House wren (Troglodytes aedon), tree swallow (Tachycineta bicolor), and eastern bluebird (Sialia sialis) tissues collected in study areas (SAs) downstream of Midland, Michigan (USA) contained concentrations of polychlorinated dibenzofurans (PCDFs) and polychlorinated dibenzo-p-dioxins (PCDDs) greater than in upstream reference areas (RAs) in the region. The sum of concentrations of PCDD/DFs (ΣPCDD/DFs) in eggs of house wrens and eastern bluebirds from SAs were 4- to 22-fold greater compared to those from RAs, whereas concentrations in tree swallow eggs were similar among areas. Mean concentrations of ΣPCDD/DFs and sum 2,3,7,8-tetrachlorodibenzo-p-dioxin equivalents (ΣTEQsWHO-Avian), based on 1998 WHO avian toxic equivalency factors, in house wren and eastern bluebird eggs ranged from 860 (430) to 1500 (910) ng/kg wet weight (ww) and 470 (150) to 1100 (510) ng/kg ww, respectively, at the most contaminated study areas along the Tittabawassee River, whereas mean concentrations in tree swallow eggs ranged from 280 (100) to 760 (280) ng/kg ww among all locations. Concentrations of ΣPCDD/DFs in nestlings of all studied species at SAs were 3- to 50-fold greater compared to RAs. Mean house wren, tree swallow, and eastern bluebird nestling concentrations of ΣPCDD/DFs and ΣTEQsWHO-Avian ranged from 350 (140) to 610 (300) ng/kg ww, 360 (240) to 1100 (860) ng/kg ww, and 330 (100) to 1200 (690) ng/kg ww, respectively, at SAs along the Tittabawassee River. Concentrations of ΣTEQsWHO-Avian were positively correlated with ΣPCDD/DF concentrations in both eggs and nestlings of all species studied. Profiles of relative concentrations of individual congeners were dominated by furan congeners (69–84%), primarily 2,3,7,8-tetrachlorodibenzofuran and 2,3,4,7,8-pentachlorodibenzofuran, for all species at SAs on the Tittabawassee and Saginaw rivers but were dominated by dioxin congeners at upstream RAs.Electronic supplementary materialThe online version of this article (doi:10.1007/s00244-009-9416-6) contains supplementary material, which is available to authorized users.

Trophic magnification factors (TMFs) are field-based measurements of the bioaccumulation behavior of chemicals in food-webs. TMFs can provide valuable insights into the bioaccumulation behavior of chemicals. However, bioaccumulation metrics such as TMF may be subject to considerable uncertainty as a consequence of systematic bias and the influence of confounding variables. This study seeks to investigate the role of systematic bias resulting from spatially-variable concentrations in water and sediments and biotransformation rates on the determination of TMF. For this purpose, a multibox food-web bioaccumulation model was developed to account for spatial concentration differences and movement of organisms on chemical concentrations in aquatic biota and TMFs. Model calculated and reported field TMFs showed good agreement for persistent polychlorinated biphenyl (PCB) congeners and biotransformable phthalate esters (PEs) in a marine aquatic food-web. Model testing showed no systematic bias and good precision in the estimation of the TMF for PCB congeners but an apparent underestimation of model calculated TMFs, relative to reported field TMFs, for PEs. A model sensitivity analysis showed that sampling designs that ignore the presence of concentration gradients may cause systematically biased and misleading TMF values. The model demonstrates that field TMFs are most sensitive to concentration gradients and species migration patterns for substances that are subject to a low degree of biomagnification or trophic dilution. The model is useful in anticipating the effect of spatial concentration gradients on the determination of the TMF; guiding species collection strategies in TMF studies; and interpretation of the results of field bioaccumulation studies in study locations where spatial differences in chemical concentration exist.

Concentrations of dioxin-like compounds, primarily polychlorinated dibenzofurans (PCDFs) and polychlorinated dibenzo-p-dioxins (PCDDs), in soils and sediments downstream of Midland, Michigan (USA) were greater than upstream sites and prompted a site-specific hazard assessment of tree swallows breeding in the associated floodplains. Potential for adverse population-level effects from site-specific contaminant exposures were evaluated at study areas (SAs) along the Tittabawassee and Saginaw rivers downstream of Midland. The site-specific multiple lines of evidence approach to hazard assessment included endpoints for dietary- and tissue-based exposures, and population productivity measurements for tree swallows ([TS]; Tachycineta bicolor) measured during the 2005, 2006, and 2007 breeding seasons. Exposure to dioxin-like compounds in TS eggs were some of the greatest recorded and were similar among all upstream and downstream study sites. Conversely, concentrations in nestlings from SAs were significantly greater compared to reference areas (RAs). The pattern of relative concentrations of PCDD/DFs in eggs and nestlings at RAs was dominated by dioxin congeners, whereas at SAs it was dominated by furan congeners. No statistically significant differences were noted in exposure to PCDD/DFs or in population-level responses when compared among locations, and total clutch failures were rare. Hatching success and fledging success were weakly negatively correlated with concentrations of 2,3,7,8-tetrachlorodibenzo-p-dioxin equivalents (TEQs) in individual eggs and nestlings, respectively. On-site concentrations of TEQs in floodplain soils were some of the greatest ever reported in the environment, and several lines of evidence indicate potential population-level effects on TS overall reproductive productivity.

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Dietary exposure of house wrens (Troglodytes aedon), tree swallows (Tachycineta bicolor), and eastern bluebirds (Sialia sialis) to polychlorinated dibenzofurans (PCDFs) and polychlorinated dibenzo-p-dioxins (PCDDs) near Midland, Michigan (USA) was evaluated based on site-specific data, including concentrations of Assess (2011) 172:91-112 dietary concentrations for nestlings at study areas (SAs) were 6-to 20-fold and 2-to 9-fold greater than at proximally located reference areas (RAs), respectively. Average ingestion values of total 2,3,7,8-tetrachlorodibenzo-p-dioxin equivalents (TEQ WHO−Avian ) from site-specific bolus-based and food web-based dietary concentrations for nestlings at SAs were 31-to 121-fold and 9-to 64-fold greater than at proximally located RAs, respectively. Estimates of PCDD/DFs and TEQ WHO−Avian tissue concentrations based on nestling dietary exposures were greater than those measured. Plausible explanations include nestling metabolism of 2,3,7,8-tetrachlorodibenzofuran and assimilation rates of less than the 70% assumed to occur over the nestling growth period. Profiles of the relative concentrations of individual PCDD/DF congeners in samples of invertebrates and bolus at SAs on the Tittabawassee River downstream of the source of contamination were dominated by 1,2,3,4,6,7,8,9-octachlorodibenzo-p-dioxin (22% to 44%) and 2,3,7,8-tetrachlorodibenzofuran (18% to 50%).