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Since 2000, a surprisingly high number of macroscopical gonad alterations has been reported in whitefish (Coregonus spp.) from Lake Thun, Switzerland. This unique phenomenon is still unexplained and has received much public attention. As one possible trigger for these effects, the presence of persistent, bioaccumulative and toxic compounds acting as endocrine disruptors in the lake has been discussed. In this study, concentrations of selected persistent organic pollutants were examined in two morphs of whitefish from Lake Thun and their link to the observed abnormalities was investigated. Analyzed compound classes included polychlorinated biphenyls, polychlorinated dibenzo-p-dioxins and dibenzofurans, polychlorinated naphthalenes, polybrominated diphenyl ethers and hexabromocyclododecanes. The target substances were identified in all samples and concentrations of the analyzed compounds were highly correlated among each other. These correlations show that the analyzed substances have the same distribution pattern throughout the lake and that uptake, accumulation and elimination processes are similar. Significant differences in contaminant levels within the samples existed between the two analyzed morphs of whitefish, most likely due to different age, food patterns and growth rate. No difference in contaminant levels was observed between fish with abnormal gonads and fish with normal gonads, suggesting no causal link between the investigated lipophilic organohalogen compounds present in fish and the observed gonad abnormalities in whitefish from Lake Thun. A comparison to existing data shows that concentrations in Lake Thun whitefish are at the lower bound of contaminant levels in whitefish from Swiss lakes or from European waters.

Hexabromocyclododecanes (HBCDs) are high production volume chemicals (>20000 ty(-1)) used as flame retardants for plastics and textiles. Lately, we reported on the stereoselective isomerization of beta-HBCDs. Herein we present insights into the mechanism and kinetics of (+)gamma- to (+)alpha- and of (-)gamma- to (-)alpha-HBCD isomerization. Only two of the six bromine atoms migrated, indicating that rearrangements of gamma- to alpha-HBCDs are regio- and stereoselective as well. The apparent first-order isomerization rate constants increased from 0.0013 to 0.0031 to 0.0070 min(-1) at 120, 130, and 140 degrees C, respectively, corresponding to half-lives of 540, 230, and 99 min. Thus, a thermal treatment of materials containing gamma-HBCDs at temperatures >100 degrees C may induce the formation of alpha-HBCDs and, hence, may alter the diastereomeric ratio of a HBCD mixture. The inversion of vicinal dibromides in like-configurations (RR/SS) prevailed, whereas unlike-configurations (RS/SR) were not affected. An intramolecular, stereoselective migration of neighboring bromine atoms via a four-center transition state would explain the observed stereoisomer pattern and first-order kinetics. Despite the fact that vicinal dibromides in HBCDs prefer synclinal (gauche) conformations, antiperiplanar (staggered) conformations are assumed to facilitate concerted 1.2-shifts of both bromine atoms. A conformation analysis revealed that under kinetic control, only those bromine atoms in the more flexible part of the molecules are migrating, whereas those in the conserved triple-turn motive were not affected. Thus, this structural motive, common to all alpha-, beta-, and gamma-HBCDs, is more rigid and less reactive than the flexible part, containing the reacting dibromides in like-configurations.

With the recent ban of pentabromodiphenyl ether (technical PentaBDE) and octabromodiphenyl ether (technical OctaBDE) mixtures in the European Union (EU) and in parts of the United States, decabromodiphenyl ether (technical DecaBDE) remains as the only polybrominated diphenyl ether (PBDE) based flame retardant available, today. The EU risk assessment report for DecaBDE identified a high level of uncertainty associated with the suitability of the current risk assessment approach for secondary poisoning by debromination of DecaBDE to toxic lower brominated diphenylethers. Addressing this still open question, we investigated concentrations and temporal trends of DecaBDE, NonaBDE, and OctaBDE congeners in the sediments of Greifensee, a small lake located in an urban area close to Zürich, Switzerland. PBDE appeared first in sediment layers corresponding to the mid 1970s. While total Tri-HeptaBDE (BDE-28, -47, -99, -100, -153, -154 and -183) concentrations leveled off in the mid 1990s to about 1.6 ng/g dw (dry weight), DecaBDE levels increased steadily to 7.4 ng/g dw in 2001 with a doubling time of 9 years. Hexabromocyclododecanes (HBCD) appeared in Greifensee sediments in the mid 1980s. They are an important class of flame retardants that are being used in increasing amounts, today. As was observed for DecaBDE, HBCD concentrations were continuously increasing to reach 2.5 ng/g dw in 2001. Next to DecaBDE, all 3 NonaBDE congeners (BDE-208, BDE-207, and BDE-206) and at least 7 out of the 12 possible OctaBDE congeners (BDE-202, BDE-201, BDE-197/204, BDE-198/203, BDE-196/200, BDE-205, and BDE-194) were detected in the sediments of Greifensee. Highest concentrations were found in the surface sediments with 7.2, 0.26, 0.14, and 1.6 ng/g dw for Deca-, Nona-, Octa-, and the sum of Tri-HeptaBDE, respectively. While DecaBDE and NonaBDE were found to increase rapidly, the increase of OctaBDE was slower. Congener patterns of Octa- and NonaBDE present in sediments of Greifensee did not change with time. Consequently, there was no evidence for sediment mediated long-term transformation of PBDE within the observed time span of almost 30 years. Despite the high persistence of DecaBDE, environmental debromination occurs, as shown by the detection of a shift in congener patterns of Octa- and NonaBDE in sediments, compared to the respective congener patterns in technical PBDE products. The OctaBDE congener BDE-202 was detected in sediments, representing a transformation product that is not reported in any of the technical PBDE products. Comparison of OctaBDE congener patterns in sediments with OctaBDE congener patterns from known sources reveals that (i) they were distinctively different from the congener patterns in technical PBDE products and (ii) that they were similar to the OctaBDE patterns in house dust and photodegradation products of DecaBDE, suggesting contributions from these sources.

Hexabromocyclododecanes (HBCDs) are high production volume chemicals currently produced in quantities exceeding 20000ty(-1). They are used as flame retardants for plastics and textiles. HBCDs are thermally labile compounds, rapidly decomposing at temperatures above 250 degrees C to form bromine radicals, which scavenge other radicals formed during pyrolysis. But certain HBCD stereoisomers must reach the environment without decomposition, because their levels in soils, sediments, and biota are increasing worldwide. The fate of individual HBCD stereoisomers during production, product use, disposal, and transformation in the environment remains unclear. Herein we report on the thermally induced, highly selective isomerization of (+) and (-)beta-HBCD. Regio- and stereoselective migration of only two of the six bromine atoms resulted in the racemization of both beta-HBCDs. First order rate constants (k(rac)) increased from 0.005, 0.011, 0.021, to 0.055min(-1) at 130, 140, 150, and 160 degrees C, corresponding to half life times tau(1/2) of 143, 63, 29, and 14min, respectively. From the deduced kinetic model, we conclude that any thermal treatment of enantiomerically enriched beta-HBCDs in the range of 100-160 degrees C will result in a loss of most optical activity within few hours. The simultaneous inversion of two asymmetric centers occurred with perfect stereocontrol. Selectively, vicinal dibromides with the RR- and the SS-configurations migrated at these temperatures. An intramolecular reaction mechanism with a four-center transition state is postulated, based on the obtained stereoisomer pattern and the observed reaction kinetics. Crystal structure analysis revealed that all vicinal dibromides in beta-HBCDs prefer synclinal (gauche) conformations. However, an antiperiplanar (staggered) conformation is assumed to facilitate the concerted 1.2-shifts of both bromine atoms, resulting in an inversion of both neighboring carbon atoms. First experiments with other HBCD stereoisomers suggest that the presented isomerization mechanism is of relevance for those stereoisomers as well.

Hexabromocyclododecanes (HBCDs) are high production volume chemicals used as flame retardants for plastics and textiles. They are currently produced in quantities exceeding 20,000 t/y. Despite this fact, the correct stereochemistry of most HBCDs is still not known. Six stereocenters are formed during bromination of cyclododecatrienes, resulting in mixtures of different stereoisomers. Considering all elements of symmetry, 16 different stereoisomers including six pairs of enantiomers as well as 4 meso forms are possible theoretically. Recently, we isolated 8 of the 16 possible stereoisomers from a technical HBCD mixture and assigned their relative configurations. Herein, we report on the isolation of 6 enantiomerically pure alpha-, beta-, and gamma-HBCDs, obtained from preparative chiral-phase liquid chromatography, and we present their absolute configurations, which were determined from X-ray diffraction analysis. The absolute configuration of (-) alpha-HBCD was found to be (1R,2R,5S,6R,9R,10S), while the one of (+) beta-HBCD is assigned to (1S,2S,5S,6R,9S,10R), whereas the one of (-) gamma-HBCD corresponds to (1S,2S,5S,6R,9R,10S). The given structural information allows the unambiguous identification of the six most important HBCD stereoisomers, which typically account for more than 95% of technical HBCDs. In addition, we compared the solid-state conformations of racemic and enantiomerically pure alpha-, beta-, and gamma-HBCDs. In all cases, vicinal dibromides adopted a synclinal (sc) conformation with torsion angles of 69+/-6 degrees. A unique structural motive was common to all examined HBCD solid-state conformations. This conserved structure was described as an extended triple turn consisting of an arrangement of three pairs of synclinal and two antiperiplanar torsion angles.

Remote alpine lakes do not receive any direct aquatic inputs from anthropogenic activities. Therefore, these ecosystems may receive persistent organic compounds (POPs) by direct atmospheric deposition, only. Consequently, fish dwelling in these ecosystems represent an excellent indicator for the long-term atmospheric input of bioaccumulating and persistent contaminants. In the present study, fish from seven remote alpine lakes, located between 2062 and 2637 m above sea level in south eastern Switzerland (Grisons), were investigated. Lipid-based fish tissue concentrations of pesticides including dichlorodiphenyltrichloroethane (DDT) and its transformation products (2,4'-DDT, 4,4'-DDT, 2,4'-dichlorodiphenyldichloroethane (DDD), 4,4'-DDD, 2,4'-dichlorodiphenyldichloroethene (DDE), 4,4'-DDE), as well as dieldrin, heptachlor exo-epoxide (HPEX), hexachlorobenzene (HCB), hexachlorocyclohexanes (HCH), polychlorinated biphenyls (PCB), polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/F), and polybrominated diphenyl ethers (PBDE) were measured. In addition, seven synthetic musk compounds (Crysolide (ADBI), Phantolide (AHMI), Fixolide (AHTN), Traseolide (ATII), Galaxolide (HHCB), musk ketone (MK), and musk xylene (MX)) were determined. Concentrations of PCB, PCDD/F, and PBDE were in the same range as in fish from the major lakes situated in the Swiss plateau, indicating mainly atmospheric input of these persistent compounds. In contrast, concentrations of synthetic musks which are used as fragrances in laundry detergents and cosmetic products were distinctly lower than concentrations in fish from Swiss plateau lakes which receive inputs from waste water treatment plants.

Tetrabromobisphenol A (TBBPA), hexabromocyclododecane (HBCD), and decabromodiphenyl ether (DecaBDE) are high production volume chemicals used as flame retardants in plastics for products such as electronic equipment, insulation panels, and textiles. The environmental safety of brominated flame retardants, especially their persistence, bioaccumulation, and toxicity is a controversial topic. Here, we studied and compared the degradation of TBBPA, HBCD, and DecaBDE under anaerobic conditions in digested sewage sludge. The half-lives of TBBPA and a technical HBCD mixture were 0.59 and 0.66 d, respectively. The fact that (+/-)-alpha-HBCD exhibited an almost doubled half-life compared to (+/-)-beta-HBCD and (+/-)-gamma-HBCD is an important finding with respect to the discussion on the persistence of individual HBCD stereoisomers and the recent reports on strong relative enrichment of alpha-HBCD in biota. We found no statistically significant enantioselective degradation of alpha-, beta-, or gamma-HBCD. Half-lives of TBBPA and a technical HBCD mixture were not dependent on the presence of additional nutrients or primers. Concentrations of TBBPA and a technical HBCD mixture decreased also in sterile control samples, however, at a rate that was more than a factor of 50 smaller than in incubations under non-sterile conditions. Compared to TBBPA and a technical HBCD mixture, DecaBDE exhibited a much longer half-life of 7 x 10(2)d in the same system. Pseudo-first-order degradation rate constants decreased according to the following sequence: TBBPA congruent with(+/-)-gamma-HBCD congruent with(+/-)-beta-HBCD>(+/-)-alpha-HBCD>>DecaBDE. Preliminary investigations suggest that degradation of TBBPA, HBCD, and DecaBDE occurs in full-scale anaerobic digesters, as well.

Brominated flame retardants (BFRs) are synthetic additives mainly used in electrical and electronic appliances and in construction materials. The properties of some BFRs are typical for persistent organic pollutants, and certain BFRs, in particular some polybrominated diphenyl ether (PBDE) congeners and hexabromocyclododecane (HBCD), are suspected to cause adverse health effects. Global consumption of the most demanded BFRs, i.e., penta-, octa-, and decaBDE, tetrabromobisphenol A (TBBPA), and HBCD, has doubled in the 1990s. Only limited and rather uncertain data are available regarding the occurrence of BFRs in consumer goods and waste fractions as well as regarding emissions during use and disposal. The knowledge of anthropogenic substance flows and stocks is essential for early recognition of environmental impacts and effective chemicals management. In this paper, actual levels of penta-, octa-, and decaBDE, TBBPA, and HBCD in waste electrical and electronic equipment (WEEE) as a major carrier of BFRs are presented. These BFRs have been determined in products of a modern Swiss recycling plant applying gas chromatography/electron capture detection and gas chromatography/mass spectrometry analysis. A substance flow analysis (SFA) technique has been used to characterize the flows of target substances in the recycling process from the bulk WEEE input into the output products. Average concentrations in small size WEEE, representing the relevant electric and electronic appliances in WEEE, sampled in 2003 amounted to 34 mg/kg for pentaBDE, 530 mg/kg for octaBDE, 510 mg/kg for decaBDE, 1420 mg/kg for TBBPA (as an additive), 17 mg/kg for HBCD, 5500 mg/kg for bromine, and 1700 mg/kg for antimony. In comparison to data that have been calculated by SFA for Switzerland from literature for the 1990s, these measured concentrations in small size WEEE were 7 times higher for pentaBDE, unexpectedly about 50% lower for decaBDE, and agreed fairly well for TBBPA (as an additive) and octaBDE. Roughly 60% of the total bromine input determined by SFA based on X-ray fluorescence analysis of the output materials of the recycling plant cannot be assigned to the selected BFRs. This is an indication for the presence of other brominated substances as substitutes for PBDEs in electrical and electronic equipment. The presence of BFRs, in particular PBDEs in the low grams per kilogram concentration range, in the fine dust fraction recovered in the off-gas purification system of the recycling plant reveals a high potential for BFR emissions from WEEE management and point out the importance for environmentally sound recycling and disposal technologies for BFR-containing residues.