Speciation and toxicity of arsenic in mining-affected lake sediments in the Quinsam watershed, British Columbia.

Anthropogenic arsenic inputs into fresh water lakes in the Quinsam watershed, British Columbia, were probed by using multiple methods of inquiry including sediment coring combined with (210)Pb dating, a principal components analysis of elemental composition of sediments, arsenic speciation, bioaccessibility, and toxicity testing. The quantification of arsenic inputs from anthropogenic sources was not trivial because a variety of processes redistribute the element throughout lakes. However, elevated arsenic and sulfate concentrations in Long Lake, a lake that receives arsenic from a seep, suggest that this lake is influenced by mine operations. X-ray absorption near edge structure (XANES) spectra reveal similar arsenic speciation for all sediments within the studied lakes. Bioaccessibility tests, which in this study were used to approximate the solubility and availability of arsenic to benthic organisms, indicate moderate bioaccessibility of arsenic in sediments (7.9-35%). Toxicity testing indicates that not all benthic organisms should be used for evaluating arsenic toxicity, and suggests that the amphipod, Corophium volutator, shows promise as a candidate for widespread use for arsenic sediment toxicity testing.

Arsenic speciation in freshwater snails and its life cycle variation.

Terrestrial snails are consumed by humans occasionally and they are an important food source for many creatures including fish and birds. Little is known about arsenic speciation in these gastropods, let alone life cycle variations. Here we report on the arsenic speciation in freshwater snails from Pender Island and Vancouver Island, B.C., Canada, which was determined on methanol/water extracts (43-59% extraction efficiency) by using high performance liquid chromatography-inductively coupled plasma-mass spectrometry (HPLC-ICP-MS) and HPLC-electrospray tandem mass spectrometry. The tetramethylarsonium ion, oxo-arsenosugars and thio-arsenosugars are the main arsenic species encountered. Arsenobetaine, which is commonly found in the marine environment, is minor. Live bearing snails Viviparidae sp. from Pender Island were maintained in aquaria and the arsenic speciation in the unborn, newly born, and adult animals was monitored. Oxo-arsenosugars predominate in the adults, whereas thio-arsenosugars seem to predominate in juveniles, suggesting that these arsenicals are snail metabolites.

Tissue uptake, mortality, and sublethal effects of monomethylarsonic acid (MMA(V)) in nestling zebra finches (Taeniopygia guttata).

Monosodium methanearsonate (MSMA), an arsenic-based pesticide, has been used since the mid 1980s in attempts to suppress mountain pine beetle (Dendroctonus ponderosae) outbreaks in British Columbia, Canada. It was previously shown that cavity nesting forest birds forage and breed in MSMA-treated pine stands. The present study was designed to investigate the effects of ecologically relevant oral exposure to MSMA, including tissue distribution, growth parameters, and general health, including survival and immune function, of a model passerine, the zebra finch (Taeniopygia guttata). Nestling finches were orally dosed for 20 d from hatching to fledging with 4, 8, 12, 24, 36, or 72 microg/g bw/d of monomethylarsonic acid (MMA(V), which corresponds to MSMA at physiological pH). Preliminary trials showed complete mortality at 36 and 72 microg/g bw/d, and repeat trials also resulted in high mortality at 24 microg/g bw/d. Surviving nestlings showed dose-dependent trends in accumulation of arsenic in blood and specific tissues, and decreased tarsi and wing cord length upon fledging. There were no observed effects of dosing on measured immune function (phytohemagglutinin [PHA], hematocrit, and leukocrit). The data obtained suggest that passerine nestlings may be at risk of mortality and reduced growth due to exposure to MSMA under current environmental conditions.

Dose-dependent uptake, elimination, and toxicity of monosodium methanearsonate in adult zebra finches (Taeniopygia guttata).

Monosodium methanearsonate (MSMA), an arsenic-based pesticide, has been used for the past 10 years in attempts to suppress mountain pine beetle (Dendroctonus ponderosae) outbreaks in British Columbia, Canada. Previous studies have shown that cavity nesting forest birds such as woodpeckers forage and breed in MSMA treated pine stands. Here we examined the effects of MSMA in the laboratory using the zebra finch (Taeniopygia guttata), with the objective to examine tissue distribution and sublethal toxic effects in a model avian species. Zebra finches were exposed to this pesticide at doses similar to those found in bark beetle samples from MSMA stands of trees treated in the southern interior of British Columbia (8, 24, and 72 microg/g/d and a control group). Results showed high excretion (>90%) of arsenic in all dose groups, as well as dose-dependent trends in accumulation of arsenic in the blood (p < 0.001) and specific tissues. Monomethylarsonic acid, MMA (V), was the predominant form of arsenic in the blood plasma. Dimethylarsinic acid was the major form of arsenic found in the liver (83%) and kidney (61%) tissues. The brain tissue contained primarily the MMA (V) form (57%). Significant weight loss occurred in the two highest dose groups (p < 0.05). Birds in the highest dose group lost up to 15% of initial body mass.

Arsenic accumulation in bark beetles and forest birds occupying mountain pine beetle infested stands treated with monosodium methanearsonate.

The arsenic-based pesticide, monosodium methanearsonate (MSMA), is presently being evaluated for re-registration in Canada and the United States and has been widely used in British Columbia to help suppress Mountain Pine Beetle (MPB) outbreaks. We assessed the availability and exposure of MSMA to woodpeckers and other forest birds that may prey directly on contaminated bark beetles. Total arsenic residues in MPB from MSMA treated trees ranged from 1.3-700.2 microg g(-1) dw (geometric mean 42.0 microg g(-1)) with the metabolite monomethyl arsonic acid (MMAA) contributing 90-97% to the total arsenic extracted. Live adult and larval beetles were collected from treated trees and reached concentrations up to 327 microg g(-1) dw. MPBs from reference trees had significantly lower arsenic concentrations averaging 0.19 microg g(-1) dw. Woodpeckers foraged more heavily on MSMAtreesthat contained beetles with lower arsenic residues, suggesting those trees had reduced MSMAtranslocation and possibly greater live beetle broods. Blood samples from five species of woodpeckers and other forest passerines breeding within 1 km of MSMA stands contained elevated levels of total arsenic but with large individual variability (geometric mean = 0.18 microg g(-1) dw, range 0.02-2.20 microg g(-1). The results indicate that there is significant accumulation and transfer of organic arsenic within the food chain at levels that may present a toxicity risk to avian wildlife.

Bioaccessibility and excretion of arsenic in Niu Huang Jie Du Pian pills.

Traditional Chinese medicines (TCMs) often contain significant levels of potentially toxic elements, including arsenic. Niu Huang Jie Du Pian pills were analyzed to determine the concentration, bioaccessibility (arsenic fraction soluble in the human gastrointestinal system) and chemical form (speciation) of arsenic. Arsenic excretion in urine (including speciation) and facial hair were studied after a one-time ingestion. The pills contained arsenic in the form of realgar, and although the total arsenic that was present in a single pill was high (28 mg), the low bioaccessibility of this form of arsenic predicted that only 4% of it was available for absorption into the bloodstream (1 mg of arsenic per pill). The species of arsenic that were solubilized were inorganic arsenate (As(V)) and arsenite (As(III)) but DMAA and MMAA were detected in urine. Two urinary arsenic excretion peaks were observed: an initial peak several (4-8) hours after ingestion corresponding to the excretion of predominantly As(III), and a larger peak at 14 h corresponding predominantly to DMAA and MMAA. No methylated As(III) species were observed. Facial hair analysis revealed that arsenic concentrations did not increase significantly as a result of the ingestion. Arsenic is incompletely soluble under human gastrointestinal conditions, and is metabolized from the inorganic to organic forms found in urine. Bioaccessible arsenic is comparable to the quantity excreted. Facial hair as a bio-indicator should be further tested.

Chromatographic separation and identification of products from the reaction of dimethylarsinic acid with hydrogen sulfide.

The reaction of dimethylarsinic acid (DMAV) with hydrogen sulfide (H2S) is of biological significance and may be implicated in the overall toxicity and carcinogenicity of arsenic. The course of the reaction in aqueous phase was monitored, and an initial product, dimethylthioarsinic acid, was observed by using LC-ICP-MS and LC-ESI-MS. Dimethylarsinous acid was observed as a minor product. A second slower-forming product was identified, and the electrospray mass chromatograms for this species produced ions at m/z 275, 171, and 137 in positive mode. To aid in the identification of this slower-forming product, crystalline standards of sodium dimethyldithioarsinate and dimethylarsino dimethyldithioarsinate were prepared and re-characterized by using improved spectroscopic and structural analysis techniques. An aqueous solution of sodium dimethyldithioarsinate produced a single major chromatographic peak that matched the retention time (7.6 min) of the slower-forming product and contained similar molecular ions at m/z 275, 171, and 137 via LC-ESI-MS. The dimethylarsino dimethyldithioarsinate standard produced four aqueous phase species one of which coeluted with the slower forming product. This coeluting peak also produced the identical ESI-MS ions as the slower-forming product of DMAV + H2S. ESI-MS/MS experiments conducted on sodium dimethyldithioarsinate in deuterated water produced molecular ions at m/z 276, 173, and 137. Subsequent collisionally activated dissociation (CAD) experiments on m/z 276 did not produce a product ion at m/z 173. These data indicate that two different species are present in solution, while NMR data indicate that only dimethyldithioarsinic acid exists in aqueous solutions. This discrepancy was investigated by conducting NMR studies on the acidic solution of sodium dimethyldithioarsinate after taking this solution to dryness. The resolubilized solution produced a proton NMR signal characteristic of dimethylarsino dimethyldithioarsinate. Therefore, it was concluded that the ESI-MS ion at m/z 275 associated with the slowly forming second reaction product and the sodium dimethyldithioarsinate compound is a product of the ESI desolvation process.

Trace element distribution during the reproductive cycle of female and male spiny and Pacific scallops, with implications for biomonitoring.

Trace element concentrations and contents in gills, gonad, kidneys, mantle, muscle and remainder during the reproductive cycle of female and male spiny and Pacific scallops, from the Strait of Georgia, BC, Canada, were quantified by using ICPMS. The elements investigated were chromium, manganese, iron, cobalt, nickel, selenium, molybdenum, cadmium, tin and mercury. For all ten elements, the tissue distribution was to some extent influenced by species, sex and reproductive status. The implications of the present study in relation to the design of biomonitoring programmes are: (1) care should be taken to ensure an equal/constant sex composition when making interannual comparisons of pooled samples. Preferably the sexes should be monitored separately. (2) the practice of obtaining pooled samples in the interspawn phase is applicable only to monitoring long-term trends in contaminant levels, while the reproductive status should be heeded when studying short-term changes. (3) the present study confirms that direct temporal or spatial comparisons of absolute accumulated element concentrations are only valid intraspecifically.

Arsenic compounds in the haemolymph of the Dungeness crab, Cancer magister, as determined by using HPLC on-line with inductively coupled plasma mass spectrometry.

Arsenobetaine, two arsenosugars, dimethylarsinate and several unidentified arsenic species were detected in extracts of the haemolymph of the Dungeness crab, Cancer magister, by using HPLC-ICP-MS. This is the first report of the presence of arsenosugars in the haemolymph/blood of marine animals. Total, extractable and residual arsenic concentrations were determined by ICP-MS. The concentration of total arsenic was in the range of 1.4-3.8 [micro sign]g ml(-1). Nearly all (98%) the arsenic was found to be extractable, and accounted for primarily by arsenobetaine, two arsenosugars and dimethylarsinate. The results demonstrate that arsenic compounds present in the diet of crabs are not fully metabolized in the gut. They are, at least partly, taken up into the haemolymph. The concurrence of arsenobetaine and arsenosugars suggests that the use of repeated haemolymph sampling in crustaceans could facilitate investigations into the kinetics of the biotransformation pathways of arsenic compounds. Finally, the present study clearly demonstrates the unique capabilities of HPLC-ICP-MS for the detection and identification of minor arsenic components amongst the predominant arsenobetaine.

Do arsenosugars pose a risk to human health? The comparative toxicities of a trivalent and pentavalent arsenosugar.

Seafood frequently contains high concentrations of arsenic (approximately 10-100 mg/kg dry weight). In marine algae (seaweed), this arsenic occurs predominantly as ribose derivatives known collectively as arsenosugars. Although it is clear that arsenosugars are not acutely toxic, there is a possibility of arsenosugars having slight chronic toxicity. In general, trivalent arsenicals are more toxic than their pentavalent counterparts, so in this work we examine the hypothesis that trivalent arsenosugars might be significantly more toxic than pentavalent arsenosugars in vitro. We compared the in vitro toxicity of (R)-2,3-dihydroxypropyl-5-deoxy-5-dimethylarsinoyl-beta-D-riboside, a pentavalent arsenosugar, to that of its trivalent counterpart, (R)-2,3-dihydroxypropyl-5-deoxy-5-dimethylarsino-beta-D-riboside. The trivalent arsenosugar nicked plasmid DNA, whereas the pentavalent arsenosugar did not. The trivalent arsenosugar was more cytotoxic (IC50 = 200 microM, 48 h exposure) than its pentavalent counterpart (IC50 > 6000 microM, 48 h exposure) in normal human epidermal keratinocytes in vitro as determined via the neutral red uptake assay. However, both the trivalent and the pentavalent arsenosugars were significantly less toxic than MMA(III), DMA(III), and arsenate. Neither the pentavalent arsenosugar nor the trivalent arsenosugar were mutagenic in Salmonella TA104. The trivalent arsenosugar was readily formed by reaction of the pentavalent arsenosugar with thiol compounds, including, cysteine, glutathione, and dithioerythritol. This work suggests that the reduction of pentavalent arsenosugars to trivalent arsenosugars in biology might have environmental consequences, especially because seaweed consumption is a significant environmental source for human exposure to arsenicals.

Arsenic speciation in human urine: are we all the same?

We studied the arsenic speciation in human urine samples by using high-performance liquid chromatography-inductively coupled plasma-mass spectrometry (HPLC-ICP-MS). We investigated the arsenic speciation in the urine collected from nine volunteers during a 3-day period after a meal of blue mussels, Mytilus edulis. We also studied the effect of cooking on the arsenic speciation. Arsenobetaine and dimethylarsinic acid (DMAA) were the major arsenic metabolites found in the urine samples. Significant amounts of unknown metabolites were also detected. The excretion patterns of arsenic from individuals were generally similar except for two subjects. One of whom excreted high amounts of arsenobetaine even though no arsenic-rich food was eaten for 3 days before the experiment. The results reveal that we need a better understanding of the metabolism of arsenic compounds by human.

Sequential anaerobic-aerobic treatment of soil contaminated with weathered Aroclor 1260.

Soil contaminated with weathered Aroclor 1260 was bioremediated by sequential anaerobic and aerobic laboratory-scale treatment. The initial concentration was 59 microg of PCBs/g of soil. Following 4 months of anaerobic treatment with an enrichment culture, all of the major components in Aroclor 1260 were completely or partially transformed to less chlorinated PCB congeners. The major products of reductive dechlorination were 24-24-tetrachlorobiphenyl and 24-26-tetrachlorobiphenyl, and the average chlorine substituents per PCB molecule decreased from 6.4 to 5.2. The molar concentration of PCBs did not decrease during the anaerobic treatment. All of the major products formed during the anaerobic treatmentwere degraded in the subsequent aerobic treatment using Burkholderia sp. strain LB400. After 28 days of the aerobic treatment, the concentration of PCBs was reduced to 20 ug/g of soil. PCBs were not significantly removed in aerobic treatments unless they were bioaugmented with LB400. Also, PCB degradation was not detected in soil bioaugmented with LB400 without prior anaerobic treatment. These results confirm the potential for extensive biological destruction of highly chlorinated, weathered PCB congeners in soil.