jan tříska global change research centre as cr České budějovice

OCCURRENCE OF PCBs IN THE CZECH REPUBLIC.

BIODEGRADATION OF BIPHENYL AS A MODEL STUDY FOR BIODEGRADATION

OF ITS CHLORINATED DERIVATIVES.

Jan TřískaGlobal 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 CUSTOMERSBARVY 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 THELONG-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

1

2

3 45 6 7

8

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

1

24

5

8

1

2 4 5

8

1

24 5

8

The contribution of PCBs and PCDDs/Fs to total TEQ

Contents of Cl-PEST and PCBs in the soil

BIODEGRADATION OF PCBsBIODEGRADATION OF PCBs

• AEROBICALLY AS A GROWTH AEROBICALLY AS A GROWTH SUBSTRATE SUBSTRATE ((bacterial, less chlorinated faster)bacterial, less chlorinated faster)

• AEROBICALLY BY COMETABOLISM AEROBICALLY BY COMETABOLISM ((bacteria or white-rot fungi „bacteria or white-rot fungi „Phanerochaete Phanerochaete

chrysosporium“chrysosporium“))• ANAEROBICALLY BY REDUCTIVE ANAEROBICALLY BY REDUCTIVE

DEHALOGENATION (DEHALOGENATION (unknown mechanism)unknown mechanism)

MAJOR METABOLIC SEQUENCE OF PCBs DEGRADATION BY AEROBIC MICROORGANISMS

Clx Clx

OHH

HOH( A ) ( B )

OH

OH ( C )O

OH

COOH

Clx Clx

COOH

Clx

( D )

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

water in(25°C)

water out

cooler

air supply

porous glass Siran withimmobilized cells

mineral medium

fritted glass

temperaturecontrol bath

MONITORING OF THE ORANGE COLOUR DEVELOPMENT

Wav elength (nm)200 250 300 350 400 450 500

Abso

rban

ce (A

U)

1

1.5

2

2.5

3

3.5

Solanum nigrum

Cl Cl

OH

Cl

OH+

Cl

OH

Cl

OH

Cl

+

Cl OHCl