Contaminants of emerging concern in Caspian tern compared to herring gull eggs from Michigan colonies in the Great Lakes of North America.

A broad suite of 87 contaminants of emerging concern (CECs), including 26 polybrominated diphenyl ethers (PBDEs), 23 non-PBDEs halogenated FRs (NPHFRs), 16 organophosphate esters (OPEs), 4 perfluorinated sulfonates (PFSAs), 13 perfluorinated carboxylic acids (PFCAs) and 5 emerging perfluoroalkyl acids (PFAAs) or precursors, were determined in 30 individual Caspian tern (listed as a threatened species in the U.S. State of Michigan) eggs collected in 2013 and 2014 from Michigan nesting sites on Two Tree Island (St, Mary's River), Charity Reef (Saginaw Bay) and Channel-Shelter Island (a Confined Disposal Facility (CDF) in Saginaw Bay). The same CEC suite was determined in 10 herring gull eggs on the Pipe Island Twins in the lower St. Mary's River. In tern eggs, the order of concentrations were ΣPFSA (mean: 793 ng/g wet weight (ww); range: 116-4690 ng/g ww) > ΣPFCAs (131; 30.4-506 ng/g ww) ≈ ΣPBDEs (86.7; 32.4-189 ng/g ww) ¼ ΣNPHFRs (0.67; ND-4.3 ng/g ww) ≈ ΣOPEs (0.46; ND-2.89 ng/g ww). Compared to gull eggs collected from the same area, tern egg exposure contained significantly lower concentrations of ΣPBDE, but with up to 10 times greater mean concentrations of ΣPFSAs and ΣPFCAs. This study highlights the importance of consistent monitoring in eggs of different Great Lakes birds of PBDEs, perfluorooctane sulfonate (PFOS) and perfluoro-4-ethylcyclohexane sulfonate (PFEtCHxS) given that: 1) PBDE concentrations in all analyzed avian eggs exceeded or approached a concentration of 29 ng/g ww, which for birds is the current Canadian FEQG (Federal Environmental Quality Guideline); 2) ΣPBDE concentrations were comparable to lowest observed effect concentration (LOEC) values reported in the literature; 3) PFOS concentrations in Caspian tern eggs were extremely high with many eggs across sites exceeding 1 ppm, and with the greatest being up to 4.7 ppm; and 4) PFEtCHxS, a potentially persistent and bioaccumulative substance, showed a detection frequency of 100% in 40 of the analyzed eggs.

Spatial and temporal comparisons of legacy and emerging flame retardants in herring gull eggs from colonies spanning the Laurentian Great Lakes of Canada and United States.

In the Laurentian Great Lakes basin of North America, an increasing number of chemicals of emerging concern (CECs) are being investigated, including legacy and replacement flame retardants (FRs). In the present study, 14 polybrominated diphenyl ethers (PBDEs), 23 non-PBDEs halogenated FRs (NPHFRs) and 16 organophosphate ester FRs (OPE-FRs) were analyzed in 100 individual eggs collected in 2012 and 2013 and in 15 egg pools of herring gulls collected in 2012 from 20 colonies across the entire Laurentian Great Lakes basin. For CEC-FRs in eggs from all colonies, 14 PBDEs, 12 NPHFRs and 9 OPE-FRs were quantifiable in at least one of the 115 analyzed samples. The mean sum PBDE (Σ14PBDE) concentrations ranged from 244 to 657 ng/g wet weight (ww), and on average were 1-2 orders of magnitude greater than the Σ12NPHFR concentrations (13.8-35.6 ng/g ww), and 2-3 orders of magnitude greater than Σ9OPE-FR concentrations (0.31-2.14 ng/g ww). Mean Σ14PBDE and sum of syn- and anti-Dechlorane Plus isomer (Σ2DDC-CO) concentrations in eggs from colonies within Laurentian Great Lakes Areas of Concern (AOCs) were in most cases greater than in eggs from nearby colonies outside of AOCs. Comparing CEC-FR concentrations in eggs collected in 2012-2013 to those previously measured in eggs collected approximately 7 years earlier (2006 and 2008) showed that Σ7PBDE (BDE-28, -47, -100, -99, -154,-153 and -183) mean concentrations in eggs from 6 colonies were approximately 30% less than they were in eggs from the same colonies from the earlier time period, whereas 3 current-use FR (BDE-209, HBCDD and Σ2DDC-CO) concentrations were significantly greater (p<0.05) than previously measured. Between 2006 and 2013 there were significant changes in individual PBDE patterns for BDE-71, -138, -153, -203, -206 and -207. Among all of the examined CEC-FRs, concentrations of Σ4PBDE (BDE-47, -99, -100 and -153) and HBCDD in gull eggs from all colonies were greater than or comparable to their lowest observed effect concentrations (LOECs) based on in ovo egg injection studies. Overall, the current profiles of a broad suite of FRs in Laurentian Great Lakes herring gull eggs highlights the need to better understand e.g., exposure-effect implications and metabolism of FRs, i.e. OPE-FRs, and emphasizes the importance of continued monitoring of CEC-FRs whose concentrations appear to be increasing, including BDE-209, HBCDD and DDC-COs.

Perfluorinated sulfonate and carboxylate compounds and precursors in herring gull eggs from across the Laurentian Great Lakes of North America: Temporal and recent spatial comparisons and exposure implications.

Chemicals of emerging concern (CECs) in the basin of the Laurentian Great Lakes of North America include per- and poly-fluoroalkyl substances (PFASs) classified as perfluoroalkyl acids. We investigated several PFASs, and specifically 13 C4-C16 perfluorinated carboxylic acids (PFCAs), 4 (C4, C6, C8 and C10) perfluorinated sulfonates (PFSAs), perfluoro-4-ethylcyclohexane sulfonate (PFEtCHxS) and selected precursors (e.g. perfluorobutane sulfonamide and perfluorooctane sulfonamide) in herring gull (Larus argentatus) eggs collected in 2012-2013 from 19 Canadian and U.S. colony sites across the Great Lakes. C6, C8 and C10 PFSAs, PFEtCHxS, and C7-14 and C16 PFCAs were quantifiable at >97% of the 114 egg samples. PFEtCHxS concentrations ranged from n.d. to 3.1ng/g ww (highest in Lake Michigan eggs). Mean Σ4PFSA (92 to 97% perfluorooctane sulfonate (PFOS)) and Σ9PFCA concentration ranges were 44 to 740 and 4.8 to 118ng/g ww, respectively. Σ4PFSA showed a clear increasing concentration trend from the northwest to the southeast colonies. Also, Σ4PFCA to Σ9PFSA concentration ratios in gull eggs were greater in eggs from Lake Superior relative to colonies in the other lakes. PFOS concentrations in some egg samples were greater than some of the known lowest observed effect concentrations (LOECs) measured and reported in captive bird model studies. This study showed the increasing complexity of PFAS-CECs, and emphasized the importance of continuing monitoring of bioaccumulative PFAS in Great Lakes herring gulls.

Translating ecological risk to ecosystem service loss.

Hazardous site management in the United States includes remediation of contaminated environmental media and restoration of injured natural resources. Site remediation decisions are informed by ecological risk assessment (ERA), whereas restoration and compensation decisions are informed by the natural resource damage assessment (NRDA) process. Despite similarities in many of their data needs and the advantages of more closely linking their analyses, ERA and NRDA have been conducted largely independently of one another. This is the 4th in a series of papers reporting the results of a recent workshop that explored how ERA and NRDA data needs and assessment processes could be more closely linked. Our objective is to evaluate the technical underpinnings of recentmethods used to translate natural resource injuries into ecological service losses and to propose ways to enhance the usefulness of data obtained in ERAs to the NRDA process. Three aspects are addressed: 1) improving the linkage among ERA assessment endpoints and ecological services evaluated in the NRDA process, 2) enhancing ERA data collection and interpretation approaches to improve translation of ERA measurements in damage assessments, and 3) highlighting methods that can be used to aggregate service losses across contaminants and across natural resources. We propose that ERA and NRDA both would benefit by focusing ecological assessment endpoints on the ecosystem services that correspond most directly to restoration and damage compensation decisions, and we encourage development of generic ecosystem service assessment endpoints for application in hazardous site investigations. To facilitate their use in NRDA, ERA measurements should focus on natural resource species that affect the flow of ecosystem services most directly, should encompass levels of biological organization above organisms, and should be made with the use of experimental designs that support description of responses to contaminants as continuous (as opposed to discrete) variables. Application of a data quality objective process, involving input from ERA and NRDA practitioners and site decision makers alike, can facilitate identification of data collection and analysis approaches that will benefit both assessment processes. Because of their demonstrated relationships to a number of important ecosystem services, we recommend that measures of biodiversity be targeted as key measurement endpoints in ERA to support the translation between risk and service losses. Building from case studies of recent successes, suggestions are offered for aggregating service losses at sites involving combinations of chemicals and multiple natural resource groups. Recognizing that ERA and NRDA are conducted for different purposes, we conclude that their values to environmental decision making can be enhanced by more closely linking their data collection and analysis activities.

A pramoxine-based anti-itch lotion is more effective than a control lotion for the treatment of uremic pruritus in adult hemodialysis patients.

OBJECTIVE: The objective of this study was to evaluate the efficacy of a commercially available anti-itch lotion containing 1% pramoxine hydrochloride versus control lotion in the treatment of uremic pruritus in adult hemodialysis patients. METHODS: This was a randomized, double-blind, controlled comparative trial set in a community hemodialysis center. The study population comprised 28 individuals (mean age 53.5) with moderate to severe uremic pruritus who had been receiving hemodialysis for at least 3 months. All participants were recruited from one community hemodialysis center. Topical anti-itch lotion containing 1% pramoxine was applied twice daily to all affected areas of pruritus for 4 weeks. The main outcome measure was a reduction in itch intensity. Secondary outcomes included increases in the investigator's global assessment and improvement in skin hydration. RESULTS: There was a 61% decrease in itch intensity in the treatment group, whereas a 12% reduction in itch intensity was observed in the control group. The rate of decline in itching was also greater in the treatment arm versus the control arm. No significant differences were displayed in other studied disease-related variables. CONCLUSION: Our study shows that individuals using pramoxine 1% lotion experienced a reduction in pruritus to a greater degree than those using the control lotion. This safe, convenient and effective topical lotion may potentially benefit the large number of patients affected by pruritus associated with end-stage renal disease.

Nondestructive scat sampling in assessment of mink (Mustela vison) exposed to polychlorinated dibenzofurans (PCDFs).

The mink (Mustela vison) is often utilized as a sentinel species for ecological assessments at sites where contaminants of concern include dioxins and dioxin-like compounds. Utilizing mink scat as a nondestructive tool to determine internal exposure to dioxin-like compounds may allow for rapid, accurate estimates of exposure without the need to capture mink or their prey. To determine the relationships between concentrations of polychlorinated dibenzofurans (PCDFs) in tissues (liver and adipose) and those in scat, mink were fed PCDFs in scat during a controlled laboratory study for 180 days. Mink were fed a control diet, diets with three doses of 2,3,4,7,8-pentachlorodibenzofuran (2,3,4,7,8-PeCDF) or 2,3,7,8-tetrachlorodibenzofuran (2,3,7,8-TCDF), and a diet with an environmentally relevant mixture of the two congeners. Concentrations of PCDFs in liver and adipose were measured after 0, 90, and 180 days of exposure. Concentrations of the two PCDF congeners in mink scat were determined after 2, 23, 45, 90, and 180 days of exposure. Concentrations of both PCDF congeners in scat were significantly correlated with those in liver and adipose tissue (r(2) = 0.94-0.97, p < 0.01). This indicates that measurements of concentrations of both PCDFs in scat can be used to predict concentrations of PCDFs in liver and adipose. Assimilation and elimination characteristics of 2,3,4,7,8-PeCDF or 2,3,7,8,-TCDF and a mixture of the two congeners by mink could be predicted from concentrations of these congeners in scat. Overall, concentrations of PCDFs in mink scat can be used as a rapid and inexpensive nondestructive method to predict concentrations of PCDFs in mink when certain assumptions are met.

Plasma to egg conversion factor for evaluating polychlorinated biphenyl and DDT exposures in great horned owls and bald eagles.

The benefits of nondestructive sampling techniques, such as plasma sampling, to directly measure contaminant exposure levels in at-risk or protected raptor populations are many. However, such assays are generally inconsistent with the most certain source of toxicity reference values, which are based on feeding studies and quantified as dietary or "in ovo" (egg-based) concentrations. An accurate conversion factor to translate nondestructive plasma-based contaminant concentrations to comparable egg-based concentrations will prove valuable to risk assessors investigating the potential effects of chemical exposures to raptors. We used databases describing the concentrations of total polychlorinated biphenyls (PCBs) in great horned owls (GHO; Bubo virginianus) and total PCBs and p,p'-dichlorodiphenyldichloroethylene (p,p'-DDE) in bald eagles (Haliaeetus leucocephalus) from the Great Lakes region (Michigan, Wisconsin, USA) to develop a relationship to predict concentrations of PCBs and DDE in eggs. To develop a robust predictive relationship, all of the source data included concentrations of both total PCBs and/or DDE for nestling blood plasma and egg samples collected from within discrete active nesting territories and, in most instances, the same nest. The key characteristics (slope and elevation) of each relationship were tested for differences related to species and geographic region. Predicted variability of relationships were examined and compared to variability associated with natural systems. The results of statistical testing indicate that applying the conversion factors between species (GHO to bald eagle) and among geographic regions yields predicted egg concentrations that are not statistically dissimilar and are within the natural variability observed for residue concentrations among eggs of raptors within species and region.

Effects of chronic dietary exposure to environmentally relevant concentrations to 2,3,7,8-tetrachlorodibenzo-p-dioxin on survival, growth, reproduction and biochemical responses of female rainbow trout (Oncorhynchus mykiss).

Adult female rainbow trout were exposed to dietary 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) at concentrations of 1.8, 18 and 90 ng TCDD/kg (ww) food for up to 300 day. At the end of the exposure fish were spawned and the reproductive outcomes were assessed. TCDD was accumulated into tissues and eggs in a dose-dependent manner with steady state being achieved after 50-100 day of exposure. Biochemical and hematological parameters were monitored at 50, 100, 150, and 200 day after the beginning of exposure. The survival of adult female trout was reduced in a dose-dependent manner by exposure to TCDD in the diet. Fish fed 1.8 ng TCDD/kg, moist weight of diet, showed significantly reduced survival compared with those fed the control diet. TCDD also affected survival of fry from females fed 1.8 ng TCDD/kg. Observed adverse effects in adult fish were as sensitive as early life-stage endpoints. Liver EROD activity was only moderately increased in all exposure groups after 250+ day of exposure. Low rates of edema and deformities were observed in fry from all treatment groups including controls. This study has demonstrated adverse effects of TCDD to both adults and fry at concentrations comparable to current environmental concentrations. This suggests that direct adult toxicity as well as reproductive endpoints need to be incorporated in the current risk assessment paradigm for these compounds.