insufficient. MethodMice were exposed from animal feed prepared with four arsenic species (iAsIII, iAsV, MMA, and DMA) at a dose of 30 mg/kg according to the arsenic species proportion in rice for 30 days and 60 days. The levels of total arsenic (tAs) and arsenic species in mice feces and urine samples were determined using ICP-MS and HPLC-ICP-MS, respectively. 16S rRNA and ITS gene sequencing were conducted on microbial DNA extracted from the feces samples. ResultsAt 30 days and 60 days exposure, the tAs levels excreted from urine were 0.0092 and 0.0093 mg/day, and tAs levels in feces were 0.0441 and 0.0409 mg/day, respectively. We found significant differences in arsenic species distribution in urine and feces (p < 0.05). In urine, the predominant arsenic species were iAsIII (23% and 14%, respectively), DMA (55% and 70%, respectively), and uAs (unknown arsenic, 14% and 10%, respectively). In feces, the proportion of major arsenic species (iAsV, 26% and 21%; iAsIII, 16% and 15%; MMA, 14% and 14%; DMA, 19% and 19%; and uAs, 22% and 29%, respectively) were evenly distributed. Microbiological analysis (MRPP test, α- and β-diversities) showed that diversity of gut bacteria was significantly related to arsenic exposure through food, but diversity of gut fungi is less affected. Manhattan plot and LEfSe analysis showed that arsenic exposure significantly changes microbial taxa, which might be directly associated with arsenic metabolism and diseases mediated by arsenic exposure, such as Deltaproteobacteria, Polynucleobacter, Saccharomyces, Candida, Amanitaceae, and Fusarium. Network analysis was used to identify the changing hub taxa in feces along with arsenic exposure. Function predicting analysis indicated that arsenic exposure might also significantly increase differential metabolic pathways and would disturb carbohydrates, lipid, and amino acids metabolism of gut bacteria. ConclusionsThe results demonstrate that subchronic arsenic exposure via food significantly changes the gut microbiome, and the toxicity of arsenic in food, especially in staples, should be comprehensively evaluated in terms of the disturbance of microbiome, and feces might be the main pathway through which arsenic from food exposure is excreted and bio-transformed, providing a new insight into the investigation of bio-detoxification for arseniasis.

A method for rapid determination of arsenic species in vegetables using microwave-assisted extraction followed by detection with HPLC hyphenated to inductively coupled plasma-mass spectrometry.

Driven by the significant need for characterization of the chemical speciation of arsenic in food, this work developed a method for rapid determination of four common arsenic species, namely, arsenite, arsenate, monomethyl arsenic acid, and dimethyl arsenic acid, in vegetables using microwave-assisted extraction, followed by detection with high-performance liquid chromatography hyphenated to inductively coupled plasma-mass spectrometry. Initial screening results showed that microwave-assisted extraction using 1% HNO3 exhibited the highest overall efficiencies for all arsenic species without causing significant degradation of the organic ones. With the aid of response surface methodology, the optimum conditions established for extraction of arsenic species from vegetables were: 500mg of freeze-dried vegetable sample, extracted by closed vessel microwave-assisted extraction using 10mL of 2% v/v HNO3 at 90°C for 17min. Application of the method in the analysis of 24 market vegetable samples indicates that the extraction efficiencies for total arsenic species were in the range of 91.4-106%. Arsenite and arsenate were found to be the predominant arsenic species in the vegetables, which suggests that vegetable consumption could be an important route of inorganic arsenic exposure for the population with a heavy vegetable diet in arsenic polluted regions.

Effects of roxarsone and sulfadiazine on biogas production and their degradation during anaerobic digestion

Roxarsone and sulfadiazine are typical feed additives and often occur in manure and livestock wastewater. Anaerobic digestion is a common technique for the treatment of manure and livestock wastewater. However, the influence of roxarsone and sulfadiazine on anaerobic digestion and their degradation are still unclear. In this study, the effect of roxarsone and sulfadiazine on the anaerobic digestion of synthetic wastewater and their degradation were investigated. During 70-day incubation, the presence of 200 mg L−1 sulfadiazine exhibited little influence on hydrolysis and acidification, but resulted in a temporary inhibition on methanogenesis, whereas 120 mg L−1 of roxarsone resulted in nearly complete inhibition on methanogenesis. Further, the co-existence of 100 mg L−1 sulfadiazine and 60 mg L−1 roxarsone significantly exacerbated the inhibition on anaerobic digestion. Sulfadiazine exhibited high resistance to the adsorption and biodegradation, while roxarsone was nearly completely degraded during anaerobic digestion. Nearly half of total arsenic was transferred from solution to anaerobic granular sludge. The predominant arsenic species was 4-hydroxy-3-aminophenylarsonic acid in the solution and As3+ in the sludge. These results will provide valuable information for anaerobic treatment of livestock wastewater simultaneously contaminated by roxarsone and sulfadiazine.

Lipidomic profiling of subchronic As4S4 exposure identifies inflammatory mediators as sensitive biomarkers in rats.

Arsenic sulfide compounds provide nearly all of the world's supply of arsenic. However, the risk of arsenic trisulfide exposure is still not fully investigated. Here, we systemically assessed the toxicology of As4S4 in rats by combining arsenic metabolite detection, routine testing and lipidomic profiling. It was revealed that the oral administration of As4S4 for two months increased the total arsenic content in the liver reaching a saturation level. Further analysis by anion exchange chromatography coupled with inductively coupled plasma mass spectrometry (ICP-MS) technology showed no trace of inorganic arsenic, but there was significant presence of dimethylarsinic acid (DMA), in the livers of rats. This arsenic metabolite was less toxic to rats and did not induce overt liver pathology and functional injury. In contrast, lipidomic profiling provided a comprehensive map of lipids and uncovered a more complex inflammatory response, exhibiting more sensitive change to arsenic exposure. We observed that metabolites of cyclooxygenase, including PGF2α, dhk PGF2α, 15k PGF2α, 8-iso-PGF2a, PGE2, dhk PGE2, PGD2, 15d-PGD2, and PGJ2, were significantly elevated. But mediators from lipoxygenase, cytochrome P450, docosahexaenoic acid, and eicosapentaenoic acid pathways were not markedly affected. In summary, we identified DMA as the predominant arsenic species in the livers of rats, and found cyclooxygenase-derived lipids as the inflammatory mediators before the development of overt liver injury for subchronic As4S4 exposure. These mediators could translate into potential metabolic biomarkers in early arsenic risk assessment and as targets for therapeutic intervention.

Arsenic species in rice and rice-based products consumed by toddlers in Switzerland

ABSTRACTInorganic arsenic (iAs) is a contaminant present in food, especially in rice and rice-based products. Toxicity of arsenic compounds (As) depends on species and oxidative state. iAs species, such as arsenite (As(III)) and arsenate (As(V)), are more bioactive and toxic than organic arsenic species, like methylarsonic acid (MMA(V)) and dimethylarsinic acid (DMA(V)) or arsenosugars and arsenobetaine. An ion chromatography-inductively coupled-plasma-mass spectroscopy method was developed to separate the four following arsenic anions: As(III), As(V), MMA(V) and DMA(V). Sample preparation was done in mild acidic conditions to ensure species preservation. The predominant arsenic species found in rice and rice-based products, except for rice drinks, was As(III), with 60–80% of the total As content, followed by DMA(V) and As(V). MMA(V) was measured only at low levels (<3%). Analyses of rice products (N = 105) intended for toddlers, including special products destined for infants and toddlers, such as dry form baby foods (N = 12) or ready-to-use form (N = 9), were done. It was found in this study that there is little or no margin of exposure. Risk assessment, using the occurrence data and indicated intake scenarios compared to reference BMDLs as established by EFSA, demonstrated toddlers with a high consumption of rice based cereals and rice drinks are at risk of high iAs exposure, for which a potential health risk cannot be excluded.

Dose and Diet - Sources of Arsenic Intake in Mouse in Utero Exposure Scenarios.

In humans, early life exposure to inorganic arsenic is associated with adverse health effects. Inorganic arsenic in utero or in early postnatal life also produces adverse health effects in offspring of pregnant mice that consumed drinking water containing low part per billion levels of inorganic arsenic. Because aggregate exposure of pregnant mice to inorganic arsenic from both drinking water and food has not been fully evaluated in experimental studies, quantifying arsenic exposure of the developing mouse is problematic. Here, we determined levels of total arsenic and arsenic species in natural ingredient rodent diets that are composed of many plant and animal-derived foodstuffs and in a purified ingredient rodent diet that is composed of a more restricted mixture of foodstuffs. In natural ingredient diets, total arsenic levels ranged from ∼60 to ∼400 parts per billion, and in the purified ingredient diet, total arsenic level was 13 parts per billion. Inorganic arsenic was the predominant arsenic species in trifluoroacetic acid extracts of each diet. Various exposure scenarios were evaluated using information on inorganic arsenic levels in diet and drinking water and on daily food and water consumption of pregnant mice. In a scenario in which pregnant mice consumed drinking water with 10 parts per billion of inorganic arsenic and a natural ingredient diet containing 89 parts per billion of inorganic arsenic, drinking water contributed only ∼20% of inorganic arsenic intake. Quantitation of arsenic species in diets used in studies in which drinking water is the nominal source of arsenic exposure provides more accurate dosimetry and improves understanding of dose-response relations. Use of purified ingredient diets will minimize the discrepancy between the target dosage level and the actual dosage level attained in utero exposure studies designed to evaluate effects of low level exposure to inorganic arsenic.

Do Si/As ratios in growth medium affect arsenic uptake, arsenite efflux and translocation of arsenite in rice (Oryza sativa)?

Silicon (Si) may decrease the uptake and accumulation of arsenic (As) in rice. However, the effects of Si/As ratios in growth medium on arsenic uptake, arsenite efflux to the external medium and translocation of arsenite in rice are currently unclear. Rice seedlings (Oryza sativa L.) were exposed to nutrient solutions with 10 μM arsenite [As(III)] or 10 μM arsenate [As(V)] to explore the influence of different silicic acid concentrations (0, 10, 100, 1000 μM) on arsenic uptake and translocation of arsenite with or without 91 μM phosphate for 24 h. Arsenic speciation was determined in nutrient solutions, roots, and shoots. In the arsenite treatments, different Si/As ratios (1:1, 10:1, 100:1) did not affect As(III) uptake by rice roots, however they did inhibit translocation of As(III) from roots to shoots significantly (P < 0.001) in the absence of P. In the arsenate treatments, a Si/As ratio of 100:1 significantly decreased As(V) uptake and As(III) efflux compared with the control (Si/As at 0:1), accounting for decreases of 27.4% and 15.1% for –P treatment and 47.8% and 61.1% for + P treatment, respectively. As(III) is the predominant species of arsenic in rice roots and shoots. A Si/As ratio of 100:1 reduced As(III) translocation from roots to shoots markedly without phosphate. When phosphate was supplied, As(III) translocation from roots to shoots was significantly inhibited by Si/As ratios of 10:1 and 100:1. The results indicated that in the presence of P, different silicic acid concentrations did not impact arsenite uptake and transport in rice when arsenite was supplied. However, a Si/As ratio of 100:1 inhibited As(V) uptake, as well as As(III) efflux and translocation from roots to shoots when arsenate was supplied.

Speciation of Arsenic in Fish by High-Performance Liquid Chromatography-Inductively Coupled Plasma-Mass Spectrometry

ABSTRACTArsenic speciation in fish was performed using isocratic elution with cation exchange column high-performance liquid chromatography and inductively coupled plasma-mass spectrometry detection. The separation of arsenobetaine and dimethylarsinic acid was performed in 12 min. DOLT-4 dogfish liver and NIST RM-50 albacore tuna certified reference materials were used to evaluate the accuracy for the determination of total arsenic in fish. In addition, reference materials were analyzed for arsenobetaine and dimethylarsinic acid, although they were not certified for these analytes. The limits of detection for arsenic in arsenobetaine and dimethylarsinic acid were 0.20 and 0.33 ng/mL, and the limits of quantitation were 0.58 and 1.11 ng/mL, respectively. Total arsenic and arsenic species were determined in fish using the developed method. The predominant arsenic species was arsenobetaine; the measured concentrations were from 0.43 to 12.0 mg/kg arsenic as arsenobetaine. Dimethylarsinic acid concentrations were below the limit of quantitation. The relative standard deviations were between 3.36 and 10.49 for total arsenic and 3.51 and 9.30 for arsenobetaine.

Arsenic Speciation in Honeysuckle (Lonicera japonica Thunb.) from China.

In this study, honeysuckle, a common Chinese herbal medicine, produced from different areas was investigated for total arsenic and arsenic species concentration. The total arsenic concentrations were determined by inductively coupled plasma mass spectrometry (ICP-MS) and ranged from 275 to 635μgkg(-1). A microwave-assisted procedure with 1% phosphoric acid (v/v) was used for the extraction of arsenic species in honeysuckle. The total arsenic species concentration found by liquid chromatography-inductively coupled plasma mass spectrometry (LC-ICP-MS) was in agreement with the total arsenic concentration determined by the ICP-MS analysis after the microwave digestion. Arsenate (As(V)) with an average proportion of 54.3% was the predominant arsenic species in honeysuckle. The order of concentration is as follows: As(V) > arsenite (As(III)) > dimethylarsinic acid (DMA) > arsenobetaine (AsB) > monomethylarsonic acid (MMA). The proportion of organic arsenic (24.7%) was higher than that in most terrestrial plants. Moreover, the distributions of arsenic species in the honeysuckle from different producing areas were significantly different. This study provides useful information for better understanding of the distribution of arsenic species in terrestrial plants.