The biomonitoring of trace elements, PCB and OCP in the river ecosystems of the Czech Republic Marek Liška, Milan Koželuh, Lumír Kule, Jakub Horecký, Natália Lapšanská a Jiří Streit Vltava River Authority, Czech Republic AIM OF THE BIOMONITORING PROJECT • The investigation of contamination range in the Czech rivers ecosystems for trace elements (Cd, Pb, Hg, As), PCB (9 basic congeners) and DDT, DDD, DDE, HCB • The acquisition of data for map of a contamination Czech and Moravian rivers Background of the project • organization and financial support CHMI Prague • sampling and laboratory analysis Povodí Vltavy, Povodí Labe, Povodí Moravy • Start of the project: 1999 Sampling points Biomarkers • Dreissena polymorpha long-term exposure ( 60 days) • Bentos: • Erpobdella octoculata, Asellus aquaticus, Bithynia tentaculata, Hydropsyche sp. • Fish: Leuciscus cephalus • Biofilm long-term exposure ( 60 days) Methods of sampling Methods of laboratory procedure • Dreissena separation of biomass from shells • Fish - separation of dorsal muscles • Benthos - sampling - kicking method, selection of species • Biofilm - wipe of biofilm layer • homogenization • lyofilization • analysis of desiccate and fat • microwave digestion • extraction, cleaning • AAS – ETA, analysis of heavy metals. (ICP – MS) • Gas Chromatography • check of analysis - SRM 2974 Results – cadmium and lead biofilm- cadmium m g /k g makrozoobentos - cadmium 8,0 5,0 7,0 4,5 6,0 4,0 5,0 3,5 4,0 3,0 3,0 2,5 2,0 2,0 1,5 1,0 1,0 0,0 Hydropsyche Sphaerium ZE L ZI D H VE R Erpobdella LA N LO U LY S NE S NI S O BR PO H SR B TO P US T VA L Bithynia BO Asellus BE C H 0,0 DE B DE C DE H IV A L R D ZI ZE VE VA L T P TO US B H PO SR LA N LO U LY S NE S NI S O BR BE CH BO H DE B DE C DE H IV A 0,5 biofilm - lead makrozoobentos - lead 60,0 40,0 120,0 30,0 100,0 20,0 80,0 10,0 60,0 0,0 40,0 20,0 ZE L ZI D VE R Sphaerium TO P US T VA L Hydropsyche NE S NI S O BR PO H SR B Erpobdella LA N LO U LY S Bithynia H DE B DE C DE H IV A Asellus BO H 0,0 BE C BE IV A LA N LO U LY S NE S NI S OB R PO H SR B TO P US T VA L VE R ZE L ZI D 140,0 CH BO H DE B DE C DE H 50,0 Results – mercury and PCB fish - mercury makrozoobentos - mercury mg/kg 2,5 2,0 5,1 1,8 1,6 2,0 1,4 1,5 1,2 1,0 1,0 0,8 0,6 0,5 0,4 0,0 Bithynia Erpobdella Hydropsyche VA L VE R ZE L ZI D 0,0 B EC H B O H D EB D EC D EH IV A LA N LO U LY S N ES N I O S B R PO H SR TOB P U ST V A L V ER ZE L ZI D Asellus LY S NE S NI S OB R PO H SR B TO P US T H IV A LA N LO U C DE B DE DE BE CH BO H 0,2 Sphaerium fish - sum of PCB makrozoobentos - sum of PCB ug/k g 800 500 700 450 400 350 600 500 300 250 400 300 200 B EC H 0 Asellus Bithynia Erpobdella Hydropsyche Sphaerium O H D E B D E C D E H IV A LA N LO U LY S N E S N IS O B R P O H S R B TO P U S T V AL V ER ZE L ZI D L D ZI ZE H SR B TO P U ST VA L VE R PO IS BR O ES N N S LY N U LO LA IV A EH D D D BO C BE EC 50 H 0 EB 150 100 H 100 B 200 Asellus Bithynia Erpobdella Erpobdella Hydropsyche Hydropsyche Sphaerium Sphaerium B E C H B O H D E D B E D C E H IV LA A N LO U LY N S E S N IS O B R P O P H R M S R TOB P U S T V A V L E R ZE L ZI D ZI ZE VE D L R S NI S O BR PO H SR B TO P US T VA L NE CH BO H DE B DE C DE H IV A LA N LO U LY S BE ug/kg 350 150 50 0 120 100 60 20 0 C H BO H D EB D E D C EH IV LA A N LO U LY N S ES N I O S BR PO H SR TOB U P ST VA VE L R ZE L ZI D BE Bithynia ZI D Asellus ZE L CH BO H D EB DE C D EH IV A LA N LO U LY S N ES NI S OB R PO H SR B TO P U ST VA L VE R BE Results – DDE and HCB makrozooentos - p,p DDE ug/kg 70 Dreissena - p,p DDE 300 60 250 50 200 40 100 30 20 10 0 makrozoobentos - HCB 25 fish - HCB 140 20 80 15 10 40 5 0 Key questions to the selection of suitable biomarkers • Frequency of occurrence on the locality • Affinity to the locality/migration • Capacity of bioaccumulation (organic/anorganic compounds) • Biomass of the species • Cost/benefit - per one sample Influence on the bioaccumulation • • • • • • Period of sampling Age of the organism Food strategy Bioavailability of pollutant for organisms Bioaccumulation capacity Kinetic of bioaccumulation Age/Content Cd and Pb concentration of cadmium x biomass of the individual 1,5 1 y = -0,7431x - 0,2561 log mg Cg/kg 0,5 r = 0,714 0 -0,5 concentration of lead x biom ass of the individual -1 -1,5 1,5 Macrozoobenthos -2 -2,5 y = -0,4098x + 0,5784 r = 0,665 1 -1 -0,5 0 0,5 1 1,5 2 2,5 log weight (mg) log mg Pb/kg -3 0,5 0 -0,5 con ce n trati on of m e rcu ry x bi om ass of th e i n di vi du al 10 -1 -1 0 0,5 1 log weight (mg) 8 Hg mg/kg -0,5 6 4 Fish 2 0 0 500 1000 weight (g) 1500 1,5 2 2,5 Capacity of biomarkers for pollutants cadmium fish Ase HCB fish Bit mercury Bit fish Erp Hyd Erp Bit Sph biofilm Ase Ase Erp Hyd biofilm Dreiss lead fish p,p DDE Ase Bit Sph Hyd Sph Dreiss Dreiss biofilm sum of PCB Ase Ase Erp Hyd Sph Dreiss Hyd biofilm Erp Erp fish biofilm Sph biofilm Dre iss Bit fish Bit Hyd Dreiss Sph Correlation between species Hydropsyche, Asellus, Erpobdella, biofilm Hyd/Erp cadmium Hyd/Ase mercury 1,8 1,6 0,6 Hyd/Ase cadmium 1,4 0,5 1,2 1,8 1,0 0,4 1,6 0,8 0,3 1,4 0,6 1,2 0,2 0,4 1,0 y = 0,7745x R2 = 0,8054 0,2 0,0 0,0 0,5 1,0 1,5 0,6 2,0 y = 0,735x 2 R = 0,6691 0,1 0,8 0,0 y = 0,7872x R 2 = 0,8946 0,4 0,2 0,0 0,2 0,4 0,6 0,8 0,0 0,0 0,5 1,0 1,5 2,0 Hyd/Ase lead Hyd/biofilm lead substitution 18 140 16 14 120 12 100 10 80 8 60 6 40 4 y = 1,1876x 2 2 R = 0,7609 0 0,00 y = 7,5024x 2 R = 0,5043 20 0 5,00 10,00 15,00 0 5 10 15 20 Ability of bioaccumulation by biomarkers Cd: fish<Sphaerium<Bithynia<Hydropsyche<Erpobdella<Asellidae<Dreissena<biofilm Pb: fish<Dreissena<Sphaerium<Bithynia<Erpobdella<Asellidae<Hydropsyche<biofilm Hg: Sphaerium<Bithynia<Hydropsyche<Dreissena<Asellidae<Erpobdella<biofilm<fish PCB: Sphaerium<Bithynia<biofilm<Asellidae<Dreissena<Erpobdella<Hydropsyche<fish HCB: Dreissena<Sphaerium<Bitynia<Erpobdella<Hydropsyche<fish<biofilm< Asellidae DDT: Sphaerium<Bithynia<biofilm<Asellidae<Dreissena<Hydropsyche<Erpobdella<fish The Best of... Conclusions • Acquisition of relevant data for representative map of contamination Czech and Moravian rivers • Optimization of the monitoring focus for the next period • Specification of the best species for biomonitoring • Specification of the species for mutual substitution • Data are not still sufficient for evaluation of the long term trend (high variability among years) Future prospect • Create the evaluation and calibration system for measured data • Inclusion of monitoring of new compounds (biochemical markers, MUSK, PBDE, phthalate esters, hormone) • Open database for further organisms (juvenile stage of fish and other benthic species) • Evaluation of the relationship between content of compounds in biomarkers and in „virtual fish“ Thank you for your attention [email protected]
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