OCCURRENCE OF PCBs IN THE CZECH REPUBLIC. BIODEGRADATION OF BIPHENYL AS A MODEL STUDY FOR BIODEGRADATION OF ITS CHLORINATED DERIVATIVES. Jan Tříska Global Change Research Centre AS CR České Budějovice PRODUCTION OF PCBs AROCLOR (MONSANTO, USA, UK) CLOPHEN (BAYER, FRG) PYRALEN, PHENOCLOR (PRODELAC, FRANCE) FLIX (SPAIN) SOVOL, SOVTOL (USSR) FENCLOR (ITALY) KANECLOR (JAPAN) CZECHOSLOVAKIA DELOR 103 (AROCLOR 1242) DELOR 104 (AROCLOR 1248) DELOR 105 (AROCLOR 1254) DELOR 106 (AROCLOR 1260) HYDELOR DELOTHERM PRODUCTION OF PCBs DISTRIBUTION OF PCBs CAPACITORS 36% PLASTICIZERS 27% TRANSFORMERS 19% HYDRAULIC FLUIDS 10% HEAT CARRIERS 6% DIFFERENT USAGE 2% (paint additives, additives for pesticides, polishing waxes, carbon copy papers, printing inks and pastes, roofing felts, motor oils etc.) PRODUCTION IN THE CZECHOSLOVAKIA CHEMKO STRÁŽSKE ( ca. 20 000 t) MAIN CUSTOMERS BARVY A LAKY PRAHA (PAINTS) VŘESOVÁ (MINING INDUSTRY) ČKD PRAHA (TRANSFORMERS) PETROCHEMA DUBOVÁ (HYDRAULIC FLUIDS) ZEZ ŽAMBERK (CAPACITORS) CHZJD BRATISLAVA (PESTICIDES) ROAD BUILDING AND CONSTRUCTION FIRMS * ESTIMATED LOSS ca. 4 000 t (20%) !!! 30 mg/m2 !!! THE SAMPLING SITES AND SUMMARY OF RESULTS THE FIRST DESCRIPTION OF THE LONG-RANGE TRANSPORT OF POPs IN MOUNTAIN ECOSYSTEM Holoubek I., Čáslavský J., Vančura R., Kočan A., Chovancová J., Petrík J., Drobná B., Cudlín P., Tříska J.: Project Tocoen: The fate of selected organic pollutants in the environment. Part XXIV. The contents of PCBs and PCDDs/Fs in high-mountain soils, Toxicol. Environ. Chem. 45, 189-197 (1994) Blais J.M., Schindler D.W., Muir D.C.G., Kimpe L.E., Donald D.B., Rosenberg B.: Accumulation of persistent organic compounds in mountains of western Canada, Nature 395, 585-588 (1998) STARTING POINTS OF THE PROJECT • ca. 72% of the forests in the CR are damaged • chemical factors could play an important role (long-range transport of POPs) • spruce forests cover ca. 75% of the total surface of the CR • impact of pollution to the spruce forest is higher (leaf surface index and wax) • ILE AS CR has permanent research plots in the high mountain around the whole CR BASIC DESCRIPTION OF THE RESEARCH PLOTS 3 4 5 6 7 2 8 1 THE MAIN GOALS OF THE PROJECT • DETERMINATION OF THE PATTERN OF OCCURRENCE AND THE UPTAKE WAYS OF POPs PHYTOTOXICALLY IMPORTANT FOR MONTANE SPRUCE POPULATION • DETERMINATION OF IMPORTANT POPs IN THE NEEDLES AND HUMUS LAYER • BIODEGRADATION OF LOW CHLORINATED PCBs BY BACTERIA AND/OR PLANTS 4 2 1 5 8 2 4 5 8 1 4 2 5 8 1 The contribution of PCBs and PCDDs/Fs to total TEQ Contents of Cl-PEST and PCBs in the soil BIODEGRADATION OF PCBs • AEROBICALLY AS A GROWTH SUBSTRATE (bacterial, less chlorinated faster) • AEROBICALLY BY COMETABOLISM (bacteria or white-rot fungi „Phanerochaete chrysosporium“) • ANAEROBICALLY BY REDUCTIVE DEHALOGENATION (unknown mechanism) MAJOR METABOLIC SEQUENCE OF PCBs DEGRADATION BY AEROBIC MICROORGANISMS ( A) OH H H OH OH OH O (B) OH ( C ) COOH COOH ( D) Clx Clx Clx Clx Clx UNUSUAL BIODEGRADATION PRODUCTS D.AHMAD, M.SYLVESTRE, M.SONDOSSI, R.MASSÉ: Journal of General Microbiology (1991), 137, 1375-1385 UNUSUAL BIODEGRADATION PRODUCTS G.KÖLLER, M.MÖDER, K.CZIHAL: Chemosphere (2000), 41, 1827-1834 UNUSUAL BIODEGRADATION PRODUCTS G.KUNCOVÁ, J.TŘÍSKA, N.VRCHOTOVÁ, O.PODRAZKÝ: Materials Science and Engineering C 21 (2002), 195-201 cooler temperature control bath water out mineral medium porous glass Siran with immobilized cells water in (25°C) fritted glass air supply MONITORING OF THE ORANGE COLOUR DEVELOPMENT 3.5 Absorbance (AU) 3 2.5 2 1.5 1 200 250 300 350 400 450 500 Wav elength (nm) Solanum nigrum Cl Cl Cl OH Cl HO Cl Cl OH Cl + Cl + HO OH