Polychlorinated dibenzo-p-dioxins, polychlorinated dibenzofurans and non-ortho-PCBs in eggs of white-tailed sea eagles collected along the Swedish coast in the Baltic Sea.

Concentrations of polychlorinated dibenzo-p-dioxins (PCDD), polychlorinated dibenzofurans (PCDF), and dioxin-like non-ortho-PCBs were measured in white-tailed sea eagle (WTSE) eagle eggs collected along the Swedish coast of the Baltic Sea during the period 1992-2004. The eggs represent two different subpopulations with significantly different nestling brood sizes; the Baltic Proper (BP) with an approximately normal nestling brood size (1.62), and the south Bothnian Sea (sBS) with reduced nestling brood size (1.22) combined with a significantly higher rate of dead eggs. The aim was to investigate if this difference in reproductive outcome was linked to differences in exposure to dioxin-like compounds. Three eggs collected in Greenland in 2000 were included in the study to provide a reference sea eagle population outside of the Baltic Sea region. The concentrations of ∑PCDD, ∑PCDF and ∑non-ortho-PCB in the two subpopulations from the Baltic Sea (BS) region ranged from 0.41-4.1, 1.2-5.3 and 180-970 ng/g lipids, respectively, while in the Greenland population the ranges were 0.11-0.16, 0.22-0.33 and 57-83 ng/g lipid, respectively. 2,3,4,7,8-PCDF was the predominant congener in all areas and accounted for on average 31-49% of the total ∑PCDD/F concentrations. The total toxic equivalents (TEQ) in sBS WTSEs were higher (approximately 39 ng TEQ/g lipid) than reported in eggs for many other birds, and the major contributors to the TEQ in the Baltic Sea were the non-ortho-PCBs. A principal component analysis (PCA) showed a difference in congener pattern between the two Baltic regions that was statistically significant (Hotelling's T(2) test). We found no significant differences in the total TEQ between the two populations (sBS-BP) and thus no evidence was found linking the reproductive impairment in WTSE in sBS to the concentrations of PCDD/Fs or non-ortho-PCBs in the eggs.

Comparison of organohalogen compounds in a white-tailed sea eagle egg laid in 1941 with five eggs from 1996 to 2001.

Eggs laid by white-tailed sea eagles (Haliaeetus albicilla), one in 1941 and five eggs between 1996 and 2001, all from the same geographical region of the Baltic Sea, were screened for organohalogen substances. The 1941 egg contained hexachlorobenzene (HCB), but did not contain either of the pesticides hexachlorocyclohexane (HCH) or p,p'-DDT, nor any metabolites of the latter. In contrast, the more recent eggs (REs) contained all of these compounds. Of the seven polychlorinated biphenyls (PCBs) analyzed (CB28, -52, -101, -118, -138/-163, -153 and 180), only the more highly chlorinated congeners were detected in the 1941 sample, with CB153 followed by CB180 showing the highest concentrations. All eggs demonstrated the same congener pattern with respect to the more highly chlorinated PCBs, but concentrations were approximately 70-230 times higher in the REs. All of the polychlorinated-p-dioxin and dibenzofuran (PCDD/Fs) congeners analyzed were detected in the eggs, with the dominant congener being 2,3,4,7,8-PeCDF (1250pg/gl.w. in 1941 and 1540pg/gl.w. (GM) for the REs, respectively). None of the other congeners exceeded 400pg/gl.w., and the concentrations of 2,3,7,8-TCDD, 2,3,7,8-TCDF and 1,2,3,7,8-PeCDF were all lower in the REs. None of five congeners of polybrominated diphenyl ethers (PBDEs) found in the REs was detected in the egg from 1941. The three methoxylated brominated diphenyl ethers (MeO-BDEs) analyzed were found at similar levels and with a similar congener pattern in REs as in the egg from 1941. In conclusion, this study has shown the absence of DDE and PBDE and the presence of HCB and PCBs in a white-tailed sea eagle egg laid in 1941, and a strong increase of PCBs, DDE and PBDE in white-tailed sea eagle eggs from the same area in 1996-2001. The MeO-BDEs were found in similar concentrations in the analyzed eggs. The 1941 sample shows substantial concentrations of PCDD/Fs, noteworthy in the same magnitude as in the recent samples, illustrating the historical and recent exposure of these compounds.

Levels of brominated flame retardants and methoxylated polybrominated diphenyl ethers in eggs of white-tailed sea eagles breeding in different regions of Sweden.

Forty-four unhatched eggs from white-tailed sea eagle (Haliaeetus albicilla), collected in four regions in Sweden in 1992-2005, were analysed for contents of polybrominated diphenyl ethers (PBDEs), polybrominated biphenyl (PBB), hexabromocyclododecane (HBCD) and naturally occurring methoxylated polybrominated diphenyl ethers (MeO-PBDEs). Two freshwater areas-Lapland in the arctic zone (LAP) and inland lakes in central and southern Sweden (INL), and two brackish marine areas in the Baltic Sea-the south Bothnian Sea (SB) and the Baltic Proper (BP)-were chosen for comparison of the concentrations and congener distributions in white-tailed sea eagles with different diet and migratory patterns. The geometric mean (GM) concentrations (ng/g lipid weight (l.w.)) of ∑(5)PBDE (BDE-47, -99, -100, -153, and -154) were 720 (LAP), 1500 (INL), 4 100 (SB) and 4 300 (BP), whereas BDE-209 was not detectable in any of the samples. The GM concentrations for HBCD content in LAP, INL, SB and BP were 60, 90, 150 and 140ng/g l.w., respectively, whereas the corresponding values for BB-153 were 20, 30, 100 and 120ng/g l.w. In general, the eggs from all four regions demonstrated similar patterns of PBDE congeners, with concentrations in descending order of BDE-47, -100, -99, -153 and -154. The ∑(3)-MeO-BDEs (6-MeO-BDE47, 2'-MeO-BDE68, 5-Cl-6-MeO-BDE47) for these same regions (as above) were 80, 40, 340 and 240ng/g l.w., respectively. ∑(3)-MeO-BDEs for LAP and INL (freshwaters) were significantly different, whereas those for SB and BP were not. The presence of MeO-PBDEs in all of the inland samples indicates that there is an as-yet-unidentified source of these compounds in the freshwater ecosystem. Between the two more contaminated subpopulations from the Baltic Sea coast, SB showed significantly lower productivity than BP, but no correlation was found between productivity and PBDE, PBB and HBCD at the concentrations found in this study.

The XT-tube extractor: a hollow fiber-based supported liquid membrane extractor for bioanalytical sample preparation.

A new supported liquid membrane extractor for bioanalytical sample preparation is presented. The extractor consists of a polypropylene hollow fiber mounted inside a PTFE tube by means of a cross-connector and a tee-connector. All parts are commercially available, inexpensive, and easily assembled. An organic solvent in the pores of the fiber forms a liquid membrane that separates the sample, which is pumped along the outside of the fiber, from the acceptor phase, which is pumped inside. The length of the hollow fiber may easily be varied to meet different demands on extractive surface and extract volumes. To test the system, the strongly acidic plasticizer/flame retardant metabolite diphenyl phosphate ester (DPhP), with a pKa value of 0.26, was extracted from urine. DPhP was protonated using 4 M hydrochloric acid and extracted into an acceptor phase at pH 9. Thirty extractions were made with the same liquid membrane without any decrease in extraction efficiency and with a relative standard deviation <7%. An analyte concentration enrichment of 5-10 times was achieved in the extraction step, giving a limit of detection (S/N = 3) of 0.014 microg/mL with LC/ESI-MS and 0.18 microg/mL with CE-UV. The effects on extraction efficiency using different sample pH, organic solvents, sample flow rates, and lengths of the fiber were evaluated.