Twenty years later: PBDEs in fish from U.S. sites with historically extreme contamination.

Shortly after their production ban PBDE environmental levels retreated from their peak (circa 2000), but rates of decrease appear to be slowing. Therefore, to update environmental PBDE trends, this study re-examined a U.S. riverine system found in 1999 to have the highest PBDE fish tissue (fillet) burdens in the world. Archived 2018-2020 fish tissues were analyzed for PBDEs and results compared to 1999-2000 and 2007 levels. On a positive note, levels decreased by >75% over 20 years. However, PBDEs were still detectable at each collection site (n = 16) and in 93% of the samples. The highest PBDE level (16,300 ng g-1 lipid weight) was observed in fish from the Dan R., downstream from the Hyco R. (where the world's highest level was previously reported). Levels within Hyco R. fish have declined at an annual rate of 30% through 2007. However, reductions during the subsequent 12 years have diminished to only 1.2%. Fillet levels since 2007 actually increased at an estimated annual rate of 8% immediately downstream from the Hyco R. Congener profiles varied between species, likely due to hepatic enzyme debromination, indicating single congener-based health risk evaluations may not be sufficiently protective. Within North America, PBDE fish levels in this freshwater system were twice those of North America's Great Lakes and exceeded by 10-fold those in carp examined from Illinois, USA., another historical hotspot. Average fish PBDE levels also exceed maxima observed in European and Asian riverine systems and were 1000's of times higher than the environmental quality standard (EQS) set by European Parliament (0.0085 ng g-1 wet weight, aquatic biota). Therefore, to protect human health and the environment, PBDE monitoring should remain a priority for regulatory agencies with the goal to identify and eliminate their source and to consider their potential health impacts in the context of other co-existing (emerging and legacy) contaminants.

Prenatal exposure to replacement flame retardants and organophosphate esters and childhood adverse respiratory outcomes.

BACKGROUND: The association of prenatal exposure to organophosphate esters (OPEs) and replacement brominated flame retardants (RBFRs) with respiratory outcomes has not been previously investigated in humans, despite reports that these chemicals can cross the placenta and alter lung development as well as immune functions. METHODS: In a cohort of 342 pregnant women recruited between 2003 and 2006 in the greater Cincinnati, Ohio Metropolitan area, we measured indoor dust OPEs and RBFRs at 20 weeks of gestation and urinary OPEs at 16 and 26 weeks of gestation and at delivery. We performed generalized estimating equations and linear mixed models adjusting for covariates to determine the associations of prenatal OPEs and RBFRs exposures with adverse respiratory outcomes in childhood, reported every six months until age 5 years and with lung function at age 5 years. We used multiple informant modeling to examine time-specific associations between maternal urinary OPEs and the outcomes. RESULTS: Dust concentrations of triphenyl phosphate (TPHP) (RR: 1.40, 95% CI: 1.18-1.66), 2-ethylhexyl-2,3,4,5-tetrabromobenzoate (RR: 1.51, 95% CI: 1.23-1.85), and bis(2-ethylhexyl) tetrabromophthalate (RR: 1.57, 95% CI: 1.28-1.94) were associated with higher risk of wheezing during childhood. Dust TPHP concentrations were associated with higher risk of respiratory infections (RR: 1.43, 95% CI: 1.08-1.94), and dust tris-(2-chloroethyl) phosphate concentrations were associated with hay fever/allergies (RR: 1.11, 95% CI: 1.01-1.21). We also found that dust tris-(2-chloroethyl) phosphate loadings were associated with lower lung function. Urinary OPEs mainly at week 16 of gestation tended to be associated with adverse respiratory outcome, while bis(1-chloro-2-propyl) phosphate and diphenyl phosphate at delivery were associated with lower risk of hay fever/allergies. CONCLUSIONS: In-utero exposure to OPEs and RBFRs may be a risk factor for adverse respiratory outcomes in childhood, depending on the timing of exposure.

Sorption of representative organic contaminants on microplastics: Effects of chemical physicochemical properties, particle size, and biofilm presence.

Microplastic pollution has attracted mounting concerns worldwide. Microplastics may concentrate organic and metallic contaminants; thus, affecting their transport, fate and organismal exposure. To better understand organic contaminant-microplastic interactions, our study explored the sorption of selected polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs), α-hexabromocyclododecane (α-HBCDD), and organophosphate flame retardants (OPFRs) on high-density polyethylene (HDPE) and polyvinylchloride (PVC) microplastics under saline conditions. Sorption isotherms determined varied between chemicals and between HDPE and PVC microplastics. Log Freundlich sorption coefficients (Log KF) for the targeted chemicals ranged from 2.01 to 5.27 L kg-1 for HDPE, but were significantly lower for PVC, i.e., ranging from Log KF data (2.84 - 8.58 L kg-1). Significant correlations between chemicals' Log KF and Log Kow (octanol-water partition coefficient) indicate that chemical-dependent sorption was largely influenced by their hydrophobicity. Sorption was evaluated using three size classes (< 53, 53 - 300, and 300 - 1000 µm) of lab-fragmented microplastics. Particle size did not significantly affect sorption isotherms, but influenced the time to reach equilibrium and the predicted maximum sorption, likely related to microplastic surface areas. The presence of biofilms on HDPE particles significantly enhanced contaminant sorption capacity, indicating more complex sorption dynamics in the chemical-biofilm-microplastic system. Our findings offer new insights into the chemical-microplastic interactions in marine environment.

Microplastics exacerbate virus-mediated mortality in fish.

Microplastics are a persistent and increasing environmental hazard. They have been reported to interact with a variety of biotic and abiotic environmental stressors, but the ramifications of such interactions are largely unknown. We investigated virus-induced mortalities in a commercially important salmonid following exposure to microplastics, plastic microfibers, and natural (non-plastic) microparticles. Microplastics or microparticles alone were not lethal. Mortality increased significantly when fish were co-exposed to virus and microplastics, particularly microfibers, compared to virus alone. This presents the unique finding that microplastics (not natural microparticulate matter) may have a significant impact on population health when presented with another stressor. Further, we found that mortality correlated with host viral load, mild gill inflammation, immune responses, and transmission potential. We hypothesize that microplastics can compromise host tissues, allowing pathogens to bypass defenses. Further research regarding this mechanism and the interplay between microplastics and infectious disease are paramount, considering microplastics increasing environmental burden.

Long-Term Exposure to Environmentally Relevant Doses of Large Polystyrene Microplastics Disturbs Lipid Homeostasis via Bowel Function Interference.

The question of whether long-term chronic exposure to microplastics (MPs) could induce dose- and size-dependent adverse effects in mammals remains controversial and poorly understood. Our study explored potential health risks from dietary exposure to environmentally relevant doses of polystyrene (PS) MPs, through a mouse model and integrated analyses of the interruptions of fecal microbial metagenomes and plasma lipidomes. After 21 weeks of exposure to the MPs (40-100 µm), mice mainly exhibited gut microbiota dysbiosis, tissue inflammation, and plasma lipid metabolism disorder, although no notable accumulation of MPs was observed in the gut or liver. The change of the relative abundance of microbiota was strongly associated with the exposure dose and size of MPs while less significant effects were observed in gut damage and abnormal lipid metabolism. Moreover, multiomics data suggested that the host abnormal lipid metabolism was closely related to bowel function disruptions, including gut microbiota dysbiosis, increased gut permeability, and inflammation induced by MPs. We revealed for the first time that even without notable accumulation in mouse tissues, long-term exposure to MPs at environmentally relevant doses could still induce widespread health risks. This raises concern on the health risks from the exposure of humans and other mammals to environmentally relevant dose MPs.

Polystyrene microplastics reduce abundance of developing B cells in rainbow trout (Oncorhynchus mykiss) primary cultures.

Environmental microplastic pollution (including polystyrene, PS) may have detrimental effects on the health of aquatic organisms. Accumulation of PS microplastics has been reported to affect innate immune cells and inflammatory responses in fish. To date, knowledge on effects of microplastics on the antibody response is still very limited. Here, we investigated effects of small (0.8-20 µm) PS microplastics on the abundance of B lineage cells in primary cultures of developing immune cells from the anterior kidney of rainbow trout. Both purchased PS microbeads and PS microparticles generated from consumer products were used as microplastic sources. We first show that rainbow trout phagocytic B cells efficiently took up small (0.83-3.1 µm) PS microbeads within hours of exposure. In addition, our data revealed that PS microplastic exposure most significantly decreased the abundance of a population of non-phagocytic developing B cells, using both flow cytometry and RT-qPCR. PS microplastics-induced loss of developing B cells further correlated with reduced gene expression of RAG1 and the membrane form of immunoglobulin heavy chains mu and tau. Based on the induced loss of developing B cells observed in our in vitro studies, we speculate that in vivo, chronic PS microplastic-exposure may lead to suboptimal IgM/IgT levels in response to pathogens in teleost species. Considering the highly conserved nature of vertebrate B lymphopoiesis it is likely that PS microplastics will similarly reduce antibody responses in higher vertebrate species, including humans. Further, RAG1 provides an effective biomarker to determine effects of PS microplastics on B cell development in teleost species.

A noninvasive environmental monitoring tool for brominated flame-retardants (BFRs) assisted by conservation detection dogs.

Fecal matter is a useful noninvasive/nondestructive media for evaluating contaminants in wildlife, as residues therein have been observed to correlate with body burdens. Conservation detection dog-handler teams can be used to optimize the acquisition of fecal samples. To build on previous work, sentinel-species' (i.e. mink (Mustela vison) and otter (Lontra canadensis)) fecal matter was opportunistically located by a detection dog team along the tri-river system of Missoula, Montana, USA. Sediments were also collected. Samples were used to develop an analytical method from fecal matter to determine habitat exposure to the brominated flame-retardants (BFRs): polybrominated diphenyl ethers (PBDEs), hexabromocyclododecane (HBCDD), 2-ethylhexyl 2, 3, 4, 5-tetrabromobenzoate (EH-TBB), di (2-ethylhexyl)-2, 3, 4, 5-tetrabromophthalate (BEH-TEBP) and decabromodiphenyl ethane (DBDPE). Sediments contained PBDEs (BDE-99 and BDE-209) and EH-TBB at detection rates of 67%, 33% and 67%, respectively. BDE-99, -209 and EH-TBB were also detected in mink and otter feces, at rates of 81%, 25% and 81%, respectively; plus BEH-TEBP at 13%. BFR levels correlated positively with human population density except along the lower Bitterroot River, where BDE-209 sediment and feces levels exceeded other sites by several orders of magnitude. Fecal matter body burden estimates indicated marginal PBDE exposure. However, exposure to their replacements, EH-TBB and BEH-TEBP, were at levels that may adversely affect healthy Mustelidae populations. Proof-of-concept was achieved; validation results were within established standards for the development of analytical methods. The established application of conservation dog-handler teams to facilitate the collection of fecal matter for BFR analysis represents a valuable, but currently underutilized environmental monitoring tool.

Microplastics affect sedimentary microbial communities and nitrogen cycling.

Microplastics are ubiquitous in estuarine, coastal, and deep sea sediments. The impacts of microplastics on sedimentary microbial ecosystems and biogeochemical carbon and nitrogen cycles, however, have not been well reported. To evaluate if microplastics influence the composition and function of sedimentary microbial communities, we conducted a microcosm experiment using salt marsh sediment amended with polyethylene (PE), polyvinyl chloride (PVC), polyurethane foam (PUF) or polylactic acid (PLA) microplastics. We report that the presence of microplastics alters sediment microbial community composition and nitrogen cycling processes. Compared to control sediments without microplastic, PUF- and PLA-amended sediments promote nitrification and denitrification, while PVC amendment inhibits both processes. These results indicate that nitrogen cycling processes in sediments can be significantly affected by different microplastics, which may serve as organic carbon substrates for microbial communities. Considering this evidence and increasing microplastic pollution, the impact of plastics on global ecosystems and biogeochemical cycling merits critical investigation.

Organophosphate esters in a cohort of pregnant women: Variability and predictors of exposure.

Organophosphate esters (OPEs) are a group of chemicals used as flame retardants and plasticizers that replaced polybrominated diphenyl ethers in consumer products such as furniture and electronics. To characterize exposure to OPEs during fetal development, we measured urinary OPE metabolite concentrations in women twice during pregnancy (16 and 26 weeks' gestation) and at delivery (n = 357). We also previously quantified house dust OPE parent compound concentrations at 20 weeks' gestation (n = 317). Diphenyl phosphate (DPHP) had the highest geometric mean urinary concentrations (1.5-2.3 µg/g creatinine), followed by bis(1,3-dichloro-2-propyl) phosphate (BDCIPP; 0.75-0.99 µg/g creatinine), and bis(2-chloroethyl) phosphate (BCEP; 0.72-0.97 µg/g creatinine), while dibutyl phosphate (DNBP) had the lowest concentrations (0.25-0.28 µg/g creatinine). Urinary OPE metabolites were moderately correlated with each other at 26 weeks (rs: 0.23-0.38, p < 0.001) while the correlations at 16 weeks and delivery were slightly weaker. Intra-class correlations for urinary metabolites measured at three time points were poor (0.16-0.34), indicating high variability within individuals. Dust concentrations of OPE parent compounds were associated with BCEP, BDCIPP, and DPHP concentrations in urine at some but not all time points. In linear mixed models of urinary OPE metabolite concentrations, household size was inversely associated with BCEP concentrations, and being non-white was associated with lower BDCIPP and DPHP concentrations. Urine samples collected in the summer had the highest OPE metabolite concentrations. This study highlights the need to collect multiple urine samples during pregnancy to define exposure patterns and investigate potential periods of susceptibility.

Concentrations and loadings of organophosphate and replacement brominated flame retardants in house dust from the home study during the PBDE phase-out.

Polybrominated diphenyl ethers, a class of flame retardants and endocrine disruptors, have been substituted in new products by organophosphate (OPFR) and replacement brominated flame retardants (RBFR). OPFRs and RBFRs readily migrate from consumer products into dust where humans are exposed via incidental ingestion and inhalation. We quantified concentrations and loadings of OPFRs and RBFRs in house dust samples (n = 317) collected from the homes of Cincinnati women between 2003 and 2006 and examined their associations with demographic and house characteristics. Tris-(1-chloro-2-propyl)-phosphate (TCIPP, geometric mean [GM]: 2140 ng g-1, range: 70.1-166,000 ng g-1), tris-(1,3-dichloro-2-propyl)-phosphate (TDCIPP, GM: 1840 ng g-1, range: 55.2-228,000 ng g-1), triphenyl phosphate (TPHP, GM: 1070 ng g-1, range: 34.1-62,100 ng g-1), 2-ethylhexyl-2,3,4,5-tetrabromobenzoate (EH-TBB, GM: 59.5 ng g-1, range: 2.82-7800 ng g-1), and bis-(2-ethylhexyl)-tetrabromophthalate (BEH-TEBP, GM: 121 ng g-1, range 2.17-13,600 ng g-1) were all detected in >90% of dust samples; tris-(2-chloroethyl)-phosphate (TCEP, GM: 669 ng g-1, range: 56.8-160,000 ng g-1) was detected in 80.1% of samples. Concentrations of EH-TBB and BEH-TEBP increased in house dust from 2003 to 2006. The number of people living in the home, race, education, floor type, and year of sample collection were associated with some OPFR and RBFR concentrations and loadings. This study suggests that OPFRs and RBFRs were ubiquitous in house dust during the PBDE phase-out and justifies more research on the consequences of exposure to these environmental chemicals.

Brominated and organophosphate flame retardants along a sediment transect encompassing the Guiyu, China e-waste recycling zone.

e-Waste recycling using crude techniques releases a complex, yet incompletely characterized mixture of hazardous materials, including flame retardants (FRs), to the environment. Their migration downstream and the associated risks also remain undocumented. We examined 26 FRs (18 brominated (BFRs: 12 polybrominated diphenyl ether (PBDE) congeners, plus 6 alternatives) and 8 organophosphate esters (OPEs)) in surficial sediments of the Lian River. Sampling encompassed the river's origin, through the Guiyu e-waste recycling zone, to its mouth, as well as associated tributaries. OPE exceeded BFR concentrations in most sediments, despite their far greater water solubilities. Among OPEs, tris(1-chloro-2-propyl) phosphate dominated upstream, but shifted to triphenyl phosphate in Guiyu and downstream sediments. For PBDEs, Deca-BDE dominated upstream, but Penta-BDE prevailed in Guiyu and at many downstream sites. Among emerging alternative BFRs, decabromodiphenyl ethane dominated upstream, transitioning to 1,2-bis(2,4,6,-tribromophenoxy)ethane in Guiyu sediments. Penta-BDE (BDE-47 + -99, 668-204,000 ng g-1, ∑PBDEs 2280-287,000 ng g-1), tetrabromobisphenol A (2,720-41,200 ng g-1), 1,2-bis(2,4,6,-tribromophenoxy)ethane (222-9870 ng g-1) and triphenyl phosphate (4260-1,710,000 ng g-1, OPEs 6010-2,120,000 ng g-1) concentrations in Guiyu sediments were among the highest reported in the world to date. The continuing dominance of these e-waste indicative FRs in sediments downstream of Guiyu suggested that FR migration from Guiyu occurred. Hazard quotients >1.0 indicated that the extreme sediment concentrations of individual FRs posed ecological risks in most Guiyu reach and downstream areas. Simultaneous exposure to multiple FRs likely increased risks. However, risks may be mediated if FRs were associated with strong sorbents, e.g. carbon black from burned debris, hydrophobic polymer fragments, or resided as additives within polymer fragments.

Assessment of legacy and emerging contaminants in an introduced catfish and implications for the fishery.

Since introduction into the Chesapeake Bay watershed in the 1970s, blue catfish (Ictalurus furcatus) populations have increased, impacting native species. One strategy suggested to limit their growing numbers is to expand the existing commercial fishery. However, the promotion of human consumption of this large, omnivorous fish may increase exposure to contaminants of concern (COC). However, there are few published data on contaminants in blue catfish. To evaluate this possibility, we measured COC (PCBs, PBDEs, OCs, Hg) in individual fillets and compared levels to established consumption advisory limits. James River (near Richmond, Virginia) and Upper Potomac River (downstream of Washington DC) fish exhibited higher burdens of most COC than those from the lower James and rural Rappahannock rivers. Fish sex and δ15N values (surrogate for trophic position) did not correlate with COC concentrations. Potomac River fish exhibited greatest δ15N, perhaps related to local wastewater inputs. Despite differences in human population densities among watersheds, fish mercury (Hg) levels were similar. Most fillets surpassed US EPA advisory limits for unrestricted consumption (> 16 meals/month) for Hg and PCBs. Hg and PCB advisories in the region typically restrict consumption to two 220 g meals/month. Hence, individuals who rely on fish for a large portion of their diet may be exposed to unacceptable Hg and PCB concentrations. COC levels typically increased with fish length; in particular, fish > 550 mm often exceeded unrestricted consumption limits for chlordanes and DDTs. PBDEs, pentachloroanisole, hexachlorobenzene, and mirex levels were generally below established advisories. However, because fish advisories are based on the expected consequences from single contaminants and a single or limited number of toxicological endpoints, consumers face greater risks due to cumulative effects from all coincident COCs, as well as additional exposure pathways, such as other food and air. The additional data on contaminant levels reported here will increase the accuracy of forecasted risks. However, it also illustrates the complexity in communicating the risks from multi-contaminant exposure.

Examination of contaminant exposure and reproduction of ospreys (Pandion haliaetus) nesting in Delaware Bay and River in 2015.

A study of ospreys (Pandion haliaetus) nesting in the coastal Inland Bays of Delaware, and the Delaware Bay and Delaware River in 2015 examined spatial and temporal trends in contaminant exposure, food web transfer and reproduction. Concentrations of organochlorine pesticides and metabolites, polychlorinated biphenyls (PCBs), coplanar PCB toxic equivalents, polybrominated diphenyl ethers (PBDEs) and other flame retardants in sample eggs were generally greatest in the Delaware River. Concentrations of legacy contaminants in 2015 Delaware Bay eggs were lower than values observed in the 1970s through early 2000s. Several alternative brominated flame retardants were rarely detected, with only TBPH [bis(2-ethylhexyl)-tetrabromophthalate)] present in 5 of 27 samples at <5 ng/g wet weight. No relation was found between p,p'-DDE, total PCBs or total PBDEs in eggs with egg hatching, eggs lost from nests, nestling loss, fledging and nest success. Osprey eggshell thickness recovered to pre-DDT era values, and productivity was adequate to sustain a stable population. Prey fish contaminant concentrations were generally less than those in osprey eggs, with detection frequencies and concentrations greatest in white perch (Morone americana) from Delaware River compared to the Bay. Biomagnification factors from fish to eggs for p,p'-DDE and total PCBs were generally similar to findings from several Chesapeake Bay tributaries. Overall, findings suggest that there have been improvements in Delaware Estuary waterbird habitat compared to the second half of the 20th century. This trend is in part associated with mitigation of some anthropogenic contaminant threats.

Addressing the Issue of Microplastics in the Wake of the Microbead-Free Waters Act-A New Standard Can Facilitate Improved Policy.

The United States Microbead-Free Waters Act was signed into law in December 2015. It is a bipartisan agreement that will eliminate one preventable source of microplastic pollution in the United States. Still, the bill is criticized for being too limited in scope, and also for discouraging the development of biodegradable alternatives that ultimately are needed to solve the bigger issue of plastics in the environment. Due to a lack of an acknowledged, appropriate standard for environmentally safe microplastics, the bill banned all plastic microbeads in selected cosmetic products. Here, we review the history of the legislation and how it relates to the issue of microplastic pollution in general, and we suggest a framework for a standard (which we call "Ecocyclable") that includes relative requirements related to toxicity, bioaccumulation, and degradation/assimilation into the natural carbon cycle. We suggest that such a standard will facilitate future regulation and legislation to reduce pollution while also encouraging innovation of sustainable technologies.

Human Indoor Exposure to Airborne Halogenated Flame Retardants: Influence of Airborne Particle Size.

Inhalation of halogenated flame-retardants (HFRs) released from consumer products is an important route of exposure. However, not all airborne HFRs are respirable, and thus interact with vascular membranes within the gas exchange (alveolar) region of the lung. HFRs associated with large (>4 µm), inhalable airborne particulates are trapped on the mucosal lining of the respiratory tract and then are expelled or swallowed. The latter may contribute to internal exposure via desorption from particles in the digestive tract. Exposures may also be underestimated if personal activities that re-suspend particles into the breathing zone are not taken into account. Here, samples were collected using personal air samplers, clipped to the participants' shirt collars (n = 18). We observed that the larger, inhalable air particulates carried the bulk (>92%) of HFRs. HFRs detected included those removed from commerce (i.e., polybrominated diphenyl ethers (Penta-BDEs: BDE-47, -85, -100, -99, and -153)), their replacements; e.g., 2-ethylhexyl 2,3,4,5-tetrabromobenzoate (TBB or EH-TBB); bis(2-ethylhexyl) 3,4,5,6-tetrabromophthalate (TBPH or BEH-TEBP) and long-produced chlorinated organophosphate-FRs (ClOPFRs): tris(2-chloroethyl)phosphate (TCEP), tris(1-chloro-2-propyl)phosphate (TCPP or TCIPP), and tris(1,3-dichloro-2-propyl)phosphate (TDCPP or TDCIPP). Our findings suggest estimates relying on a single exposure route, i.e., alveolar gas exchange, may not accurately estimate HFR internal dosage, as they ignore contributions from larger inhalable particulates that enter the digestive tract. Consideration of the fate and bioavailability of these larger particulates resulted in higher dosage estimates for HFRs with log Koa < 12 (i.e., Penta-BDEs and ClOPFRs) and lower estimates for those with log Koa > 12 (i.e., TBB and TBPH) compared to the alveolar route exposure alone. Of those HFRs examined, the most significant effect was the lower estimate by 41% for TBPH. The bulk of TBPH uptake from inhaled particles was estimated to be through the digestive tract, with lower bioavailability. We compared inhalation exposure estimates to chronic oral reference doses (RfDs) established by several regulatory agencies. The U.S. Environmental Protection Agency (EPA) RfD levels for several HFRs are considered outdated; however, BDE-99 levels exceeded those suggested by the Dutch National Institute for Public Health and the Environment (RIVM) by up to 26 times. These findings indicate that contributions and bioavailability of respirable and inhalable airborne particulates should both be considered in future risk assessments.

Chesapeake Bay fish-osprey (Pandion haliaetus) food chain: Evaluation of contaminant exposure and genetic damage.

From 2011 to 2013, a large-scale ecotoxicological study was conducted in several Chesapeake Bay (USA) tributaries (Susquehanna River and flats, the Back, Baltimore Harbor/Patapsco Rivers, Anacostia/ middle Potomac, Elizabeth and James Rivers) and Poplar Island as a mid-Bay reference site. Osprey (Pandion haliaetus) diet and the transfer of contaminants from fish to osprey eggs were evaluated. The most bioaccumulative compounds (biomagnification factor > 5) included p,p'-dichlorodiphenyldichloroethylene (DDE), total polychlorinated biphenyls (PCBs), total polybrominated diphenyl ethers (PBDEs), and bromodiphenyl ether (BDE) congeners 47, 99, 100, and 154. This analysis suggested that alternative brominated flame retardants and other compounds (methoxytriclosan) are not appreciably biomagnifying. A multivariate analysis of similarity indicated that major differences in patterns among study sites were driven by PCB congeners 105, 128, 156, 170/190, and 189, and PBDE congeners 99 and 209. An integrative redundancy analysis showed that osprey eggs from Baltimore Harbor/Patapsco River and the Elizabeth River had high residues of PCBs and p,p'-DDE, with PBDEs making a substantial contribution to overall halogenated contamination on the Susquehanna and Anacostia/middle Potomac Rivers. The redundancy analysis also suggested a potential relation between PBDE residues in osprey eggs and oxidative DNA damage in nestling blood samples. The results also indicate that there is no longer a discernible relation between halogenated contaminants in osprey eggs and their reproductive success in Chesapeake Bay. Osprey populations are thriving in much of the Chesapeake, with productivity rates exceeding those required to sustain a stable population. Environ Toxicol Chem 2016;35:1560-1575. Published 2016 Wiley Periodicals Inc. on behalf of SETAC. This article is a US Government work and, as such, is in the public domain in the United States of America.

Hexabromocyclododecane flame retardant in Antarctica: Research stations as sources.

Historical persistent organic pollutants (POPs) are banned from Antarctica under international treaty; but contemporary-use POPs can enter as additives within polymer and textile products. Over their useful lives these products may release additives in-situ. Indeed, we observed 226 and 109 ng/g dry weight (dw) of the total concentrations of α-, ß- and γ-hexabromocyclododecane (HBCD) in indoor dust from McMurdo Station (U.S.) and Scott Station (New Zealand), respectively. Sewage sludge collected from wastewater treatment facilities at these stations exhibited ∑HBCD of 45 and 69 ng/g dw, respectively. Contaminants originally within the bases may exit to the local outdoor environment via wastewaters. Near McMurdo, maximum ∑HBCD levels in surficial marine sediments and aquatic biota (invertebrates and fish) were 2350 ng/g (total organic carbon basis) and 554 ng/g lipid weight, respectively. Levels declined with distance from McMurdo. Our results illustrate that Antarctic research stations serve as local HBCD sources to the pristine Antarctic environment.

Decadal re-evaluation of contaminant exposure and productivity of ospreys (Pandion haliaetus) nesting in Chesapeake Bay Regions of Concern.

The last large-scale ecotoxicological study of ospreys (Pandion haliaetus) in Chesapeake Bay was conducted in 2000-2001 and focused on U.S. EPA-designated Regions of Concern (ROCs; Baltimore Harbor/Patapsco, Anacostia/middle Potomac, and Elizabeth Rivers). In 2011-2012, ROCs were re-evaluated to determine spatial and temporal trends in productivity and contaminants. Concentrations of p,p'-DDE were low in eggs and below the threshold associated with eggshell thinning. Eggs from the Anacostia/middle Potomac Rivers had lower total PCB concentrations in 2011 than in 2000; however, concentrations remained unchanged in Baltimore Harbor. Polybrominated diphenyl ether flame retardants declined by 40%, and five alternative brominated flame retardants were detected at low levels. Osprey productivity was adequate to sustain local populations, and there was no relation between productivity and halogenated contaminants. Our findings document continued recovery of the osprey population, declining levels of many persistent halogenated compounds, and modest evidence of genetic damage in nestlings from industrialized regions.

Halogenated flame-retardant concentrations in settled dust, respirable and inhalable particulates and polyurethane foam at gymnastic training facilities and residences.

Halogenated flame-retardants (FRs) are used in a wide array of polymer-containing products. Animal studies and structure-activity modeling exercises suggest that FR exposure may result in detrimental toxicological effects. Workers with extended contact with such polymers (e.g., electronic dismantlers, carpet installers and aircraft personnel) have previously been observed to exhibit elevated body burdens of FRs, e.g., polybrominated diphenyl ethers (PBDEs). Recently, elevated PBDE blood levels were also reported in a non-occupational exposure group, gymnasts. These levels were hypothesized to be related to the large volumes of FR-treated polyurethane foam in gymnastics facilities. To further our understanding of workers' potential exposure, we analyzed FR concentrations in indoor dust and size-fractionated air particulates (respirable (<4 µm) and inhalable (>4 µm)) from gymnastic studios. Values were compared to samples from the homes of coaches employed at these facilities. Polyurethane foam blocks (i.e., pit foam) were also analyzed to characterize potential FR sources. FRs examined included those used to flame-retard polyurethane foam: 8 PBDE congeners, two brominated components of Firemaster 550 (2-ethylhexyl 2, 3, 4, 5-tetrabromobenzoate (TBB) and bis(2-ethylhexyl) 3, 4, 5, 6-tetrabromophthalate (TBPH)) and three chlorinated organophosphates (tris(2-chloroethyl) phosphate (TCEP), tris(1-chloro-2-propyl) phosphate (TCPP) and tris(1,3-dichloro-2-propyl) phosphate (TDCPP)). Several additional FRs not used in polyurethane were also evaluated. These have also been detected in indoor dust and air and may also lead to adverse health effects. These include: BDE-183 and its replacement product (1, 2-bis(2, 4, 6-tribromophenoxy) ethane (BTBPE), two congeners of the deca-BDE formulation (BDE-206, -209) and their replacement decabromodiphenyl ethane (DBDPE) and hexabromocyclododecane (α-, ß-, γ-HBCD), and tetrabromobisphenol-A (TBBPA)). Pit foam contained multiple FRs at cumulative concentrations of 12,100 to 25,800 µg g(-1), or 1.2% to 2.6% by weight. TBB and TBPH were the most abundant FRs detected, followed by TDCPP and several PBDEs. The mean total FR burden detected at the gyms was 8.6-fold higher (574 µg g(-1)) than that observed in the house dust samples (66.8 µg g(-1)). However, the polyurethane additives TBB and TDCPP were the only FRs that exhibited significantly greater levels (P<0.05) in gym than house dust. Mean levels of five FRs (BDE-99, -100, -153, -209 and TDCPP) were also higher in respirable particulates from the gyms than the homes and four FRs (BDE-47, TBB, TBPH and DBDPE) were higher at the homes than the gyms; these differences were not significant (P>0.05). Several additional FRs were detected in inhalable particulates; mean levels of BDE-66, -206 and TCPP were higher in the homes and BDE-47, -85, -99, -100, -153, -209, TBB, TBPH, and TDCPP were higher at the gyms. But, only the polyurethane additives i.e., BDE-100, TBB and TDCPP were significantly greater (P<0.05) in inhalable particulates from the gyms than at the homes. In conclusion, polyurethane foam collected from gymnastic studios exhibited a variety of FR compositional signatures; likely reflective of changes in FR usage over time and by different manufacturers. FR concentrations and compositional signatures also differed between settled dust, respirable and inhalable particulates between the gyms and homes. Concentrations of FRs used in polyurethane foam were higher in gym air and dust compared to homes, particularly TBB and TDCPP - which were also the primary FRs detected in the pit foam samples. Although these results should be interpreted with caution, as the sample size was small, these findings do suggest that FR concentrations observed in dust and air particulates from the gymnastic studios are further evidence that individuals frequenting these environments are at greater risk for exposure to these polymer additives.