Distribution behaviour in body compartments and in ovo transfer of flame retardants in North American Great Lakes herring gulls.

Polybrominated diphenyl ethers (PBDEs) and other halogenated flame retardants (HFRs) continue to be an environmental concern. In the Laurentian Great Lakes, herring gulls (Larus argentatus) are an important wildlife sentinel species, although very little information is available regarding the body distribution (limited to e.g. liver and blood) of these contaminants and in relation to depuration via in ovo transfer. Maternal transfer rates and distribution were presently determined in six body compartments from eight female, Great Lakes herring gulls and separate egg compartments from their entire clutch. Among the 25 PBDEs and 23 non-PBDE HFRs assessed, only six PBDE congeners (BDE-47/99/100/153/154/209), hexabromocyclododecane (HBCDD), and Dechlorane Plus (syn- and anti-DDC-CO) were frequently detectable and quantifiable. Σ6BDE concentrations were an order of magnitude greater than non-PBDE HFR concentrations, and were greatest in the adipose (9641 ± 2436 ng/g ww), followed by egg yolk (699 ± 139 ng/g ww) > muscle (332 ± 545 ng/g ww) > liver (221 ± 65 ng/g ww) > plasma (85.4 ± 20.4 ng/g ww) > brain (54.6 ± 10.6 ng/g ww) > red blood cells (RBCs; 23.5 ± 5.6 ng/g ww) > albumen (7.3 ± 1.3 ng/g ww). Σ2DDC-CO and HBCDD were frequently below the method limit of quantification in the brain, RBCs, plasma, and albumen. Additionally, novel methoxylated-polybrominated diphenoxybenzene contaminants were detected and quantified in herring gull tissues and eggs. The primary difference in PBDE congener profiles was the resistance of both BDE-153 and -154 towards accumulation in the brain, and a corresponding increase in BDE-209 accumulation, which may suggest congener-specific differences in crossing the blood-brain barrier in herring gulls. Maternal transfer rates of PBDEs and non-PBDE HFRs were low (∼4.7 and ∼2.9 % respectively), suggesting that in ovo transfer is not a significant mode of depuration for these compounds.

Uptake, distribution, depletion, and in ovo transfer of isomers of hexabromocyclododecane flame retardant in diet-exposed American kestrels (Falco sparverius).

Hexabromocyclododecane (HBCDD) is a flame retardant and a global contaminant, yet the toxicokinetics of HBCDD diastereoisomers remains unknown in wildlife species. The present study examined in captive American kestrels (Falco sparverius) (diastereo) isomer-specific HBCDD uptake, depletion, tissue distribution, and transfer to eggs in a dietary dosing study with an HBCDD technical mixture (HBCDD-TM). Adult tissue and plasma collections were from separate cohorts of unpaired individual males (n = 10) and females (n = 10) exposed for 21 d to 800 ng/g wet weight of HBCDD-TM (in safflower oil and injected into their cockerel [brain] diet), followed by a 25-d depuration period. A separate cohort of 12 males only was used for control adult tissue and plasma collections. For egg collections, separate cohorts of 11 control pairs (n = 22 birds) and 20 HBCDD-exposed pairs (n = 40 birds) were allowed to breed, and their eggs were collected (n = 19 exposed eggs and n = 10 control eggs). The sum (Σ) HBCDD concentrations were near or below detection (<0.01-0.1 ng/g wet wt) in all control samples but quantifiable in all samples from exposed birds (no differences [p > 0.05] between males and females). Arithmetic mean ΣHBCDD concentrations were highest in fat >> eggs > liver > plasma. The mean ΣHBCDD depletion rate in plasma between the uptake and depuration periods was estimated to be 0.22 ng/g/d with a half-life of approximately 15 d. The γ-HBCDD diastereoisomer was >60% of the ΣHBCDD in plasma after the uptake period and similar to the HBCDD-TM (∼80%). After the depuration period, α-HBCDD was >70% of the HBCDD in plasma, fat, liver, and eggs; and this α-HBCDD domination indicated isomer-specific accumulation as a result of selective metabolism, uptake, protein binding, and/or in ovo transport.

Biological monitoring of PCDD/Fs and PCBs in the City of Mataró. A population-based cohort study (1995-2012).

There is great concern about the exposure to PCDD/Fs in areas near solid waste incineration (SWI) plants as, in the past, thermal waste treatment was a major source of PCDD/Fs, affecting negatively the environment and the population living nearby the area of influence. The aim of the present study was to monitor PCDD/Fs and PCBs levels in blood samples in general population living nearby a modern SWI. Up to 7 different campaigns were performed between 1995 and 2012. Overall, 104 exposed subjects (living <1000 m from the incinerator plant) and 97 non-exposed subjects (living >3000 m from the incinerator plant) were randomly selected from the municipal census of the City of Mataró in 1995. In addition, workers of the SWI plant were included in the study. Moreover, in 1999, 100 non-exposed subjects living in the nearby City of Arenys de Mar were added to the project. Overall, this study represents the longest consecutive human biomonitoring study of dioxins, furans and PCBs ever conducted in Spain. Concentrations of PCDD/Fs and PCBs were determined according to age, sex and distance to the SWI exposure in whole blood sample pools. No relevant differences in PCDD/Fs and PCBs levels were observed between SWI exposure groups. It could be noted that since 1999 all groups experienced a slight decrease in the levels of PCDD/Fs and marker PCBs. Moreover, concentrations of PCDD/Fs and marker PCBs were higher in women than in men, and in older age group in comparison to the younger ones.

A rapid method for screening of the Stockholm Convention POPs in small amounts of human plasma using SPE and HRGC/HRMS.

A rapid analytical screening method allowing simultaneous analysis of 23 persistent organic pollutants (POPs) in human plasma was developed. Sample preparation based on solid-phase extraction (SPE) with additional clean-up using small multilayer silica gel columns. SPE was performed using a custom made polystyrene-divinylbenzene sorbent for the extraction of chlorinated and brominated POPs. Special efforts to reduce sample volume and improve speed and efficiency of the analytical procedure were made. Determination of 16 polychlorinated biphenyls (PCBs), 5 organochlorine (OC) pesticides, octachlorinated dibenzo-p-dioxin (OCDD) and polybrominated diphenyl ether (BDE #47) in 0.5 mL human plasma was performed by using high resolution gas chromatography coupled to high resolution mass spectrometry (HRGC/HRMS). Recovery of POPs ranged between 46% and 110%, and reproducibility was below 25% relative standard deviation (RSD) for all target compounds, except for trans-nonachlor and OCDD, which were present only at low levels. Limits of detection (LOD) were for the PCBs between 0.8 and 117.7 pg mL(-1) plasma and for the OC pesticides between 5.9 and 89.1 pg mL(-1) plasma. The LOD for OCDD and BDE #47 were 1.4 pg mL(-1) plasma, and 9.2 pg mL(-1) plasma, respectively. The presented method was successfully applied to 1016 human plasma samples from an epidemiological study on cardiovascular disease.