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Persistent halogenated compounds in black guillemots (Cepphus grylle) from Greenland--levels, compound patterns and spatial trends.

Twenty-seven black guillemot eggs and 39 livers were analysed for polychlorinated biphenyls (PCBs), chlorinated pesticides including chlordane-related compounds and toxaphene, and polybrominated diphenylethers (PBDEs). The samples were collected at Qeqertarsuaq (Godhavn, West Greenland) and Ittoqqortoormiit (Scoresbysund, East Greenland). The concentrations of halogenated organic compounds in samples from East Greenland were somewhat higher than the corresponding concentrations from West Greenland. Differences in compound patterns were found between West and East Greenland, with higher percentages of the heavier PCB molecules, p,p(')-DDE and alpha-HCH in the samples from Ittoqqortoormiit. Similarly, different levels and different compositions were observed for eggs and livers. The eggs had generally higher concentrations of all compounds as well as higher percentages of CHB-50, CHB-62 and alpha-HCH than liver samples from the same area. Dividing the liver samples into age groups revealed increasing concentrations with age.

Animals↗

HQSAR and CoMFA approaches in predicting reactivity of halogenated compounds with hydroxyl radicals.

Two quantitative structure-activity relationship (QSAR) methods: hologram QSAR (HQSAR) and comparative molecular field analysis (CoMFa) were evaluated for predicting half-lives of the hydroxyl radicals reaction with substituted aromatic compounds. The HQSAR approach, which is topological in nature, results in a mathematical model which was more stable and has a greater predictive ability than the model derived on the 3-D CoMFA approach. Interpretations of the colour coded results of both methods are in good agreement with the proposed mechanism of the hydroxyl radical oxidation of halogenated aromatic compounds in the atmosphere.

2,4-Dichlorophenoxyacetic Acid↗

Halogenated compounds in a dated sediment core of the Teltow Canal, Berlin: time related sediment contamination.

To study the recent contamination history of DDT (1,1,1-trichloro-2,2-bis(chlorophenyl)ethane) and its metabolites, as well as methoxychlor (1,1,1-trichloro-2,2-bis(p-methoxyphenyl)ethane), chlorfenson (4-chlorophenyl-p-chlorobenzenesulfonate), and further halogenated aromatics, a sediment core was collected from the Teltow Canal in Berlin (Germany). The sampling site is located nearby a former industrial point source, where recently analyses on pre-samples have indicated high concentrations of halogenated organic compounds. The deposition time of the investigated sediments was determined by gamma-spectrometrical dating. Pollution trends of selected contaminants were attributed to a time period between 5 and 10 years. Concentration profiles reflect not only the recent pollution history of these compounds, but also the time-depending effects of the ban, restriction and termination of DDT-production in the German Democratic Republic (GDR). DDT and other chlorinated aromatic compounds were produced onsite until the late 1980s. Maximum values of 133 mg kg(-1) (dry weight) for p,p'-DDD (1,1-dichloro-2,2-bis(chlorophenyl)ethane) and approximately 100 mg kg(-1) (dry weight) for p,p'-DDMS (1-chloro-2,2-bis(chlorophenyl)ethane), main metabolites of the anaerobic degradation of DDT, were determined. The occurrence of all selected contaminants, most of which have been banned more than 10 years ago, demonstrate recent contamination pathways, and the necessity of a continuous long-term monitoring of the affected environment.

Berlin↗

Kinetic assessment of persistent halogenated xenobiotics in cell culture models: comparison of mono- and poly-halogenated compounds.

We evaluated the suitability of single and multiple cell type cultures as model systems to characterise cellular kinetics of highly lipophilic compounds with potential ecotoxicological impact. Confluent mono-layers of human skin fibroblasts, rat astrocytoma C6 cells, non-differentiated and differentiated mouse 3T3 cells were kept in culture medium supplemented with 10% foetal calf serum. For competitive uptake experiments up to four different cell types, grown on glass sectors, were exposed for 3h to (14)C-labelled model compounds, dissolved either in organic solvents or incorporated into unilamellar lecithin liposomes. Bromo-, or chloro-benzenes, decabromodiphenylether (DBP), and dichlorodiphenyl ethylene (DDE) were tested in rather high concentration of 20 microM. Cellular toxicity was low. Compound levels were related to protein, DNA, and triglyceride contents. Cellular uptake was fast and dependent on physico-chemical properties of the compounds (lipophilicity, molecular size), formulation, and cell type. Mono-halogenated benzenes showed low and similar uptake levels (=low accumulation compounds). DBP and DDE showed much higher cellular accumulations (=high accumulation compounds) except for DBP in 3T3 cells. Uptake from liposomal formulations was mostly higher than if compounds were dissolved in organic solvents. The extent of uptake correlated with the cellular content of triglycerides, except for DBP. Uptake competition between different cell types was studied in a sectorial multi-cell culture model. For low accumulation compounds negligible differences were found among C6 cells and fibroblasts. Uptake of DDE was slightly and that of DBP highly increased in fibroblasts. Well-defined cell culture systems, especially the sectorial model, are appropriate to screen for bioaccumulation and cytotoxicity of (unknown) chemical entities in vitro.

Animals↗

Oxidation of halogenated compounds by cytochrome P-450, peroxidases, and model metalloporphyrins.

Incubation of iodosylbenzene and [125I]iodobenzene with cytochrome P-450 (P-450) leads to the formation of [125I]iodosylbenzene (Burka, L.T., Thorsen, A., and Guengerich, F.P. (1980) J. Am. Chem. Soc. 102, 7615-7616), but to date it has not been possible to observe directly the oxidation of organic halides in NADPH-supported P-450 reactions because of the intrinsic instability of haloso compounds. 4-tert-Butyl-2,5-bis[1-hydroxy-1-(trifluoromethyl)- 2,2,2-trifluoroethyl]iodobenzene (RI) and the corresponding bromine analog (RBr) were utilized as model compounds because their oxidized derivatives (iodinane and brominane) are relatively stable. Several model metalloporphyrins efficiently oxidized RI to the iodinane in the presence of iodosylbenzene. Rates of reduction of Mn(V) = O tetraphenylporphin chloride by RI were considerably faster than for several other organic halides. NADPH-fortified rat liver microsomes oxidized RI to the iodinane, identified by its chromatographic retention time and characteristic UV spectrum. Purified P-450 enzymes also catalyzed the oxidation of RI to the iodinane; more selectivity among individual proteins was seen when the reaction was supported by NADPH and NADPH-P-450 reductase than by iodosylbenzene. Free thiol groups in P-450 and NADPH-P-450 reductase could be oxidized by iodosylbenzene, the iodinane or brominane, or by incubation with NADPH and RI or other organic halides. These results provide evidence that P-450 can oxidize organic halogen atoms. Iodo compounds are definitely oxidized, even though the apparent oxidation-reduction potential differences seem unfavorable. The halogen order seen for the reaction is a function of the oxidation potential. Organic bromine compounds are probably also oxidized by P-450, although the rates are much slower. Chloroperoxidase did not oxidize RI to the iodinane but horseradish peroxidase did so at a lower rate; in this case the iodinane is postulated to form via electron abstraction without oxygen transfer.

Amino Acids↗

[A method for detection of volatile organic halogenated compounds in human and animal tissues (author's transl)].

A method is described which is suitable for detecting volatile halogenated hydrocarbons boiling from 60 degrees to 150 degrees C in human and animal tissues. Fried tissue samples of 10 grams are homogenized with Na2SO4. Stripped by nitrogen in an 80 degrees C water bath the compounds are sorbed on XAD-2 columns and desorbed by pentane. The pentane extract can directly be analyzed without further clean up, either by gas-liquid chromatography or by microcoulometry. Limits of detection achieved were between 6.2 X 10(-9) g/kg for carbon tetrachloride and 49 X 10(-9) g/kg for 1,1,2-trichloroethane. The recovery in human tissue is 87% as mean value.

Animals↗