Spatiotemporal patterns and relationships among the diet, biochemistry, and exposure to flame retardants in an apex avian predator, the peregrine falcon.

Flame retardants (FR) are industrial chemicals and some are proven environmental contaminants that accumulate in predatory birds. Few studies have examined the influence of diet on FR profiles in nestling raptors and the possible physiological implications of such FR exposure. The objectives of this research were (1) to determine spatial patterns of ≤ 48 polybrominated diphenyl ether (PBDE) congeners and ≤ 26 non-PBDE FRs, including organophosphate esters (OPEs), in nestling peregrine falcons (Falco peregrinus) across the Canadian Great Lakes-St. Lawrence River Basin (GL-SLR; 2010) and in the eastern Canadian Arctic (2007); (2) to identify temporal changes in FR concentrations from the mid-2000s to 2010 in GL-SLR peregrine nestlings; (3) to investigate the role of diet using stable isotopes on exposure patterns of quantifiable FRs; and (4) to assess possible associations between circulating FRs and total (T) thyroxine (TT4) and triiodothyronine (TT3), tocopherol, retinol and oxidative status (isoprostanes). The summed concentrations of the top 5 PBDEs (Σ5) (BDE-47, -99, -100, -154, -153) were significantly higher in rural nestlings than urban nestlings in the GL-SLR, followed by the eastern Arctic nestlings. The PBDE congener profile of rural nestlings was dominated by BDE-99 (34‰), whereas BDE-209 (31‰) became dominant in the 2010 urban PBDE profile marking a shift since the mid-2000s. Low (ppb) concentrations of 25 novel non-PBDE FRs (e.g., 1,2-bis-(2,4,6-tribromophenoxy)ethane (BTBPE), decabromodiphenylethane (DBDPE)) were measured in the nestlings in at least one region, with the first report in peregrines of 15 novel non-PBDE FRs (e.g., 2-ethyl-1-hyxyl 2,3,4,5-tetrabromobenzoate (EHTBB), pentabromo allyl ether (PBPAE), tetrabromoethylcyclohexane (α-, ß-DBE-DBCH)) as well as of tris (2-butoxyethyl) phosphate (TBOEP) (0-7.5ng/g ww) > tris(2-chloroisopropyl) phosphate (TCIPP) (0.1-5.5ng/g ww) > tris(2-chloroethyl) phosphate (TCEP) (0.02-2.0ng/g ww) > tris(1,3-dichloro-2-propyl) phosphate (TDCIPP) (0-1.0ng/g ww). Within the GL-SLR, the urban nestlings' diet had significantly more terrestrial sources (greater δ13C values) than the broader, more aquatic-based diet of rural peregrines. Dietary source (δ13C) was significantly associated with concentrations of Σ5PBDE, BDE-209, EHTBB, and 2,2-4,4',5,5'-hexabromobiphenyl (BB-153), with trophic level (δ15N) also positively associated with BDE-209 levels. Compared to urban nestlings, the rural nestlings had significantly lower circulating concentrations of thyroxine (TT4), triiodothyronine (TT3), a greater proportion of TT3 relative to TT4 (TT3:TT4), tocopherol and oxidative status (isoprostanes), but higher retinol levels; the most recalcitrant PBDE congener, BDE-153, in combination with low concentrations of some novel FRs, particularly octabromotrimethylphenyllindane (OBIND), may influence circulating thyroid hormones, especially TT4, and retinol levels of peregrine falcon nestlings. These associations of FR-endocrine-biochemical measures suggest possible exposure-related changes in these birds and further study is warranted.

Effects of seabird vectors on the fate, partitioning, and signatures of contaminants in a High Arctic ecosystem.

Seabirds bioaccumulate contaminants from prey, transport them to their nesting sites, and deposit them in their excreta and carcasses, thereby focusing marine-derived contaminants into remote, terrestrial receptor sites. In the case of organochlorine chemicals transported by northern fulmars (Fulmarus glacialis) to a High Arctic seabird colony on Devon Island, Nunavut, Canada (76°13'N, 89°14'W), this contaminant pathway dominates all others. In freshwater ponds below the nesting cliffs, concentrations of organochlorine contaminants characteristic of fulmar input were 2- to 45-fold higher in sediments and water (depending on seabird input to the particular pond) than in ponds remote from the colony. Air-water fugacity quotients for the ponds decreased with seabird input, indicating that fulmar contaminant input shifts air-water partitioning to increasingly favor volatilization to air. Although contaminant evasion from water was favored, direct evidence of it was not detected in air samples. For PCBs, congener profiles of pond sediments or water became more similar to seabird sources as seabird input increased, and less similar to air profiles. Based on measurements of contaminants in fulmars and other local environmental media, this study presents the first application of fugacities and multivariate source apportionment statistics to resolve seabird biological vectors.

Seabird-driven shifts in Arctic pond ecosystems.

Migratory animals such as seabirds, salmon and whales can transport large quantities of nutrients across ecosystem boundaries, greatly enriching recipient food webs. As many of these animals biomagnify contaminants, they can also focus pollutants at toxic levels. Seabirds arguably represent the most significant biovectors of nutrients and contaminants from the ocean to the land, given their sheer numbers and global distribution. However, long-term census data on seabirds are rare. Using palaeolimnological proxies, we show that a colony of Arctic seabirds has experienced climate-induced population increases in recent decades. We then document increasing concentrations of contaminants, including polychlorinated biphenyls and cadmium, in pond sediments that are linked to biotransport by seabirds. Our findings suggest that climate-related shifts in global seabird populations will have the unexpected consequence of restructuring coastal ecosystems.

High arctic ponds receiving biotransported nutrients from a nearby seabird colony are also subject to potentially toxic loadings of arsenic, cadmium, and zinc.

The role of northern fulmars (Fulmarus glacialis) was investigated for the transport of nutrients and trace elements to a series of 10 ponds located along a gradient of seabird influence below a fulmar colony in the high Arctic (Cape Vera, Devon Island, Canada). Phosphorus, Cd, K, Zn, and As were identified as seabird-derived elements, having both a high concentration in fulmar guano and a low concentration in background pond sediments (i.e., a high biogenic enrichment factor). Fluxes of these elements were highest in the pond closest to the colony and declined exponentially with distance. Sediments in several of the ponds exceeded Canadian Sediment Quality Guidelines for the Protection of Aquatic Life set for As (5.9 mg/kg) and Cd (0.6 mg/kg), and in the pond closest to the colony, which receives the most seabird subsidies, sediments contained 343 mg/kg Zn, exceeding the threshold for probable adverse biological effects. Although nutrient subsidies from fulmars create an Arctic oasis at Cape Vera, which supports a variety of flora and fauna, the same biological transport pathway puts at risk some of these species by creating sedimentary As, Cd, and Zn concentrations at this remote site similar to those usually observed only near industrialized locations.

Fate of anthropogenic cyclic volatile methylsiloxanes in a wastewater treatment plant.

The fate of cyclic volatile methylsiloxanes (cVMS) - octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) - was evaluated in a typical secondary activated sludge wastewater treatment plant (WWTP). Water samples (influent, primary effluent, and final effluent) and sludge (primary sludge and waste activated sludge) samples were collected at overnight low, morning high, afternoon low, and evening high flows. Concentrations of cVMS in influents fluctuated with the influent flows, ranging from 0.166 to 1.13 µg L(-1), 3.47-19.3 µg L(-1), and 0.446-3.87 µg L(-1) for D4, D5, and D6, respectively. Mass balance analysis of cVMS showed the average mass of D4, D5, and D6 entering and exiting the plant in influent and effluent, respectively, were 109 g d(-1), 2050 g d(-1), 280 g d(-1), and 1.41 g d(-1), 27.0 g d(-1), 1.90 g d(-1). The total removal efficiency of cVMS was >96%. To elucidate their detailed removal mechanisms, Mackay's fugacity-based treatment plant model was used to simulate the fate of cVMS through the WWTP. Due to the unusual combination of high hydrophobicity and volatility of cVMS, volatilization in the aeration tank and adsorption to sludge were the two main pathways of cVMS removal from water in this WWTP based on the experimental and modeled results. The morning and evening high influent mass flows contributed almost equally at approximately 40% of the total daily cVMS mass, with D5 accounting for the majority of this daily loading.

Human health risk assessment of occupational and residential exposures to dechlorane plus in the manufacturing facility area in China and comparison with e-waste recycling site.

A screening level human health risk assessment based on the worst-case scenario was conducted on the occupational and residential exposures to dechlorane plus (DP) in the manufacturing facility region and an electronic-waste (e-waste) recycling site in China, which are two of the most polluted areas of DP in the world. Total estimated exposure doses (EEDs) via dietary intake, dermal contact, and inhalation was approximately 0.01 mg kg(-1) d(-1) for people living in the manufacturing facility region. In comparison, total EEDs (approximate 0.03 µg kg(-1), d(-1)) were 300-fold lower in people living near an e-waste recycling site in China. Chronic oral, dermal, and inhalation reference doses (RfDs) were estimated to be 5.0, 2.0, and 0.01 mg kg(-1)d (-1), respectively. The oral RfD was markedly greater than Mirex (2×10(-4) mg kg(-1) d(-1)) and decabromodiphenyl ether (BDE-209; 7×10(-3) mg kg(-1) d(-1)), which have been or might be replaced by DP as a flame retardant with less toxicity. Monte Carlo simulation was used to generate the probability densities and functions for the hazard index which was calculated from the EEDs and RfDs to assess the human health risk. The hazard index was three orders of magnitude lower than 1, suggesting that occupational and residential exposures were relatively safe in the manufacturing facility region and e-waste recycling site.

Review of recent advances in research on the toxicity, detection, occurrence and fate of cyclic volatile methyl siloxanes in the environment.

The fate and behavior of cyclic volatile methylsiloxanes (cVMS) octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) in the environment were reviewed. We evaluated their usage data and patterns, physico-chemical properties, toxicology, partitioning and degradation, methods of detection, and concentrations. The use of cVMS as an intermediate in the formation of silicone polymers, personal care and household products has resulted in their widespread environmental exposure; they have been detected in biogas, air, water, soil, biosolid, sediment, and biota samples. Modeled and experimental results suggest that cVMS may be subject to long-range atmospheric transport, but have low potential to contaminate the Arctic. For D4 and D5, there was no evidence of trophic biomagnification in aquatic food webs, while some aquatic organisms demonstrated a high degree of bioconcentration and bioaccumulation. High concentrations of cVMS observed in indoor air and biosolids resulted from point sources. Concentrations of cVMS in water, sediment, and soil were all below their no-observed-effect-concentrations.

Determination of cyclic volatile methylsiloxanes in water, sediment, soil, biota, and biosolid using large-volume injection-gas chromatography-mass spectrometry.

Several methods were developed to detect the cyclic volatile methylsiloxanes (cVMSs) including octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) in water, sediment, soil, biota, and biosolid samples. Analytical techniques employed to optimize measurement of this compound class in various matrices included membrane-assisted solvent extraction in water, liquid-solid extraction for sediment, soil, biota, and biosolid samples. A subsequent analysis of the extract was conducted by large-volume injection-gas chromatography-mass spectrometry (LVI-GC-MS). These methods employed no evaporative techniques to avoid potential losses and contamination of the volatile siloxanes. To compensate for the inability to improve detection limits by concentrating final sample extract volumes we used a LVI-GC-MS. Contamination during analysis was minimized by using a septumless GC configuration to avoid cVMS's associated with septum bleed. These methods performed well achieving good linearity, low limits of detection, good precision, recovery, and a wide dynamic range. In addition, stability of cVMS in water and sediment was assessed under various storage conditions. D4 and D5 in Type-I (Milli-Q) water stored at 4°C were stable within 29d; however, significant depletion of D6 (60-70%) occurred only after 3d. Whereas cVMS in sewage influent and effluent were stable at 4°C within 21d. cVMS in sediment sealed in amber glass jars at -20°C and in pentane extracts in vials at -15°C were stable during 1month under both storage conditions.