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Arsenicals are proven carcinogens in humans and it imposes significant health impacts on both humans and animals. Recently monomethylarsonous acid (MMA(III)), the toxic metabolite of arsenic has been identified in human urine and believed to be more acutely toxic than arsenite and arsenate. Arsenic also affects the activity of a number of haem biosynthesis enzymes. As a part of 2-year arsenic carcinogenicity study, young female C57BL/6J mice were given drinking water containing 0, 100, 250 and 500 microg/L arsenic as MMA(III)ad libitum. 24 h urine samples were collected at 0, 1, 2, 4, 8 weeks and every 8 weeks for up to 104 weeks. Urinary arsenic speciation and porphyrins were measured using HPLC-ICP-MS and HPLC with fluorescence detection respectively. DMA(V) was a major urinary metabolite detected. Significant dose-response relationship was observed between control and treatment groups after 1, 4, 24, 32, 48, 56, 88, 96 and 104 weeks. The level of uroporphyrin in 250 and 500 microg As/L group is significantly different from the control group after 4, 8, 16, 32, 56, 72, 80, 96 and 104 weeks. Coproporphyrin I level in 500 microAs/L group is significantly different from control group after 8, 24, 32, 40, 56, 72, 80, 88 and 104 weeks. After 4 weeks the level of coproporphyrin III concentration significantly increased in all the treatment groups compared to the control except week 16 and 48. Our results show urinary DMA(V) and porphyrin profile can be used as an early warning biomarker for chronic MMA(III) exposure before the onset of cancer.
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PMID:Urinary arsenic and porphyrin profile in C57BL/6J mice chronically exposed to monomethylarsonous acid (MMAIII) for two years. 1770 74

Eight trace elements were determined using ICP-MS in 78 fruiting body samples of 22 edible mushroom species. The mushrooms were collected from four sites in a rural area, unpolluted by human activity. Median values (dry matter) were as follows: Arsenic (As) 1.45 mg kg(-1), barium (Ba) 1.41 mg kg(-1), cobalt (Co) 0.28 mg kg(-1), copper (Cu) 47.0 mg kg(-1), rubidium (Rb) 130 mg kg(-1), silver (Ag) 2.95 mg kg(-1), thallium (Tl) 0.02 mg kg(-1) and vanadium (V) 0.25 mg kg(-1). Higher trace element accumulation was observed in samples of Macrolepiota procera, Macrolepiota rhacodes, Lycoperdon perlatum, Lycoperdon gigantea and Xerocomus chrysenteron for As and Cu, and in samples of Cantharellus cibarius and of genera Boletus and Suillus for Rb.
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PMID:Levels of eight trace elements in edible mushrooms from a rural area. 1785 81

The E.U. Directive on incineration of waste regulates the harmful emissions of particles and twelve toxic elements, including copper, chromium, and arsenic. More information is critically needed on the speciation and behavior of these trace elements during combustion, including the effects of different process variables, as well as of different fuels and fuel mixtures. Using a 15 kW pellets-fueled grate burner, experiments were performed to determine the fate of copper, chromium, and arsenic during combustion of chromate copper arsenate (CCA) preservative wood. The effects of co-combustion of CCA-wood with peat were also studied since peat fuels previously have proved to generally reduce ash related problems. The fate and speciation of copper, chromium, and arsenic were determined from analysis of the flue gas particles and the bottom ash using SEM-EDS, XRD, XPS, and ICP-AES. In addition, chemical equilibrium model calculations were performed to interpret the experimental findings. The results revealed that about 5% copper, 15% chromium, and 60% arsenic were volatilized during combustion of pure CCA-wood, which is lower than predicted volatilization from the individual arsenic, chromium, and copper oxides. This is explained by the formation of more stable refractory complex oxide phases for which the stability trends and patterns are presented. When co-combusted with peat, an additional stabilization of these phases was obtained and thus a small but noteworthy decrease in volatilization of all three elements was observed. The major identified phases for all fuels were CuCrO2(s), (Fe, Mg, Cu)(Cr, Fe, Al)04(s), Cr2O3(s), and Ca3(AsO4)2(s). Arsenic was also identified in the fine particles as KH2AsO4(s) and As2O3(s). A strong indication of hexavalent chromium in the form of K2CrO4 or as a solid solution between K3Na(CrO4)2 and K3Na(SO4)2 was found in the fine particles. Good qualitative agreement was observed between experimental data and chemical equilibrium model calculations.
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PMID:Fate of Cu, Cr, and As during combustion of impregnated wood with and without peat additive. 1794 5

The association between arsenic exposure from drinking water and toenail arsenic concentrations appears to be non-linear at low exposure levels. To investigate whether this observation is a result exposure misclassification, a dietary exposure assessment was conducted in a cohort of 47 women concurrently enrolled in a prospective longitudinal biomonitoring study in Pabna, Bangladesh. Arsenic intake was evaluated using a duplicate diet study design which collected food and water samples for a total of 6 days. Total inorganic arsenic was measured in 24-hour composite food samples (N=282) using inductively coupled plasma-mass spectrometry coupled with a dynamic reaction cell (ICP-DRC-MS). Average annual tubewell arsenic concentrations and toenail arsenic concentrations were computed for each participant using biomonitoring data from the prospective study. Separate multivariate regression models evaluated the association between drinking water, total dietary intake, and total dietary dose with toenail arsenic, a biomarker of internal dose. In these models, dietary intakes were adjusted using the residual method to provide estimate that was independent of water arsenic concentrations. Median daily arsenic intake from food and drinking water was 48.3 microg/day and 4.2 microg/day. Taking into consideration participant's body weight, the median daily arsenic dose was 1.0 microg/kg-day from food and 0.1 microg/kg-day from drinking water although drinking water exposure was highly skewed and was the dominant exposure route for the upper 25th percentile of the distribution. The regression model that used total daily arsenic intake from food (beta=0.46; 95%CI: 0.18-0.73) and drinking water (95%CI: 0.26-0.38) explained the most variability in toenail arsenic concentrations (R(2)(a)=0.71). The effect estimates for food and drinking water are similar suggesting that both sources have a similar contribution to internal dose.
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PMID:Association between total ingested arsenic and toenail arsenic concentrations. 1795 83

Agaricus bisporus mushrooms were grown in compost amended with either arsenic-contaminated mine waste or an arsenate solution, to a final concentration of approximately 200 microg g(-1). Fungi were cultivated at a small-scale mushroom facility in Vineland (ON), where the controlled environment allowed for a large number of fruiting bodies (mushrooms) to be produced. The total arsenic concentrations as well as speciation were examined for each treatment over several harvests (breaks). Total concentrations were determined by acid digestion and inductively coupled plasma mass spectrometry (ICP-MS) detection and ranged from 2.3 to 16 microg g(-1) dry mass in treatment mushrooms. Arsenic compounds were extracted from mushrooms with methanol/water (1:1 v/v), and separated by high-performance liquid chromatography (HPLC, anion/cation exchange) before detection with ICP-MS. Fruiting bodies from all treatments contained arsenite, dimethylarsinic acid (DMA), and arsenobetaine (AB), and to a lesser extent arsenate and trimethylarsine oxide (TMAO). The ratio of arsenic compounds did not vary greatly over the first three harvests. AB was absent in compost not inoculated with A. bisporus supporting the hypothesis that AB is a product of fungal, not microbial, arsenic metabolism. X-ray absorption spectroscopy results lead us to hypothesize that AB plays a role in nutrient translocation within the fruiting body, as well as maintaining turgor pressure to ensure the mushroom cap remains elevated for maximum spore dispersal.
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PMID:Arsenic speciation analysis of cultivated white button mushrooms (Agaricus bisporus) using high-performance liquid chromatography-inductively coupled plasma mass spectrometry, and X-ray absorption spectroscopy. 1799 33

Arsenic induces clinical remission in patients with acute promyelocytic leukemia and has potential for treatment of other cancers. The current study examines factors influencing sensitivity to arsenic using human malignant melanoma cell lines. A375 and SK-Mel-2 cells were sensitive to clinically achievable concentrations of arsenite, whereas SK-Mel-3 and SK-Mel-28 cells required supratherapeutic levels for toxicity. Inhibition of glutathione synthesis, glutathione S-transferase (GST) activity, and multidrug resistance protein (MRP) transporter function attenuated arsenite resistance, consistent with studies suggesting that arsenite is extruded from the cell as a glutathione conjugate by MRP-1. However, MRP-1 was not overexpressed in resistant lines and GST-pi was only slightly elevated. ICP-MS analysis indicated that arsenite-resistant SK-Mel-28 cells did not accumulate less arsenic than arsenite-sensitive A375 cells, suggesting that resistance was not attributable to reduced arsenic accumulation but rather to intrinsic properties of resistant cell lines. The mode of arsenite-induced cell death was apoptosis. Arsenite-induced apoptosis is associated with cell cycle alterations. Cell cycle analysis revealed arsenite-sensitive cells arrested in mitosis whereas arsenite-resistant cells did not, suggesting that induction of mitotic arrest occurs at lower intracellular arsenic concentrations. Higher intracellular arsenic levels induced cell cycle arrest in the S-phase and G(2)-phase in SK-Mel-3 and SK-Mel-28 cells, respectively. The lack of arsenite-induced mitotic arrest in resistant cell lines was associated with a weakened spindle checkpoint resulting from reduced expression of spindle checkpoint protein BUBR1. These data suggest that arsenite has potential for treatment of solid tumors but a functional spindle checkpoint is a prerequisite for a positive response to its clinical application.
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PMID:Sensitivity to sodium arsenite in human melanoma cells depends upon susceptibility to arsenite-induced mitotic arrest. 1832 21

Synchrotron-based X-ray fluorescence (S-XRF) was utilized to locate arsenic (As) in polished (white) and unpolished (brown) rice grains from the United States, China, and Bangladesh. In white rice As was generally dispersed throughout the grain, the bulk of which constitutes the endosperm. In brown rice As was found to be preferentially localized at the surface, in the region corresponding to the pericarp and aleurone layer. Copper, iron, manganese, and zinc localization followed that of arsenic in brown rice, while the location for cadmium and nickel was distinctly different, showing relatively even distribution throughout the endosperm. The localization of As in the outer grain of brown rice was confirmed by laser ablation ICP-MS. Arsenic speciation of all grains using spatially resolved X-ray absorption near edge structure (micro-XANES) and bulk extraction followed by anion exchange HPLC-ICP-MS revealed the presence of mainly inorganic As and dimethylarsinic acid (DMA). However, the two techniques indicated different proportions of inorganic:organic As species. A wider survey of whole grain speciation of white (n=39) and brown (n=45) rice samples from numerous sources (field collected, supermarket survey, and pot trials) showed that brown rice had a higher proportion of inorganic arsenic present than white rice. Furthermore, the percentage of DMA present in the grain increased along with total grain arsenic.
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PMID:Speciation and localization of arsenic in white and brown rice grains. 1835 Oct 71

Arsenic (As) uptake in human occurs via the food chain mainly. The Joint FAO/WHO Expert Committee on Food Additives has established the provisional tolerable weekly intake level for As as an inorganic As (iAs) value, because iAs in food is much more toxic than organic As. In this study, we studied an acid based partial-digestion method for the complete extraction of arsenicals from rice. HPLC/ICP-MS was used to determine the concentration of iAs selectively. The conditions adopted to extract arsenicals from a 0.5 g of finely ground rice sample were addition of 2 mL of 0.15 mol/L nitric acid and heating at 80 degrees C for 2 hr. The LOD and LOQ for iAs were 0.0024 and 0.0079 mg/kg dry weight, respectively. Recovery studies showed good accuracy. When the method was applied to ten short-grain brown rice samples, the iAs concentrations were 0.108-0.227 mg/kg dry weight and the total As concentrations were 0.118-0.260 mg/kg dry weight. Although dimethylarsinic acid was also detected in most samples, the percentage of iAs content in total As content was 62.2-96.3%. Thus, iAs was the principal As species in the short-grain brown rice samples tested.
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PMID:Evaluation of a nitric acid-based partial-digestion method for selective determination of inorganic arsenic in rice. 1850 45

Most infectious diseases are accompanied by a change in levels of several trace elements in the blood. However, it is not known whether changes in the gastrointestinal uptake of trace elements contribute to this event. Coxsackievirus B3 (CVB3), adapted to Balb/c mice, was used to study whether infection induces gene expression of metallothionein (MT1) and divalent-metal transporter 1 (DMT1) in the intestine and liver and hepcidin in the liver, as well as whether trace elements in these tissues are changed accordingly. Quantitative expression of CVB3, MT1, DMT1 and hepcidin was measured by real-time RT-PCR and six trace elements by ICP-MS on days 3, 6 and 9 of the infection. The copper/zinc (Cu/Zn) ratio in serum increased as a response to the infection. High concentrations of virus were found in the intestine and liver on day 3 and in the intestine on day 6. MT1 in the intestine and liver increased on days 3 and 6. The increase of MT1 in the liver correlated positively with Cu and Zn. Hepcidin in the liver showed a non-significant increase on days 3 and 6 of the infection, whereas DMT1 in the intestine decreased on day 9. Accordingly, iron (Fe) in the liver increased progressively during the disease, whereas in the intestine DMT1 was negatively correlated to Fe. Arsenic (As), cadmium (Cd) and mercury (Hg) were found to decrease to various degrees in the intestine, serum and liver. Thus, enteroviral infections, and possibly many other infections, may cause a change in the gastrointestinal uptake of both non-essential and essential trace elements.
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PMID:Gastrointestinal uptake of trace elements are changed during the course of a common human viral (Coxsackievirus B3) infection in mice. 1856 24

Two approaches were undertaken to characterize the arsenic (As) content of Chinese rice. First, a national market basket survey (n = 240) was conducted in provincial capitals, sourcing grain from China's premier rice production areas. Second, to reflect rural diets, paddy rice (n = 195) directly from farmers fields were collected from three regions in Hunan, a key rice producing province located in southern China. Two of the sites were within mining and smeltery districts, and the third was devoid of large-scale metal processing industries. Arsenic levels were determined in all the samples while a subset (n = 33) were characterized for As species, using a new simple and rapid extraction method suitable for use with Hamilton PRP-X100 anion exchange columns and HPLC-ICP-MS. The vast majority (85%) of the market rice grains possessed total As levels < 150 ng g(-1). The rice collected from mine-impacted regions, however, were found to be highly enriched in As, reaching concentrations of up to 624 ng g(-1). Inorganic As (As(i)) was the predominant species detected in all of the speciated grain, with As(i) levels in some samples exceeding 300 ng g(-1). The As(i) concentration in polished and unpolished Chinese rice was successfully predicted from total As levels. The mean baseline concentrations for As(i) in Chinese market rice based on this survey were estimated to be 96 ng g(-1) while levels in mine-impacted areas were higher with ca. 50% of the rice in one region predicted to fail the national standard.
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PMID:High percentage inorganic arsenic content of mining impacted and nonimpacted Chinese rice. 1867 41


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