An examination of the factors influencing the bioaccumulation of methylmercury at the base of the estuarine food web.

Estuarine systems have received ongoing mercury (Hg) inputs from both point sources and regional contamination and have high legacy Hg in sediments. This is an environmental concern given that coastal seafood is an important vector for human exposure to methylmercury (MeHg). The base of the food chain represents the most important trophic steps for MeHg bioaccumulation. The magnitude of the uptake by phytoplankton, and their consumers, is influenced by many factors, in addition to sediment and water MeHg concentrations, that impact MeHg assimilation into phytoplankton and the trophic transfer to higher trophic levels, both benthic and pelagic. For forage fish, such as mummichogs (Fundulus heteroclitus), abiotic and biotic (bioenergetic) factors can influence their MeHg content, and diet is also important as they feed both on benthic and pelagic prey. Given that the importance of sediment MeHg versus pelagic MeHg sources has been debated, we updated a phytoplankton bioaccumulation model, and coupled this with a bioaccumulation model for MeHg concentration in mummichog tissue to examine the controlling factors for sites, from Maine to Maryland, USA, ranging widely in their Hg concentrations and other variables. The study highlighted the importance of DOC in modulating uptake into the pelagic food web, but also demonstrated the importance of diet in controlling mummichog MeHg. Finally, the relative importance of MeHg source - sediment or water column - was correlated with the level of Hg contamination. Sediment-derived MeHg was a more important source for highly Hg contaminated systems. As water column and sediment MeHg are not strongly correlated for the studied ecosystems, their importance as a source of MeHg to mummichogs varies with location. The study highlights the differences across ecosystems in MeHg bioaccumulation pathways, and that uptake into phytoplankton is an important variable controlling forage fish concentration.

Tracing the sources and depositional history of mercury to coastal northeastern U.S. lakes.

Mercury (Hg) deposition was reconstructed in sediment cores from lakes in two coastal U.S. National Parks: Acadia National Park (ANP) and Cape Cod National Seashore (CCNS), to fill an important spatial gap in Hg deposition records and to explore changing sources of Hg and processes affecting Hg accumulation in these coastal sites. Recent Hg deposition chronology was assessed using (1) a newly developed lead-210 (210Pb) based sediment age model which employs 7Be to constrain deposition and sediment mixing of 210Pb-excess, (2) coinciding Pb flux and isotope ratios (206Pb/207Pb), and (3) Hg isotope ratios and their response to changes in Hg flux. At both sites, Hg flux increased substantially from pre-1850 levels, with accumulation in ANP peaking in the 1970s, whereas in CCNS, Hg levels were highest in recent sediments. Negative values of δ202Hg and Δ199Hg indicated terrestrially-derived Hg was a major constituent of Hg flux to Sargent Mountain Pond, ANP, although recent decreases in Hg flux were in agreement with precipitation Hg records, indicating a rapid watershed response. By contrast, δ202Hg and Δ199Hg profiles in Long Pond, CNNS reflect direct Hg deposition, but disturbances in the sedimentary record were indicated by bomb fallout radionuclide inventories and by peaks in both Pb and Hg isotope depth profiles. These cores provided poor reconstructions of atmospheric deposition and reveal responses that are decoupled from emissions reduction due to complex post-depositional redistribution of atmospheric metals including Hg. The application of multiple tracers of Hg deposition provide insight into the sources and pathways governing Hg accumulation in these lakes.

Exposure to arsenolipids and inorganic arsenic from marine-sourced dietary supplements.

Dietary supplements sourced from marine environments, such as fish oils and seaweed-based supplements, are widely consumed to boost nutrient intakes, including by vulnerable populations such as pregnant women. Like other marine foods, these supplements are also a potential source of exposure to arsenic, including the known toxic species, inorganic arsenic, and the cytotoxic, lipid-soluble arsenic compounds, arsenic hydrocarbons. A study of 32 marine-sourced supplements found higher total arsenic concentrations (>1000 ng g-1) in supplements made from seaweed, krill and calanus oil, and in fish and fish liver products marketed as "unprocessed". Inorganic arsenic was only detectable in the seaweed samples, and was elevated (8900 ng g-1) in one product. Arsenic hydrocarbons were not detected in krill oil samples but were present at concentrations from 169 to 2048 ng g-1 in "unprocessed" fish and fish liver oil, and calanus oil. Survey data from the New Hampshire Birth Cohort Study (NHBCS) found 13.5% of pregnant women (n = 1997) reported taking fish oil supplements; and of those, most did so daily (75.6%, 6 or more times per week). Only a small percentage (9%) of those who reported consuming fish oil used products associated with higher arsenic levels. Higher urinary arsenic concentrations were found among women who consumed fish oil compared with those who did not, and specifically higher arsenobetaine and dimethyl arsenic concentrations. Dietary supplements are becoming common components of modern diets, and some marine-sourced dietary supplements are a source of inorganic arsenic and arsenic hydrocarbons.

Historic contamination alters mercury sources and cycling in temperate estuaries relative to uncontaminated sites.

Mercury (Hg) is a global and persistent pollutant which can be methylated to more toxic forms (methylmercury; MeHg) in natural systems. Both forms pose a health risk to humans and wildlife, and exposure often begins in aquatic environments. Therefore, quantifying aquatic concentrations and identifying source pathways is important for understanding biotic exposure. In this study, data from estuaries in the Northeast United States were combined to evaluate how point source contamination impacts the concentration and source dynamics of water column total and MeHg with an emphasis on sediment versus non-sediment sources. Partial least squares regression models were implemented to identify a set of variables most related to water column MeHg and total Hg (HgT) across the estuaries. The main findings suggest that contaminated sites have strong internal recycling of HgT that dominates over external inputs, and this leads to elevated concentrations of HgT and MeHg in the local water columns. However, HgT sources in uncontaminated estuarine systems have a strong connection to the local watershed with dissolved HgT linked to dissolved organic carbon, and particulate HgT linked to watershed land use and estuarine mixing. There was little correlative evidence that water column MeHg concentrations were linked to sediment in such systems, but unlike HgT, the concentrations were also not clearly linked to the watershed. Instead, in situ methylation of dissolved water column HgT appeared to dominate the MeHg source pathway. The results suggest that Hg point-source contaminated sites should be considered independently from non-contaminated sites in terms of management, and that land use plays an important indirect role in coastal MeHg dynamics.

Patterns in forage fish mercury concentrations across Northeast US estuaries.

Biogeochemical conditions and landscape can have strong influences on mercury bioaccumulation in fish, but these effects across regional scales and between sites with and without point sources of contamination are not well understood. Normal means clustering, a type of unsupervised machine learning, was used to analyze relationships between forage fish (Fundulus heteroclitus and Menidia menidia) mercury (Hg) concentrations and sediment and water column Hg and methylmercury (MeHg) concentrations, ancillary variables, and land classifications within the sub-watershed. The analysis utilized data from 38 sites in 8 estuarine systems in the Northeast US, collected over five years. A large range of mercury concentrations and land use proportions were observed across sites. The cluster correlations indicated that for Fundulus, benthic and pelagic Hg and MeHg concentrations were most related to tissue concentrations, while Menidia Hg was most related to water column MeHg, reflecting differing feeding modes between the species. For both species, dissolved MeHg was most related to tissue concentrations, with sediment Hg concentrations influential at contaminated sites. The models considering only uncontaminated sites showed reduced influence of bulk sediment MeHg for both species, but Fundulus retained sediment drivers at some sites, with dissolved MeHg still highly correlated for both. Dissolved organic carbon (DOC), chlorophyll, land use, and other ancillary variables were of lesser importance in driving bioaccumulation, though DOC was strongly related within some clusters, likely in relation to dissolved Hg. Land use, though not of primary importance, showed relationships opposite to those observed in freshwater, with development positively correlated and forests and agriculture negatively correlated with tissue concentrations across clusters and species. Clusters were composed of sites from geographically distinct systems, indicating the greater importance of small scale drivers of MeHg formation and uptake into the food web over system or region-wide influences.

Effects of temperature, salinity, and sediment organic carbon on methylmercury bioaccumulation in an estuarine amphipod.

Mercury (Hg) is a global contaminant that poses a human health risk in its organic form, methylmercury (MeHg), through consumption of fish and fishery products. Bioaccumulation of Hg in the aquatic environment is controlled by a number of factors expected to be altered by climate change. We examined the individual and combined effects of temperature, sediment organic carbon, and salinity on the bioaccumulation of MeHg in an estuarine amphipod, Leptocheirus plumulosus, when exposed to sediment from two locations in the Gulf of Maine (Kittery and Bass Harbor) that contained different levels of MeHg and organic carbon. Higher temperatures and lower organic carbon levels individually increased uptake of MeHg by L. plumulosus as measured by the biota-sediment accumulation factor (BSAF), while the effect of salinity on BSAF differed by sediment source. Multi-factor statistical modeling using all data revealed a significant interaction between temperature and organic carbon for both sediments, in which increased temperature had a negative effect on BSAF at the lowest carbon levels and a positive effect at higher levels. Our results suggest that increased temperature and carbon loading, of a magnitude expected as a result from climate change, could be associated with a net decrease in amphipod BSAF of 50 to 71%, depending on sediment characteristics. While these are only first-order projections, our results indicate that the future fate of MeHg in marine food webs is likely to depend on a number of factors beyond Hg loading.

Bioaccumulation of methylmercury in wood frogs and spotted salamanders in Vermont vernal pools.

Mercury (Hg) has accumulated in forested landscapes in the Northeastern U.S., and hotspots with enhanced deposition have been identified throughout the region. Due to a variety of favorable landscape characteristics, including relatively high dissolved organic carbon (DOC), fluctuating water levels, and low pH and dissolved oxygen, vernal pools provide ideal conditions for the conversion of Hg to its more toxic and bioavailable form, methylmercury (MeHg). Yet little is known about the concentrations, speciation, and bioavailability of Hg in vernal pools, or its bioaccumulation in vernal pool fauna and potential export into terrestrial systems. We investigated the role of forest cover type on the bioaccumulation of MeHg in wood frog (Lithobates sylvatica) and spotted salamander (Ambystoma maculatum) eggs, larvae, and adults, and investigated relationships among MeHg and water chemistry (pH, DOC). Water samples from pools located in coniferous stands had greater concentrations of THg and MeHg compared to deciduous pool water, and showed significant positive correlation to DOC (r = 0.683, P < 0.001) and correlated negatively with pH (r = -0.613, P < 0.001). Methylmercury levels in amphibian embryos were similar between the two species (L. sylvatica mean = 5.4 ng/g dw; A. maculatum mean = 3.5 ng/g dw). Concentrations of MeHg increased substantially in larvae, and were significantly greater in A. maculatum (mean = 237.6 ng/g ± 18.5 SE) than L. sylvatica larvae (62.5 ng/g ± 5.7 SE). Forest cover type did not explain variation in MeHg concentration among amphibian embryos or larvae. Methylmercury levels in adult tissue samples were significantly greater in A. maculatum (mean = 79.9 ng/g ± 8.9 SE) compared to L. sylvatica (mean = 47.7 ng/g ± 9.7 SE). This research demonstrates that vernal pools are important hotspots where amphibians bioaccumulate MeHg, which may then be transferred to terrestrial ecosystems. The abundance of amphibian larvae suggests they could be important bioindicators for monitoring MeHg loading and bioavailability.

Preliminary investigation of polymer-based in situ passive samplers for mercury and methylmercury.

Development of an in situ passive sampler for mercury (Hg), and its toxic form, methylmercury (MeHg), using simple polymer films, was explored for the potential to make an efficient and environmentally relevant monitoring tool for this widespread aquatic pollutant. The sulfur-containing polymers polysulfone (PS), and polyphenylene sulfide (PPS), were found to accumulate both MeHg and inorganic Hg (iHg), whereas polyethylene (PE) sorbed iHg but not MeHg, and polyoxymethylene (POM) and polyethersulfone (PES) films had low affinity for both Hg species. Uptake rates of Hg species into polymers were linear over two weeks, and dissolved organic matter at natural levels had no effect on partitioning of MeHg or iHg to the polymers. Sorption of MeHg to PS and PPS from three estuarine sediments correlated with uptake into diffusive gel-type samplers over time, and in PPS, with accumulation by the estuarine amphipod, Leptocheirus plumulosus. These polymers had lower MeHg adsorption rates, but are simpler to assemble, than diffusive gel-type samplers. Higher contaminant concentrations in polymer and gel-type samplers corresponded with porewater concentrations across sediments, suggesting they sample the dissolved MeHg pool, whereas MeHg levels in amphipods were more elevated with higher bulk sediment MeHg, which may reflect feeding strategy. While polymers with higher affinity for MeHg and iHg are needed for some environmental applications, this work suggests a simple sampling approach has potential for time-integrated, environmentally-meaningful MeHg monitoring in contaminated sediments.

Opportunities and Challenges for Dietary Arsenic Intervention.

The diet is emerging as the dominant source of arsenic exposure for most of the U.S. population. Despite this, limited regulatory efforts have been aimed at mitigating exposure, and the role of diet in arsenic exposure and disease processes remains understudied. In this brief, we discuss the evidence linking dietary arsenic intake to human disease and discuss challenges associated with exposure characterization and efforts to quantify risks. In light of these challenges, and in recognition of the potential longer-term process of establishing regulation, we introduce a framework for shorter-term interventions that employs a field-to-plate food supply chain model to identify monitoring, intervention, and communication opportunities as part of a multisector, multiagency, science-informed, public health systems approach to mitigation of dietary arsenic exposure. Such an approach is dependent on coordination across commodity producers, the food industry, nongovernmental organizations, health professionals, researchers, and the regulatory community. https://doi.org/10.1289/EHP3997.

Author Correction: Distinct arsenic metabolites following seaweed consumption in humans.

A correction to this article has been published and is linked from the HTML and PDF versions of this paper. The error has not been fixed in the paper.

Distinct arsenic metabolites following seaweed consumption in humans.

Seaweeds contain arsenic primarily in the form of arsenosugars, which can be metabolized to a wide range of arsenic compounds. To characterize human exposure to arsenic from seaweed consumption, we determined concentrations of arsenic species in locally available seaweeds, and assessed urinary arsenic compounds in an experimental feeding study. A total of 11 volunteers consumed 10 g per day of three types of seaweeds (nori, kombu, and wakame) for three days each, while abstaining from rice and seafood following a three-day washout period. Urinary arsenosugars and their metabolites (including dimethyl arsenate (DMA), thio-dimethylarsinoylethanol (thio-DMAE), thio-dimethylarsinoylacetate (thio-DMAA), and thio-DMA) were measured in spot urine samples prior to seaweed consumption, and in 24-hour urine samples while consuming seaweed. Commercial products made from whole seaweed had substantial concentrations of arsenic (12-84 µg/g), dominated by arsenosugars. Intact arsenosugars along with DMA, thio-DMAA, thio-DMAE all increased in urine after ingesting each type of seaweed, and varied between seaweed types and between individuals. Only trace levels of the known toxic metabolite, thio-DMA, were observed, across individuals. Thio-DMAE and thio-DMAA are unique products of arsenosugar breakdown, thus assessment of these compounds may help to identify dietary intake of arsenic from seaweed from other exposure pathways.

Concentrations and speciation of arsenic in New England seaweed species harvested for food and agriculture.

A survey of arsenic (As) concentrations and speciation was conducted on 10 species of seaweed from commercial harvesters and from collection at two sites in New England. Concentrations of As ranged from 4 to 106 mg/kg, mostly in the form of arsenosugars, with the distribution of arsenosugar analogs varying between taxa. In brown algae, As levels were correlated with phosphate concentrations, and arsenosugar speciation reflected differences in sulfur and phosphate concentrations between taxa. Several samples of the brown algae species Laminaria digitata contained significant levels of inorganic As (2.8-20 mg/kg), the most toxic form of As. A weak acid extraction with microwave heating was compared with a weaker methanol: water extraction method, and found to give slightly higher extraction efficiency with comparable relative concentrations of inorganic As, supporting the use of this faster and simpler extraction method for monitoring. Seaweed is a niche dietary item in the U.S. but its popularity is increasing; it is also used in agriculture and livestock farming which provide potential indirect routes for human exposure. The presence of occasional high concentrations of iAs, as well as the lack of toxicity studies on organic As species, suggest that monitoring of these high As foods is warranted.

Monomethylarsonous Acid (MMAIII) Has an Adverse Effect on the Innate Immune Response of Human Bronchial Epithelial Cells to Pseudomonas aeruginosa.

UNLABELLED: Arsenic is the number one contaminant of concern with regard to human health according to the World Health Organization. Epidemiological studies on Asian and South American populations have linked arsenic exposure with an increased incidence of lung disease, including pneumonia, and chronic obstructive pulmonary disease, both of which are associated with bacterial infection. However, little is known about the effects of low dose arsenic exposure, or the contributions of organic arsenic to the innate immune response to bacterial infection. This study examined the effects on Pseudomonas aeruginosa (P. aeruginosa) induced cytokine secretion by human bronchial epithelial cells (HBEC) by inorganic sodium arsenite (iAsIII) and two major metabolites, monomethylarsonous acid (MMAIII) and dimethylarsenic acid (DMAV), at concentrations relevant to the U.S. POPULATION: Neither iAsIII nor DMAV altered P. aeruginosa induced cytokine secretion. By contrast, MMAIII increased P. aeruginosa induced secretion of IL-8, IL-6 and CXCL2. A combination of iAsIII, MMAIII and DMAV (10 pbb total) reduced IL-8 and CXCL1 secretion. These data demonstrate for the first time that exposure to MMAIII alone, and a combination of iAsIII, MMAIII and DMAV at levels relevant to the U.S. may have negative effects on the innate immune response of human bronchial epithelial cells to P. aeruginosa.

Influence of a chlor-alkali superfund site on mercury bioaccumulation in periphyton and low-trophic level fauna.

In Berlin, New Hampshire, USA, the Androscoggin River flows adjacent to a former chlor-alkali facility that is a US Environmental Protection Agency Superfund site and source of mercury (Hg) to the river. The present study was conducted to determine the fate and bioaccumulation of methylmercury (MeHg) to lower trophic-level taxa in the river. Surface sediment directly adjacent to the source showed significantly elevated MeHg (10-40× increase, mean ± standard deviation [SD]: 20.1 ± 24.8 ng g(-1) dry wt) and total mercury (THg; 10-30× increase, mean ± SD: 2045 ± 2669 ng g(-1) dry wt) compared with all other reaches, with sediment THg and MeHg from downstream reaches elevated (3-7× on average) relative to the reference (THg mean ± SD: 33.5 ± 9.33 ng g(-1) dry wt; MeHg mean ± SD: 0.52 ± 0.21 ng g(-1) dry wt). Water column THg concentrations adjacent to the point source for both particulate (0.23 ng L(-1)) and dissolved (0.76 ng L(-1)) fractions were 5-fold higher than at the reference sites, and 2-fold to 5-fold higher than downstream. Methylmercury production potential of periphyton material was highest (2-9 ng g(-1) d(-1) dry wt) adjacent to the Superfund site; other reaches were close to or below reporting limits (0. 1 ng g(-1) d(-1) dry wt). Total Hg and MeHg bioaccumulation in fauna was variable across sites and taxa, with no clear spatial patterns downstream of the contamination source. Crayfish, mayflies, and shiners showed a weak positive relationship with porewater MeHg concentration.

Pathways of CH3Hg and Hg ingestion in benthic organisms: an enriched isotope approach.

Mercury is a widespread contaminant in marine food webs, and identifying uptake pathways of mercury species, CH3Hg(+) and Hg(2+), into low trophic level organisms is important to understanding its entry into marine food webs. Enriched stable isotope tracers were used to study benthic vs. pelagic pathways of CH3Hg(+) and Hg(2+) uptake via food to the infaunal estuarine amphipod, Leptocheirus plumulosus. Algal cells differentially labeled with isotopically enriched CH3Hg(+) or Hg(2+) were added simultaneously to the sediment and water column of microcosms, and Hg species were monitored in amphipods and in sediment and water compartments. Methylation of Hg(2+) occurred during the course of the experiment, enhancing the uptake of Hg(2+) spikes. Trophic transfer of Hg from algae added to the water column was determined to be the major uptake route for amphipods, suggesting inputs of contaminated organic matter from the pelagic zone are important to mercury bioaccumulation even in organisms living in sediments.

Monomethylated trivalent arsenic species disrupt steroid receptor interactions with their DNA response elements at non-cytotoxic cellular concentrations.

Arsenic (As) is considered a top environmental chemical of human health because it has been linked to adverse health effects including cancer, diabetes, cardiovascular disease, and reproductive and developmental problems. In several cell culture and animal models, As acts as an endocrine disruptor, which may underlie many of its health effects. Previous work showed that steroid receptor (SR)-driven gene expression is disrupted in cells treated with inorganic As (arsenite, iAs(+3)). In those studies, low iAs(+3) concentrations (0.1-0.7 µM) stimulated hormone-inducible transcription, whereas somewhat higher but still non-cytotoxic levels (1-3 µM) inhibited transcription. This investigation focuses on the mechanisms underlying these inhibitory effects and evaluates the role of methylated trivalent As metabolites on SR function. Recent evidence suggests that, compared with iAs, methylated forms may have distinct biochemical effects. Here, fluorescence polarization (FP) experiments utilizing purified, hormone-bound human glucocorticoid (GR) and progesterone receptor (PR) have demonstrated that neither inorganic (iAs(+3)) nor dimethylated (DMA(+3)) species of trivalent As affect receptor interactions with glucocorticoid DNA response elements (GREs). However, monomethylated forms (monomethylarsenite, MMA(+3) and monomethylarsonic diglutathione, MADG) strongly inhibit GR-GRE and PR-GRE binding. Additionally, speciation studies of iAs(+3)-treated H4IIE rat hepatoma cells show that, under treatment conditions that cause inhibition of hormone-inducible gene transcription, the intracellular concentration of MADG is sufficient to inhibit GR-GRE and PR-GRE interactions in vivo. These results indicate that arsenic's inhibitory endocrine disruption effects are probably caused in part by methylated metabolites' disruption of SR ability to bind DNA response elements that are crucial to hormone-driven gene transcription.

Arsenic concentration and speciation in infant formulas and first foods.

Arsenic exposure to humans is pervasive, and, increasingly, studies are revealing adverse health effects at ever lower doses. Drinking water is the main route of exposure for many individuals; however, food can be a significant source of arsenic to an individual, especially if their diet is rice-based. Infants are particularly susceptible to dietary exposure, since many first foods contain rice and they have a low body mass. Here we report on arsenic concentration and speciation in infant formulas and first foods. Speciation is essential for food analysis because of the much greater toxicity of inorganic arsenic species and the possibility that arsenic in food (unlike water) may be present in either inorganic or organic forms. Infant milk formulas were low in total arsenic (2.2-12.6 ng g(-1), n=15). Non-dairy formulas were significantly higher in arsenic than dairy-based formulas. Arsenic in formula was almost exclusively inorganic and predominantly arsenic(V). Arsenic concentration in purees (n=41) and stage 3 foods (n=18) ranged from 0.3-22 ng g(-1). Rice-fortified foods had significantly higher total arsenic concentrations than non rice-based foods. Again arsenic speciation was predominantly inorganic; arsenic(III) was the main species with lower concentrations of DMA and arsenic(V) also present. These data confirm that infants are exposed to arsenic via diet, and suggest that careful attention to diet choices may limit this.

Arsenic, organic foods, and brown rice syrup.

BACKGROUND: Rice can be a major source of inorganic arsenic (Asi) for many sub-populations. Rice products are also used as ingredients in prepared foods, some of which may not be obviously rice based. Organic brown rice syrup (OBRS) is used as a sweetener in organic food products as an alternative to high-fructose corn syrup. We hypothesized that OBRS introduces As into these products. OBJECTIVE: We determined the concentration and speciation of As in commercially available brown rice syrups and in products containing OBRS, including toddler formula, cereal/energy bars, and high-energy foods used by endurance athletes. METHODS: We used inductively coupled plasma mass spectrometry (ICP-MS) and ion chromatography coupled to ICP-MS to determine total As (Astotal) concentrations and As speciation in products purchased via the Internet or in stores in the Hanover, New Hampshire, area. DISCUSSION: We found that OBRS can contain high concentrations of Asi and dimethyl-arsenate (DMA). An "organic" toddler milk formula containing OBRS as the primary ingredient had Astotal concentrations up to six times the U.S. Environmental Protection Agency safe drinking water limit. Cereal bars and high-energy foods containing OBRS also had higher As concentrations than equivalent products that did not contain OBRS. Asi was the main As species in most food products tested in this study. CONCLUSIONS: There are currently no U.S. regulations applicable to As in food, but our findings suggest that the OBRS products we evaluated may introduce significant concentrations of Asi into an individual's diet. Thus, we conclude that there is an urgent need for regulatory limits on As in food.

Arsenic speciation in food chains from mid-Atlantic hydrothermal vents.

Arsenic concentration and speciation were determined in benthic fauna collected from the Mid-Atlantic Ridge hydrothermal vents. The shrimp species, Rimicaris exoculata, the vent chimney-dwelling mussel, Bathymodiolus azoricus, Branchipolynoe seepensis, a commensal worm of B. azoricus, and the gastropod Peltospira smaragdina showed variations in As concentration and in stable isotope (δ13C and δ15N) signature between species, suggesting different sources of As uptake. Arsenic speciation showed arsenobetaine to be the dominant species in R. exoculata, whereas in B. azoricus and B. seepensis arsenosugars were most abundant, although arsenobetaine, dimethylarsinate, and inorganic arsenic were also observed, along with several unidentified species. Scrape samples from outside the vent chimneys, covered with microbial mat, which is a presumed food source for many vent organisms, contained high levels of total As, but organic species were not detectable. The formation of arsenosugars in pelagic environments is typically attributed to marine algae, and the pathway to arsenobetaine is still unknown. The occurrence of arsenosugars and arsenobetaine in these deep sea organisms, where primary production is chemolithoautotrophic and stable isotope analyses indicate food sources are of vent origin, suggests that organic arsenicals can occur in a food web without algae or other photosynthetic life.

Trace-Level Automated Mercury Speciation Analysis.

An automated system for methyl Hg analysis by purge and trap gas chromatography (GC) was evaluated, with comparison of several different instrument configurations including chromatography columns (packed column or capillary), detector (atomic fluorescence, AFS, or inductively coupled plasma mass spectrometry, ICP-MS, using quadrupole and sector field ICP- MS instruments). Method detection limits (MDL) of 0.042 pg and 0.030 pg for CH(3)Hg(+) were achieved with the automated Hg analysis system configured with AFS and ICPMS detection, respectively. Capillary GC with temperature programming was effective in improving resolution and decreasing retention times of heavier Hg species (in this case C(3)H(7)Hg(+)) although carryover between samples was increased. With capillary GC, the MDL for CH(3)Hg(+) was 0.25 pg for AFS detection and 0.060 pg for ICP-MS detection. The automated system was demonstrated to have high throughput (72 samples analyzed in 8 hours) requiring considerably less analyst time than the manual method for methyl mercury analysis described in EPA 1630.