Maeve Moriarty

Arsenic Speciation in Blue Mussels (Mytilus edulis) Along a Highly Contaminated Arsenic Gradient

Arsenic is naturally present in marine ecosystems, and these can become contaminated from mining activities, which may be of toxicological concern to organisms that bioaccumulate the metalloid into their tissues. The toxic properties of arsenic are dependent on the chemical form in which it is found (e.g., toxic inorganic arsenicals vs nontoxic arsenobetaine), and two analytical techniques, high performance liquid chromatography coupled with inductively coupled plasma mass spectrometry (HPLC-ICP-MS) and X-ray absorption spectroscopy (XAS), were used in the present study to examine the arsenic species distribution in blue mussels (Mytilus edulis) obtained from an area where there is a strong arsenic concentration gradient as a consequence of mining impacted sediments. A strong positive correlation was observed between the concentration of inorganic arsenic species (arsenic compounds with no As-C bonds) and total arsenic concentrations present in M. edulis tissues (R(2) = 0.983), which could result in significant toxicological consequences to the mussels and higher trophic consumers. However, concentrations of organoarsenicals, dominated by arsenobetaine, remained relatively constant regardless of the increasing As concentration in M. edulis tissue (R(2) = 0.307). XANES bulk analysis and XAS two-dimensional mapping of wet M. edulis tissue revealed the presence of predominantly arsenic-sulfur compounds. The XAS mapping revealed that the As(III)-S and/or As(III) compounds were concentrated in the digestive gland. However, arsenobetaine was found in small and similar concentrations in the digestive gland as well as the surrounding tissue suggesting arsenobetaine may being used in all of the mussels cells in a physiological function such as an intracellular osmolyte.

Bioaccessibility of lead and arsenic in traditional Indian medicines

Arsenic and lead have been found in a number of traditional Ayurvedic medicines, and the practice of Rasa Shastra (combining herbs with metals, minerals and gems), or plant ingredients that contain these elements, may be possible sources. To obtain an estimate of arsenic and lead solubility in the human gastrointestinal tract, bioaccessibility of the two elements was measured in 42 medicines, using a physiologically-based extraction test. The test consisted of a gastric phase at pH 1.8 containing organic acids, pepsin and salt, followed by an intestinal phase, at pH 7 and containing bile and pancreatin. Arsenic speciation was measured in a subset of samples that had sufficiently high arsenic concentrations for the X-ray absorption near edge structure analysis used. Bioaccessible lead was found in 76% of samples, with a large range of bioaccessibility results, but only 29% of samples had bioaccessible arsenic. Lead bioaccessibility was high (close to 100%) in a medicine (Mahayograj Guggulu) that had been compounded with bhasmas (calcined minerals), including naga (lead) bhasma. For the samples in which arsenic speciation was measured, bioaccessible arsenic was correlated with the sum of As(V)-O and As(III)-O and negatively correlated with As-S. These results suggest that the bioaccessible species in the samples had been oxidized from assumed As-S raw medicinal ingredients (realgar, As(4)S(4), added to naga (lead) bhasma and As(III)-S species in plants). Consumption at recommended doses of all medicines with bioaccessibile lead or arsenic would lead to the exceedance of at least one standard for acceptable daily intake of toxic elements.

Arsenic distribution and speciation in Daphnia pulex

Rat Lake, Yellowknife, Northwest Territories, is situated on arsenic-rich tailings from a historical gold mine. The abundant zooplankton species Daphnia pulex in this lake was used to study the impact of arsenic at the base of the freshwater food web; the speciation and distribution of arsenic in D. pulex and its food sources; and the origin of formation of organoarsenicals in freshwater systems. The arsenic concentration in lake water was measured as 0.25 mg L(-1), while the zooplankton organisms contained up to 35 mg kg(-1) d.w. arsenic. Plankton samples were analyzed for arsenic speciation, by using X-ray Absorption Near Edge Structure (XANES) on the whole, dried samples and High Performance Liquid Chromatography coupled to Inductively Coupled Plasma Mass Spectrometry (HPLC-ICP-MS) on water extracts. XANES data suggest that D. pulex mainly contain inorganic arsenicals with 56% of arsenic with +5 oxidation state and 10% of arsenic with +3 oxidation state, but also 34% of organoarsenic compounds that were identified with HPLC-ICP-MS as monomethylarsonate (MMA), dimethylarsinate (DMA), and arsenosugars. The most abundant of the organoarsenicals was the glycerol sugar (Sugar 1). X-ray Fluorescence (XRF) mapping of D. pulex for arsenic distribution showed that arsenic was mainly distributed in the gut of the animal, where its concentration was ten times higher than in the surrounding tissues. Moreover, the analysis of residues from extractions targeting water-soluble and lipid-soluble arsenicals suggested that part of the measured arsenic signal comes from ingested sediments, phytoplankton, or other food sources. These food sources contain inorganic arsenic only, with As(V)-O in phytoplankton and As(III)-S in sediments, suggesting the possibility that the organoarsenicals compounds detected in the tissues of the organism are created by the Daphnia.

Arsenic speciation in field-collected and laboratory-exposed earthworms Lumbricus terrestris.

Mature Lumbricus terrestris were host soils and leaf litter were collected from a former arsenic mine in Devon, UK (Devon Great Consols), a former gold mine in Ontario, Canada (Deloro), and an uncontaminated residential garden in Nottingham, UK. Arsenic concentrations determined by inductively coupled plasma-mass spectrometry (ICP-MS) in soils were 16-348 mg kg(-1), 6.0-239 mg kg(-1) in the earthworms and 8.6 mg kg(-1) in leaf litter sampled at Deloro (all dry weight). High performance liquid chromatography (HPLC-ICP-MS) analysis revealed arsenite (As(III)), arsenate (As(V)) and five organoarsenic species; arsenobetaine (AB), methylarsonate (MA(V)), dimethylarsinate (DMA(V)), arsenosugar 1 (glycerol sugar), arsenosugar 2 (phosphate sugar), and trimethylarsineoxide (TMAO) in field-collected L. terrestris. Differences were observed in the variety of organoarsenic species present between field sites. Several organoarsenic species were observed in the leaf litter (DMA(V), arsenosugar 2 and TMAO) but not AB. Depuration resulted in higher concentrations of inorganic As being detected in the earthworm whereas the concentration or variety of organoarsenic species was unchanged. Commercially sourced L. terrestris were exposed to As contaminated soil in laboratory mesocosms (1.0, 98, 183, 236, 324 and 436 mg kg(-1)) without leaf litter and were additionally analyzed using X-ray absorption near edge structure (XANES). Only inorganic As(III) and As(V) was observed. It is proposed that ingestion of leaf litter and symbiotic processes in the natural soil environment are likely sources of organoarsenic compounds in field-collected L. terrestris.

Bioaccessibility of mercury in selected Ayurvedic medicines

Five Ayurvedic medicines with mercury concentrations of 85mg/kg and higher were characterized with respect to their speciation and their bioaccessibility. X-ray absorption spectroscopy revealed that the mercury in the Ayurvedic medicines was inorganic and best matched to cinnabar, even in samples that had been hypothesized to contain mercury through plant sources only. The bioaccessibility (bioaccessible concentrations and percent bioaccessibility) was measured using two methods: a two-phase physiologically based extraction test (PBET gastric, G and gastric+intestinal phase, GI); and the fed organic estimation human simulation test (FOREhST). The percent bioaccessibility of mercury in all Ayurvedic samples was very low (<5%), corresponding to the low solubility of cinnabar, but it increased with increasing dissolved organic carbon content of the bioaccessibility solutions (PBET-G<PBET-GI<FOREhST). Filtration of FOREhST solutions reduced the bioaccessible mercury concentrations to undetectable values for most of the Ayurvedic samples. Incorporation of percent relative bioaccessibility of mercury into risk calculations decreased daily intake estimates by 29-900 times, and reduced them to acceptable levels for three of the five medicines.

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.

Methodological artefacts in the XANES analysis of hexa-coordinated pentavalent arsenic

Using XANES, we studied the recently identified hexa-coordinated pentavalent arsenic, specifically, octahedral As(V)-glycerol compound As(V)(OCH2CH(O)CH2OH)3. It is stable at all pHs tested (1–12), but is transformed to the conventional tetrahedral AsO43− compound in the presence of water. Dehydration of environmental samples (i.e., Manitoba maple leaf and hare muscle) spiked with a AsO43− standard resulted in XANES features of the As(V)-glycerol compound. Therefore the compound we hypothesize to be the As(V)-glycerol in environmental samples is likely only visible using XAS analysis, and does not appear to survive wet environments such as those in biological systems, where toxicity may be experienced, or in conventional speciation methods, which generally use aqueous separation techniques.

Insolubility of Cr2O3 in Bioaccessibility Tests Points to Requirement for a New Human Oral Reference Dose for Trivalent Chromium

ABSTRACT Bioaccessibility measurements have the potential to improve the accuracy of risk assessments and reduce the potential costs of remediation when they reveal that the solubility of chemicals in a matrix (e.g., soil) differs markedly from that in the critical toxicity study (i.e., the key study from which a toxicological or toxicity reference value is derived). We aimed to apply this approach to a brownfield site contaminated with chromium, and found that the speciation was CrIII, using a combination of alkaline digestion/diphenylcarbazide complexation and X-ray absorption near edge structure analysis. The bioaccessibility of Cr2O3, the compound on which a reference dose for CrIII is based, was substantially lower (<0.1%) than that of the CrIII in the soils, which was a maximum of 9%, giving relative bioaccessibility values of 13,000% in soil. This shows that the reference dose is based on essentially an insoluble compound, and thus we suggest that other compounds be considered for toxicity testing and derivation of reference dose. Two possibilities are CrCl3·6H2O and KCr(SO4)2·12H2O, which have been used for derivation of ecological toxicity reference values and are soluble at a range of dosing levels in our bioaccessibility tests.