Metabolism and disposition of arsenic species from controlled dosing with sodium arsenite in adult female CD-1 mice. III. Toxicokinetic studies following oral and intravenous administration.

Arsenic is a ubiquitous contaminant, with typical dietary intake below 1 µg/kg bw/d and drinking water exposures up to 50 µg/kg bw/d. Arsenic exposures are associated with human diseases and doses of toxicological concern are similar to typical dietary intake. Metabolism of arsenite to dimethylarsinate (DMAV) by arsenite-3-methyltransferase (As3MT) promotes clearance, but also generates reactive trivalent intermediates that bind extensively to cellular thiols. This study measured pentavalent and trivalent arsenic species in blood and tissues after oral and intravenous administration of arsenite (50 µg/kg bw). After oral administration, the intestine and liver contained elevated levels of AsIII and MMAIII, relative to erythrocytes, lung, and kidney, suggesting incomplete conversion to DMA during first-pass metabolism. However, blood concentrations of the predominant species, DMA, were similar for oral and intravenous dosing. While all tissues examined contained DMAIII, muscle, brain, and plasma had undetectable levels of MMAIII. Tissue levels of arsenic species were similar following intravenous vs. oral administration, except lower in the intestine. The results confirm the role of metabolism in producing fluxes of putatively toxic trivalent arsenic intermediates. Tissue dosimetry suggests that the intestine, liver, lung, and kidney could be more susceptible to effects of bound arsenic, relative to muscle and brain.

Arsenic speciation in food in Belgium. Part 2: Cereals and cereal products.

This study reports results of total arsenic (Astot) and various As species in 75 samples of cereals and cereal products bought on the Belgian market. In addition to rice, the samples were wheat, pasta, bread and some breakfast cereals. The inorganic species arsenite (AsIII) and arsenate (AsV), and the organic As compounds dimethyl arsinate (DMA) and monomethyl arsonate (MA) were the only As species detected. Mean Astot was 0.150 ±â€¯0.089 mg kg-1 in rice and 0.012 ±â€¯0.008 mg kg- in the non-rice cereals. The inorganic arsenic fraction (Asi = AsIII + AsV) dominated in all samples and was in the range 55%-100%. Significantly higher Astot and Asi concentrations were observed in white rice and brown rice compared to Basmati rice. Within the group of non-rice cereals bread and pasta showed significantly lower concentrations compared to wheat. All 30 rice samples were conform to the European maximum limits for Asi, laid down in Commission Regulation (EU) 2015/1006. Although regulatory limits certainly can help to protect consumer health, our results suggest that the currently fixed European maximum levels are, in Belgium, not expected to have any impact on the human exposure to Asi, which is a known carcinogenic substance.

Arsenic(III) and arsenic(V) speciation during transformation of lepidocrocite to magnetite.

Bioreduction of As(V) and As-bearing iron oxides is considered to be one of the key processes leading to arsenic pollution in groundwaters in South and Southeast Asia. Recent laboratory studies with simple aqueous media showed that secondary Fe(II)-bearing phases (e.g., magnetite and green rust), which commonly precipitate during bioreduction of iron oxides, captured arsenic species. The aim of the present study was to follow arsenic speciation during the abiotic Fe(II)-induced transformation of As(III)- and As(V)-doped lepidocrocite to magnetite, and to evaluate the influence of arsenic on the transformation kinetics and pathway. We found green rust formation is an intermediate phase in the transformation. Both As(III) and As(V) slowed the transformation, with the effect being greater for As(III) than for As(V). Prior to the formation of magnetite, As(III) adsorbed on both lepidocrocite and green rust, whereas As(V) associated exclusively with green rust, When magnetite precipitated, As(III) formed surface complexes on magnetite nanoparticles and As(V) is thought to have been incorporated into the magnetite structure. These processes dramatically lowered the availability of As in the anoxic systems studied. These results provide insights into the behavior of arsenic during magnetite precipitation in reducing environments. We also found that As(V) removal from solution was higher than As(III) removal following magnetite formation, which suggests that conversion of As(III) to As(V) is preferred when using As-magnetite precipitation to treat As-contaminated groundwaters.

Arsenic speciation in rice-based food for adults with celiac disease.

Celiac disease (CD) may affect up to 1% of the Western population. It is a disease whose diagnosis has been made mainly in childhood, but now the profile has changed, with one out of five newly diagnosed individuals being over 65 years old. The only treatment for this population is a gluten-free diet. Therefore, the objective of this study was to analyse the occurrence of arsenic (As) in gluten-free products, basically those rice-based, intended for celiac adult consumers. The current study demonstrated that these rice-based products contained important contents of total arsenic (t-As) (up to 120 µg kg(-1)) and inorganic arsenic (i-As) (up to 85.8 µg kg(-1)). It was estimated that the contents of t-As and i-As in rice used as the main ingredient of these foods were as high as 235 and 198 µg kg(-1), respectively. The estimated daily intake of i-As was 0.46 and 0.45 µg kg(-1) bw in women and men of 58 and 75 kg of body weight (bw), respectively. These values indicate that a health risk to these consumers cannot be excluded. Finally, legislation is needed to delimit the safety intake by health agencies and to improve the labelling of these special rice-based foods for celiac adult consumers. The label should include information about percentage, geographical origin and cultivar of the rice used; besides and if companies want to clearly prove the safety of their products, the exact content of i-As should also be included.

Arsenic species in drinking water wells in the USA with high arsenic concentrations.

Arsenic exists in ground water as oxyanions having two oxidation states, As(III) and As(V), and its concentrations vary widely and regionally across the United States (USA). Because of the difference in toxicity and removability of As(III) and As(V), arsenic speciation is important in the selection and design of an arsenic treatment systems. Identifying the arsenic species is also helpful in explaining and understanding the behavior and characteristics of arsenic in the environment. Although laboratory methods exist for speciating arsenic in water samples, the lack of a universal preservation method has led to the predominant use of field separation methods that are somewhat complex and costly. Thus, very few studies have incorporated arsenic speciation. A U.S. Environmental protection Agency (EPA) arsenic treatment research program provided a unique opportunity to speciate the naturally occurring arsenic in 65 well waters scattered across the USA with many of them being speciated monthly for up to three years. Speciation test data showed that 31 wells had predominantly As(V), 29 had predominantly As(III) and five had a mixture of both. A general pattern was found where As(III) was the dominant species in midwest ground waters where anoxic conditions and elevated iron concentrations prevailed and the well waters in the east, west and farwest had either As(III) or As(V) as the dominant species. The monthly (12-36) speciation tests results at many of these sites also found no major changes in arsenic species over time.

(Micro)spectroscopic analyses of particle size dependence on arsenic distribution and speciation in mine wastes.

The chemical speciation and distribution of potentially toxic metal(loid)s in mine wastes is critical to assessing the risks posed by these wastes and predicting the potential bioavailability of the metal(loid)s present. Of additional potential importance is the role of particle size in the fate, transport, and toxicity of contaminated mining materials. Spectroscopic analyses of size-separated mine tailings and adjacent background samples from the Randsburg Historic Mining District, California were conducted to quantify the speciation and distribution of arsenic (As) as a function of particle size. Micro-X-ray fluorescence (µXRF) mapping of separate size fractions was used to identify multiple populations of particles with different As:Fe ratios, indicating a variety of distinct arsenic-bearing species. Bulk extended X-ray absorption fine structure (EXAFS) spectroscopy identified phases including arseniosiderite, Ca2Fe3(3+)(AsO4)3O3·3H2O, and As(V) sorbed to iron hydroxides (ferrihydrite, goethite), confirming a strong statistical correlation between arsenic and iron observed in both µXRF studies and bulk chemical analyses. Differences in As speciation between the mine tailings and background samples also suggest that weathering of crystalline As-bearing phases in tailings leads to sorption of dissolved arsenic to iron hydroxides in nontailings background material.

Distribution and chemical speciation of arsenic and heavy metals in highly contaminated waters used for health care purposes (Srebrenica, Bosnia and Herzegovina).

Determination of distribution and chemical speciation of arsenic and heavy metals in five acidic springs and in the receiving river near Srebrenica (Bosnia and Herzegovina) was carried out. These waters were used for centuries, and continue to be used, for health-care purposes. The composition and properties of all springs and the river water (after all inputs) resembled that of an acid mine drainage. Very low pH (<3.3), high sulphate concentration and extremely high contents of most of the measured elements (25) are found in all springs (e.g. arsenic and iron maximal concentration of 6.6 and 500 mg L(-1), respectively). Although of small discharge, spring waters caused the decrease of the receiving river pH (from 7.3 to 3.4) and the considerable increase of the concentrations of elements. The enrichment factor for the studied elements ranged from 1.2 for Sr up to 425 for As. In acidic spring waters, all elements were predominantly present in dissolved form. Elements associated to freshly-formed hydrous ferric oxide were prevailing in particulate forms only at the two most upstream sites in the river with pH>7. Geochemical speciation modelling (PHREEQC and WHAM-VI) revealed that As was mainly present as As(V), and Fe as Fe(III). Complexation of dissolved metals by organic matter was predicted to be significant only for the two river sites with neutral pH.

Analysis of arsenic species in fish after derivatization by GC-MS.

The derivatization of organoarsenic compounds by different reagents like thioglycolates or dithiols and the subsequent analysis by GC-MS as a molecular specific technique was investigated and described. The possible derivatization reagents methyl- and ethylthioglycolate (TGM and TGE), 1,3-propane- and 1,5-pentanedithiol (PDT and PeDT), which transfer the polar and nonvolatile analytes dimethylarsenate (DMA), monomethylarsonate (MMA), arsenite and arsenate into volatile compounds, were evaluated. The application for real samples like fish material was also studied. In addition the gas chromatographic separation and resolution was optimized and experiments were carried out to determine the highest derivatization rates. Derivatization reagents were evaluated in terms of quantity and stability of the formed chemical species. All derivatization products were characterized by mass spectrometry in order to identify the separated arsenic species. The most efficient conversion of DMA and MMA was observed by using ethylthioglycolate as derivatization agent. Finally, the derivatization procedure and the GC-MS-method were validated to determine linearity, precision, selectivity, analytical limiting values and recoveries. For the proposed method a limit of detection (LOD) of 5.8 pg for DMA and 14.0 pg for MMA was found. The accuracy was established by comparing the mean value measured for DMA in the certified reference material BCR-627 (tuna fish) with the certified one. MMA was not quantified in marine samples due to its low content. In shrimp samples DMA was not detectable. For codfish a DMA-content of 0.20±0.004 mg kg(-1), for "Surströmming" an amount of 0.38±0.02 mg kg(-1) and for herring, which showed the highest amount of DMA, a content of 1.15±0.03 mg kg(-1) was determined.

Arsenic localization and speciation in the root-soil interface of the desert plant Prosopis juliflora-velutina.

The bioavailability and mobility of arsenic (As) in soils depends on several factors such as pH, organic matter content, speciation, and the concentration of oxides and clay minerals, among others. Plants modify As bioavailability in the rhizosphere; thus, the biogeochemical processes of As in vegetated and non-vegetated soils are different. Changes in As speciation induced by the rhizosphere can be monitored using micro-focused synchrotron-based X-ray fluorescence (µXRF) combined with µX-ray absorption near-edge spectroscopy (µXANES). This research investigated As speciation in the rhizosphere of mesquite (Prosopis juliflora-velutina) plants grown in a sandy clay loam treated with As(III) and As(V) at 40 mg kg(-1). Rhizosphere soil and freeze-dried root tissues of one-month-old plants were analyzed by bulk XAS. Bulk XAS results showed that As(V) was the predominant species in the soil (rhizosphere and non-vegetated), whereas As(III) was dominant in the root tissues from both As(V) and As(III) treated plants. µXAS and µXRF studies of thin sections from resin embedded soil cores revealed the As(III)-S interactions in root tissues and a predominant As-Fe interaction in the soil. This research demonstrated that the combination of bulk XAS and µXAS techniques is a powerful analytical technique for the study of As speciation in soil and plant samples.

Fast separations by capillary electrophoresis hyphenated to electrospray ionization time-of-flight mass spectrometry as a tool for arsenic speciation analysis.

Fast capillary electrophoresis (CE) hyphenated to time-of-flight mass spectrometry (TOF-MS) of four organoarsenic species (glycerol oxoarsenosugar, sulfate oxoarsenosugar, arsenobetaine, arsenocholine) are presented using short length CE capillaries under high electric field strengths of up to 1.3 kV cm(-1) with small inner diameter (ID). The separation of arsenosugars by CE is demonstrated for the first time. An aqueous formic acid solution was employed as the background electrolyte (BGE) for the separation. Various acid concentrations were evaluated for their influence on migration times, separation efficiency as well as with regard to controlling the charge of the arsenic species. A 0.1 M formic acid/ammonium formate buffer (pH 2.8) proved to be suitable for the separation of the four species. A non-aqueous BGE was tested as an alternative buffer system for fast speciation analysis. Separation of arsenobetaine and arsenocholine could even be achieved within 10 s by pressure-assisted CE. Application of the optimized method for the analysis of extracts of a seagrass and a Wakame algae sample as well as the brown algae homogenate reference material IAEA-140/TM revealed a clear signal for the glycerol arsenosugar.

Arsenic speciation in biomedical sciences: recent advances and applications.

Speciation analysis of trace elements is an important issue in biomedical and toxicological sciences because different elemental species have different effects on health and the environment. For humans, arsenic (As) is a toxic element; the toxicity of As compounds is highly dependent on its chemical form. Although inorganic As compounds are human carcinogens, organic arsenicals are relatively less toxic. This article deals with recent advances and applications of methods for As speciation in biomedical sciences, with emphasis on the specimens commonly encountered in biomedical laboratories.

Speciation of arsenic in rice and estimation of daily intake of different arsenic species by Brazilians through rice consumption.

Rice is an important source of essential elements. However, rice may also contain toxic elements such as arsenic. Therefore, in the present study, the concentration of total arsenic and five main chemical species of arsenic (As(3+), As(5+), DMA, MMA and AsB) were evaluated in 44 different rice samples (white, parboiled white, brown, parboiled brown, parboiled organic and organic white) from different Brazilian regions using high-performance liquid chromatography hyphenated to inductively coupled plasma mass spectrometry (HPLC-ICP-MS). The mean level of total arsenic was 222.8 ng g(-1) and the daily intake of inorganic arsenic (the most toxic form) from rice consumption was estimated as 10% of the Provisional Tolerable Daily Intake (PTDI) with a daily ingestion of 88 g of rice. Inorganic arsenic (As(3+), As(5+)) and dimethylarsinic acid (DMA) are the predominant forms in all samples. The percentages of species were 38.7; 39.7; 3.7 and 17.8% for DMA, As(3+), MMA and As(5+), respectively. Moreover, rice samples harvested in the state of Rio Grande do Sul presented more fractions of inorganic arsenic than rice in Minas Gerais or Goiás, which could lead to different risks of arsenic exposure.

Arsenic speciation in municipal landfill leachate.

Arsenic species in municipal landfill leachates (MLL) were investigated by HPLC-DRC-ICPMS and LC-ESI-MS/MS. Various arsenic species including arsenate (iAs(V)), arsenite (iAs(III)), monomethylarsonic acid (MMA(V)), dimethylarsinic acid (DMA(V)), as well as sulfur-containing organoarsenic species were detected. Two sulfur-containing arsenic species in a MLL were positively identified as dimethyldithioarsinic acid (DMDTA(V)) and dimethylmonothioarsinic acid (DMMTA(V)) by comparing their molecular ions, fragment patterns and sulfur/arsenic ratios with in-house synthesised thiol-organoarsenic compounds. The findings demonstrated the potential for transformation of DMA(V) to DMDTA(V) and DMMTA(V) in a DMA(V)-spiked MLL in a landfill leachate environment.

High-performance liquid chromatography-inductively coupled plasma mass spectrometry based method for the determination of organic arsenic feed additives and speciation of anionic arsenics in animal feed.

A novel method has been developed to detect two organic arsenic animal feed additives including roxarsone and p-arsanilic acid, as well as other arsenic species such as arsenite, dimethylarsinic acid, monomethylarsonic acid, arsenate, and 4-hydroxyphenylarsonic acid, by using high-performance liquid chromatography coupled to an inductively coupled plasma mass spectrometer (HPLC-ICP-MS). The influence of the type and concentrations of ion-pairing reagents on the separation efficiency of the different arsenic compounds was examined. The effects of the mobile phase pH on the retention of arsenic species on the chromatography column were studied. When a gradient elution procedure was used, the best separation of the seven arsenic species could be achieved in <20 min with a mobile phase consisting of 8% methanol and 92% aqueous tetrabutylammonium hydroxide (4 mM, pH 6.25) followed by 92% trifluoroacetic acid aqueous solution (0.1%, pH 2.0). Liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS) was used as an assistant tool to screen arsenobetain (AsB) in the feed samples by monitoring the reaction at m/z 179-->120. The extractions of arsenic compounds from formula feed samples were studied, and results showed that the extraction with methanol/water (1:1) mixture yielded the most efficient percent compound recovery and the fastest extraction time for all arsenic species. Under optimum conditions, the limits of detection were <1.7 microg of As kg(-1), and the recoveries of all seven arsenic species were >78.5% with the relative standard deviation of <10%. The ion-pair reversed phase HPLC-ICP-MS method was then successfully applied to the speciation of arsenic in feedstuff and formula feed samples.

Arsenic speciation by gradient anion exchange narrow bore ion chromatography and high resolution inductively coupled plasma mass spectrometry detection.

Based on gradient anion exchange chromatography (AEC), a new strategy in As-speciation was evaluated. A narrow bore chromatographic system with lower flow rates (

Determination of As(III) and As(V) species in some natural water and food samples by solid-phase extraction on Streptococcus pyogenes immobilized on Sepabeads SP 70 and hydride generation atomic absorption spectrometry.

The speciation of arsenic(III) and arsenic(V) by using Streptococcus pyogenes immobilized on Sepabeads SP 70 resin has been investigated with solid-phase extraction method. The arsenic levels were determined hydride generation atomic absorption spectrometry (HGAAS) in sample solutions. The procedure presented based on quantitative recoveries of As(III) as >95%. Also the As(V) recoveries were obtained as <5% using the presented method. After reduction of As(V) by using KI and ascorbic acid and waiting 1h later, the system was applied to determination of total arsenic. As(V) was found as the difference between the total As and As(III) content. Various experimental parameters such as pH, amount of microorganism, sample volume, etc. were investigated. The capacity of biosorbent for arsenic(III) was calculated as 7.3 mg/g. The preconcentration factor was found as 36. The relative standard deviation was calculated below 8%. Limit of detection was calculated as 13 ng/L. The validation of the presented procedure was tested by analysis of standard reference materials (NIST SRM 1568a Rice floor and GBW 07605 Tea) and obtained fairly compatible results. The procedure was also successfully applied to arsenic speciation and determination of some natural water and food samples.

Arsenic speciation in Portuguese in situ lichen samples.

In this work, 29 lichen samples collected in situ and representative of high loadings, medium loadings and zero loadings for factors related to natural and anthropogenic emission sources, were analyzed to determine arsenic contents and its species extractability. The studied sites showed As values between 430 and 5590 microg kg(-1). The cationic forms were extracted at most of the sites varying between 0.5% and 6.6%. Extracted anionic forms were not detected in any of the sites. In a few other sites the % of extracted As(III)--more toxic--exceeds the equivalent value of As(V). It is concluded that arsenic in native Parmelia sulcata Taylor under the form of As(V) either was kept unchanged or was partially transformed into As(III) (more frequent) or partially transformed into As(III) and dimethylarsinic acid (DMAA) or partially transformed into DMAA.

A simple and fast detection technique for arsenic speciation based on high-efficiency photooxidation and gas-phase chemiluminescence detection.

High-efficiency photooxidation (HEPO) and gas phase chemiluminescence detection (CL) combined with high-performance liquid chromatography (HPLC) and hydride generation were developed for speciation of As(III), As(V), monomethylarsonic acid (MMA) and dimethylarsinic acid (DMA). After chromatography separation, the arsenic species were passed through HEPO which performed efficient photooxidation and converted MMA and DMA to As(V) in several seconds. Then the reaction of ozone and arsine upon hydride generation produced a CL signal as the analytical parameter. The total analytical process was completed within 10 min. The effects of operational parameters such as the concentrations of hydrochloric acid and NaBH4 solution, carrier gas flow and air gas flow for ozone generation were investigated. Detection limits were 3.7, 10.3, 10.2 and 10.0 microg/L for As(III), As(V), MMA and DMA, respectively. The recoveries of the four arsenic species in human urine sample ranged from 87 to 94%.

Aquatic arsenic: toxicity, speciation, transformations, and remediation.

This paper reviews the current knowledge on the toxicity, speciation and biogeochemistry of arsenic in aquatic environmental systems. The toxicity of arsenic is highly dependent on the chemical speciation. The effects of pH, E(h), adsorbing surfaces, biological mediation, organic matter, and key inorganic substances such as sulfide and phosphate combine in a complex and interwoven dynamic fashion to produce unique assemblages of arsenic species. The number of different arsenic species found in environmental samples and an understanding of the transformations between arsenic species has increased over the past few decades as a result of new and refined analytical methods. Changes in arsenic speciation and in total arsenic content of foods upon processing have suggested possible risks associated with processed and unprocessed food. Arsenic removal from water using adsorbents, chemical oxidation, photolysis and photocatalytic oxidation techniques is also reviewed.

Survey of total arsenic and arsenic speciation in US-produced rice as a reference point for evaluating change and future trends.

Rice generally contains higher levels of arsenic than most terrestrial-based foods. Studies related to dietary intake of arsenic from rice must take into account arsenic speciation due to toxicity differences in arsenic species. In this study, microwave-assisted extraction with trifluoroacetic acid was used to prepare rice samples for arsenic speciation analysis by high-performance liquid chromatography-inductively coupled plasma mass spectrometry. Fifty-three samples collected directly from the fields in four major rice-producing states in 1980 and 1981 were analysed for total and speciated arsenic and the results were compared with each other and with results for several more recently collected samples from local markets. The average content of total arsenic was 210 ± 190 ng As g(-1). This study demonstrates that US rice samples with higher levels of total arsenic have higher levels of dimethylarsinic acid; however, inorganic arsenic levels, regardless of the total arsenic content, rarely exceed 150 ng As g(-1) dry weight. These data are consistent with more recent findings, thus establishing trends that arsenic content in US-grown rice has been relatively constant throughout the last 30 years. To the authors' knowledge, the presented data are unique in that they provide a historical reference point for arsenic distribution in US-produced rice. These data would be invaluable for several applications including long-term arsenic exposure studies, environmental clean-up assessments, and to establish models for future trends in arsenic contribution in total diet studies.