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.

Human exposure to organic arsenic species from seafood.

Seafood, including finfish, shellfish, and seaweed, is the largest contributor to arsenic (As) exposure in many human populations. In contrast to the predominance of inorganic As in water and many terrestrial foods, As in marine-derived foods is present primarily in the form of organic compounds. To date, human exposure and toxicological assessments have focused on inorganic As, while organic As has generally been considered to be non-toxic. However, the high concentrations of organic As in seafood, as well as the often complex As speciation, can lead to complications in assessing As exposure from diet. In this report, we evaluate the presence and distribution of organic As species in seafood, and combined with consumption data, address the current capabilities and needs for determining human exposure to these compounds. The analytical approaches and shortcomings for assessing these compounds are reviewed, with a focus on the best practices for characterization and quantitation. Metabolic pathways and toxicology of two important classes of organic arsenicals, arsenolipids and arsenosugars, are examined, as well as individual variability in absorption of these compounds. Although determining health outcomes or assessing a need for regulatory policies for organic As exposure is premature, the extensive consumption of seafood globally, along with the preliminary toxicological profiles of these compounds and their confounding effect on assessing exposure to inorganic As, suggests further investigations and process-level studies on organic As are needed to fill the current gaps in knowledge.

Mercury and cadmium in ringed seals in the Canadian Arctic: Influence of location and diet.

Concentrations of total mercury (THg) and total cadmium (TCd) were determined in muscle and liver of ringed seals (Pusa hispida) from up to 14 locations across the Canadian Arctic. Location, trophic position (TP) and relative carbon source best predicted the THg and TCd concentrations in ringed seals. THg concentrations in ringed seals were highest in the western Canadian Arctic (Beaufort Sea), whereas TCd was highest in the eastern Canadian Arctic (Hudson Bay and Labrador). A positive relationship between THg and TP and a negative relationship between THg and relative carbon source contributed to the geographical patterns observed and elevated THg levels at certain sites. In contrast, a negative relationship between TCd and TP was found, indicating that high TCd concentrations are related to seals feeding more on invertebrates than fish. Feeding ecology appears to play an important role in THg and TCd levels in ringed seals, with biomagnification driving elevated THg levels and a dependence on low-trophic position prey resulting in high TCd concentrations. The present study shows that both natural geological differences and diet variability among regions explain the spatial patterns for THg and TCd concentrations in ringed seals.

Local contamination, and not feeding preferences, explains elevated PCB concentrations in Labrador ringed seals (Pusa hispida).

Polychlorinated biphenyls (PCBs) in high trophic level species typically reflect the contributions of myriad sources, such that source apportionment is rarely possible. The release of PCBs by a military radar station into Saglek Bay, Labrador contaminated the local marine food web. For instance, while heavier (higher chlorinated) PCB profiles in some ringed seals (Pusa hispida) were previously attributed to this local source, differences in feeding preferences among seals could not be ruled out as a contributing factor. Herein, similar fatty acid profiles between those seals with 'local' PCB profiles and those with 'long-range' or background profiles indicate little support for the possibility that differential feeding ecologies underlay the divergent PCB profiles. Ringed seals appeared to feed predominantly on zooplankton (Mysis oculata and Themisto libellula), followed by the dusky snailfish (Liparis gibbus), arctic cod (Boreogadus saida), and shorthorn sculpin (Myoxocephalus scorpius). Principal components analysis (PCA) and PCB homolog profiles illustrated the extent of contamination of the Saglek food web, which had very different (and much heavier) PCB profiles than those food web members contaminated by 'long-range' sources. Locally contaminated prey had PCB levels that were higher (2- to 544-fold) than prey contaminated by 'long-range' sources and exceeded wildlife consumption guidelines for PCBs. The application of multivariate analyses to two distinct datasets, including PCB congeners (n=50) and fatty acids (n=65), afforded the opportunity to clearly distinguish the contribution of locally-released PCBs to a ringed seal food web from those delivered via long-ranged transport. Results from the present study strongly suggest that habitat use rather than differences in prey selection is the primary mechanism explaining the divergent PCB patterns in Labrador ringed seals.

Mercury in the marine environment of the Canadian Arctic: review of recent findings.

This review summarizes data and information which have been generated on mercury (Hg) in the marine environment of the Canadian Arctic since the previous Canadian Arctic Contaminants Assessment Report (CACAR) was released in 2003. Much new information has been collected on Hg concentrations in marine water, snow and ice in the Canadian Arctic. The first measurements of methylation rates in Arctic seawater indicate that the water column is an important site for Hg methylation. Arctic marine waters were also found to be a substantial source of gaseous Hg to the atmosphere during the ice-free season. High Hg concentrations have been found in marine snow as a result of deposition following atmospheric mercury depletion events, although much of this Hg is photoreduced and re-emitted back to the atmosphere. The most extensive sampling of marine sediments in the Canadian Arctic was carried out in Hudson Bay where sediment total Hg (THg) concentrations were low compared with other marine regions in the circumpolar Arctic. Mass balance models have been developed to provide quantitative estimates of THg fluxes into and out of the Arctic Ocean and Hudson Bay. Several recent studies on Hg biomagnification have improved our understanding of trophic transfer of Hg through marine food webs. Over the past several decades, Hg concentrations have increased in some marine biota, while other populations showed no temporal change. Marine biota also exhibited considerable geographic variation in Hg concentrations with ringed seals, beluga and polar bears from the Beaufort Sea region having higher Hg concentrations compared with other parts of the Canadian Arctic. The drivers of these variable patterns of Hg bioaccumulation, both regionally and temporally, within the Canadian Arctic remain unclear. Further research is needed to identify the underlying processes including the interplay between biogeochemical and food web processes and climate change.

Satellite telemetry informs PCB source apportionment in a mobile, high trophic level marine mammal: the ringed seal (Pusa hispida).

Marine mammals are typically poor indicators of point sources of environmental contaminants as a consequence of their often complex feeding ecologies and extensive movements, all of which mask the contributions of specific inputs. The release of polychlorinated biphenyls (PCBs) by a military radar station into Saglek Bay, Labrador (Canada) has contaminated marine sediments, bottom-feeding fish, seabirds, and some ringed seals, but attributing the PCBs in the latter highly mobile animals to this source is exceedingly difficult. In addition to the application of such tools as stable isotopes (δ(15)N and δ(13)C) and univariate and multivariate statistical exploration of contaminant patterns and ratios, we used satellite telemetry to track the movements of 13 seals in their transient use of different feeding areas. Reduced size of home range and core area (i.e., areas of concentrated use), as well as increased time in coastal inlets, were important determinants of increased PCB concentrations in seals reflecting the contribution of Saglek Bay. Seals were classified into the same feeding groups using both space use and their contaminant burdens 85% of the time, highlighting the link between feeding ecology and exposure to PCBs. While the PCB source at Saglek provided a strong local signal in a remote environment, this first use of satellite telemetry demonstrates the utility of evaluating space-use strategies to better understand contaminant exposure, and more specifically the contribution of contaminant hotspots to mobile predators.

PCB related effects thresholds as derived through gene transcript profiles in locally contaminated ringed seals (Pusa hispida).

Causal evidence linking toxic injury to polychlorinated biphenyl (PCB) exposure is typically confounded by the complexity of real-world contaminant mixtures to which aquatic wildlife are exposed. A local PCB "hotspot" on the Labrador coast provided a rare opportunity to evaluate the effects of PCBs on the health of a marine mammal as this chemical dominated their persistent organic pollutant (POP) burdens. The release of approximately 260 kg of PCBs by a military radar facility over a 30 year period (1970-2000) contaminated some local marine biota, including the ringed seal (Pusa hispida). The abundance profiles of eight health-related gene transcripts were evaluated in liver samples collected from 43 ringed seals in the affected area. The mRNA transcript levels of five gene targets, including aryl hydrocarbon receptor (Ahr), interleukin-1 ß (Il1b), estrogen receptor α (Esr1), insulin like growth factor receptor 1 (Igf1), and glucocorticoid receptor α (Nr3c1) correlated with increasing levels of blubber PCBs. PCB threshold values calculated using best-fit hockey-stick regression models for these five genes averaged 1,680±206 ng/g lw, with the lowest, most conservative, being 1,370 ng/g lw for Il1b. Approximately 14% of the seals in the region exceeded this threshold. The dominance of PCBs in the seals studied enabled an assessment of the effects of this chemical on gene transcripts involved in regulating the health of a highly mobile predator, something that is rarely possible in the world of complex mixtures.

Polychlorinated biphenyl profiles in ringed seals (Pusa Hispida) reveal historical contamination by a military radar station in Labrador, Canada.

Significant amounts of soil contaminated with polychlorinated biphenyls (PCBs) were discovered at a military radar station in Saglek Bay, Labrador, Canada, in 1996. Subsequent work showed elevated PCB concentrations in local marine sediments, in the benthic-associated food web, and in some ringed seals (Pusa hispida). The benthic-associated food web clearly reflected local PCB contamination, but the high PCB concentrations found in some ringed seals remained unexplained. In the present study, the authors assess the extent to which this local PCB source at Saglek Bay is contributing to the contamination of ringed seals in northern Labrador. Among 63 ringed seals sampled along the northern Labrador coast, 5 (8%) had PCB levels that were higher than recorded anywhere else in the Canadian Arctic. In addition, compared with seals exhibiting a long-range signal, 45% and 60% of subadults and adult males, respectively, exhibited heavier PCB congener profiles as characterized by principal components analysis, >1.6-fold higher PCB/organochlorine pesticides ratios, and higher PCB concentration-weighted average log octanol-water partition coefficient values, consistent with a local source. Despite the spatially confined nature of contaminated sediments in Saglek Bay, the influence of this PCB source is not inconsequential; PCB concentrations in locally contaminated adult males are 2-fold higher than concentrations in those exposed only to long-range PCB sources and exceed an established threshold of 1.3 mg/kg for adverse health effects in seals.

Effects-based marine ecological risk assessment at a polychlorinated biphenyl-contaminated site in Saglek, Labrador, Canada.

Although the presence and distribution of polychlorinated biphenyls (PCBs) in Arctic marine environments has been well documented, the implications for the health of biota are poorly understood. In the present study, multiple lines of evidence, including site-specific effects data, were used to assess PCB-related risks to marine biota at a contaminated military site in Saglek Bay, Labrador, Canada, from 1997 to 1999. Risks were evaluated for three components of the ecosystem: benthic invertebrates, a bottom-feeding fish (shorthorn sculpin, Myoxocephalus scorpius), and a diving seabird (black guillemot, Cepphus grylle). Average sediment PCB concentrations exceeded the Canadian interim sediment quality guideline level by 41-fold. However, sediment toxicity testing and a benthic community survey showed no evidence of adverse effects. In contrast, shorthorn sculpin and black guillemot PCB exposures (measured as sum of 55 congeners) were elevated enough to pose risks to survival or reproduction. Based on the collective evidence, the authors estimated that risks were posed by sediment PCB concentrations greater than 77 ng/g dry weight for black guillemots and 750 ng/g dry weight for shorthorn sculpins. The present study, along with two parallel studies, provided information to support the management decisions concerning potential remedial action on the contaminated sediments. This ecological risk assessment describes the steps and rationale taken to evaluate the risk posed by an area of PCB-contaminated marine sediments in an otherwise relatively pristine northern coastal environment.

Arsenic speciation in plankton organisms from contaminated lakes: transformations at the base of the freshwater food chain.

The two complementary techniques high performance liquid chromatography-inductively coupled plasma-mass spectrometry (HPLC-ICP-MS) and X-ray absorption near edge structure (XANES) analysis were used to assess arsenic speciation in freshwater phytoplankton and zooplankton collected from arsenic-contaminated lakes in Yellowknife (Northwest Territories, Canada). Arsenic concentrations in lake water ranged from 7 µg L(-1) in a noncontaminated lake to 250 µg L(-1) in mine-contaminated lakes, which resulted in arsenic concentrations ranging from 7 to 340 mg kg(-1) d.w. in zooplankton organisms (Cyclops sp.) and from 154 to 894 mg kg(-1) d.w. in phytoplankton. The main arsenic compounds identified by HPLC-ICP-MS in all plankton were inorganic arsenic (from 38% to 98% of total arsenic). No other arsenic compounds were found in phytoplankton, but zooplankton organisms showed the presence of organoarsenic compounds, the most common being the sulfate arsenosugar, up to 47% of total arsenic, with traces of phosphate sugar, glycerol sugar, methylarsonate (MMA), and dimethylarsinate (DMA). In the uncontaminated Grace Lake, zooplankton also contained arsenobetaine (AB). XANES characterization of arsenic in the whole plankton samples showed As(V)-O as the only arsenic compound in phytoplankton, and As(III)-S and As(V)-O compounds as the two major inorganic arsenic species in zooplankton. The proportion of organoarsenicals and inorganic arsenic in zooplankton depends upon the arsenic concentration in lakes and shows the impact of arsenic contamination: zooplankton from uncontaminated lake has higher proportions of organoarsenic compounds and contains arsenobetaine, while zooplankton from contaminated area contains mostly inorganic arsenic.

Reduction of PCB contamination in an Arctic coastal environment: a first step in assessing ecosystem recovery after the removal of a point source.

Studies have documented the presence of organic contaminants in Arctic marine environments due to local point sources, but little long-term data is known of the recovery process once those contaminants are removed. In this study, natural recovery of a local marine food web from a historic terrestrial source of polychlorinated biphenyls (PCBs) at Saglek Bay is examined. PCBs were measured in marine sediments, shorthorn sculpin (Myoxocephalus scorpius), and black guillemots (Cepphus grylle) to assess ecosystem recovery over an eight-year period after cleanup of the source. Surface sediment measurements indicate decreases in both the extent and average concentrations of PCBs throughout Saglek Bay. Sculpin collected near the former contaminated beach in 2006 had significantly lower PCB burdens than those collected in 1998/ 99. PCB levels have also decreased significantly in black guillemot nestlings collected from the former contaminated beach area, as well as Island (6-8 km from the source) and Reference (greater than 18 km from the source) locations. This study demonstrates the utility of using indicator species, especially the black guillemot, to monitor PCB uptake in benthic food webs. The rapid decreases in the physical and biotic PCB concentrations from the local ecosystem at Saglek Bay demonstratethe efficiency with which natural ecosystem recovery can take place in a highly energetic coastal marine environment once a chronic contaminant source is removed.

Bioremediation of weathered petroleum hydrocarbon soil contamination in the Canadian High Arctic: laboratory and field studies.

The bioremediation of weathered medium- to high-molecular weight petroleum hydrocarbons (HCs) in the High Arctic was investigated. The polar desert climate, contaminant characteristics, and logistical constraints can make bioremediation of persistent HCs in the High Arctic challenging. Landfarming (0.3 m(3) plots) was tested in the field for three consecutive years with plots receiving very little maintenance. Application of surfactant and fertilizers, and passive warming using a greenhouse were investigated. The field study was complemented by a laboratory experiment to better understand HC removal mechanisms and limiting factors affecting bioremediation on site. Significant reduction of total petroleum HCs (TPH) was observed in both experiments. Preferential removal of compounds nC16 occurred, whereas in the field, TPH reduction was mainly limited to removal of compounds nC16 was observed in the fertilized field plots only. The greenhouse increased average soil temperatures and extended the treatment season but did not enhance bioremediation. Findings suggest that temperature and low moisture content affected biodegradation of HCs in the field. Little volatilization was measured in the laboratory, but this process may have been predominant in the field. Low-maintenance landfarming may be best suited for remediation of HCs compounds

Effects of local point source polychlorinated biphenyl (PCB) contamination on bone mineral density in deer mice (Peromyscus maniculatus).

A former local source of PCBs has contaminated soil and the terrestrial food web at Saglek, Labrador. The relationship between PCB exposure and bone mineral density as an osteoporosis biomarker in deer mice (Peromyscus maniculatus) was investigated at two sites at Saglek: a contaminated Beach and a reference area. Bone mineral density was measured on the femur of twenty-six deer mice using dual-energy X-ray absorptiometry (DXA) technology. Bone mineral density was significantly lower in deer mice from the high exposure site (average whole body summation operatorPCB=5769 ng/g wet weight, n=20) than at the reference site (average whole body summation operatorPCB=79.8 ng/g wet weight, n=7). We used T-scores from the World Health Organization to determine the degree of decreased bone mineral density in exposed mice. Assuming the same biomechanical forces apply as for humans, and using a conservative factor of 1.5 (fracture risk increases 1.5 to 3 fold for every standard deviation decrease in bone mineral density), mice from the contaminated Beach are up to five folds more susceptible to fracture risk than mice from the reference area. Therefore, the PCB concentrations found locally at contaminated military sites such as Saglek are high enough to affect local wildlife.

Addressing arsenic bioaccessibility in ecological risk assessment: a novel approach to avoid overestimating risk.

The risk of arsenic exposure to deer mice (Peromyscus maniculatus) living in areas of naturally and anthropogenically elevated arsenic levels was determined using three separate calculations of arsenic daily intake: Estimated daily intake (EDI), bioaccessible EDI (BEDI), and actual daily intake (ADI). The present work is of particular interest, because the risk assessments were determined for animals naturally exposed to arsenic. Gastric fluid extraction was used to obtain bioaccessibility data for soil and plant samples collected from three study sites (background, mine forest, and tailings) in Yellowknife (NT, Canada). Calculations using the EDI indicated that deer mice living in tailings habitat (average soil arsenic concentration, 1,740 +/- 2,240 microg/g) should have been experiencing serious health effects as a result of their exposure to arsenic. Using BEDI and ADI in the risk assessment calculation, however, resulted in an order-of-magnitude decrease in calculated risk. In addition, results calculated using the BEDI and ADI were not significantly different, suggesting that using bioaccessibility provides a more realistic estimate of potential risk. The present results provide evidence that the use of EDI in traditional risk assessments may seriously overestimate the actual risk, which in some instances may result in expensive and unnecessary clean-up measures.

Ecological risk assessment of lead contamination at rifle and pistol ranges using techniques to account for site characteristics.

Spent ammunition at outdoor rifle and pistol (RP) firing ranges creates a characteristic pattern of contamination, whereby small areas surrounding backstop berms exhibit extremely high soil lead (Pb) concentrations. We characterized sources, pathways and uncertainty in contaminant accumulation for receptors at two RP ranges in southeastern Ontario. Based on these results, we performed risk calculations using kriging to estimate risk across "worst-case" species foraging ranges. Range-normalized hazard quotients (RNHQ) were then calculated to estimate risk across each receptor's foraging range. Monte Carlo simulation was used to provide +2 standard deviation (SD) risk estimates, in order to account for uncertainty in risk parameters. The American robin was found to be most at risk (RNHQ=4.10; +2SD=9.24), followed by the short-tailed shrew (RNHQ=0.113; +2SD=0.243) and the eastern cottontail (RNHQ=0.109; +2SD=0.703). Elevated risk for the American robin and short-tailed shrew was due to their small foraging ranges and habit of eating earthworms, which bioaccumulate Pb. Elevated risk for the eastern cottontail was due to vegetation accumulating Pb to levels that were considerably higher than conventional bioaccumulation models would indicate. The results of this study clearly emphasize the importance of specific characteristics of RP ranges, such as contamination patterns, dust accumulation on plant tissues, and contaminant bioaccessibility. These characteristics should be accounted for, not only in performing risk assessments, but also in choosing remedial options and in routine management practices.

Extraction and speciation of arsenic in plants grown on arsenic contaminated soils.

A sequential arsenic extraction method was developed that yielded extraction efficiencies (EE) that were approximately double those using current methods for terrestrial plants. The method was applied to plants from two arsenic contaminated sites and showed potential for risk assessment studies. In the method, plants were extracted first by 1:1 water-methanol followed by 0.1M hydrochloric (HCl) acid. Total arsenic in plant and soil samples collected from contaminated sites was mineralized by acid digestion and detected by inductively coupled plasma-atomic emission spectrometry (ICP-AES) and hydride generation-atomic absorption spectrometry (HG-AAS). Arsenic speciation was done by high performance liquid chromatography coupled with HG-AAS (HPLC-HGAAS) and by HPLC coupled with ICP-mass spectrometry (HPLC-ICP-MS). Spike recovery experiments with arsenite (As(III)), arsenate (As(V)), methylarsonic acid (MA) and dimethylarsinic acid (DMA) showed stability of the species in the extraction processes. Speciation analysis by X-ray absorption near edge spectroscopy (XANES) demonstrated that no transformation of As(III) and As(V) occurred due to sample handling. Dilute HCl was efficient in extracting arsenic from plants; however, extraction and determination of organic species were difficult in this medium. Sequential extraction with 1:1 water-methanol followed by 0.1M-HCl was most useful in extracting and speciating both organic and inorganic arsenic from plants. Trace amounts of MA and DMA in plants could be detected by HPLC-HGAAS aided by the process of separation and preconcentration of the sequential extraction method. Both organic and inorganic arsenic compounds could be detected simultaneously in synthetic gastric fluid extracts (GFE) but EEs by this method were lower than those of the sequential method. The developed sequential method was shown to be reliable and applicable to various terrestrial plants for arsenic extraction and speciation.