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Werner Brack: Field Based Approaches for Identification of RBSP

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Werner Brack: Field Based Approaches for Identification of RBSP Field Based Approaches for Identification of RBSP Werner Brack et al., Department for Effect-Directed Analysis, Helmholtz Centre for Environmental Research UFZ, Leipzig, Germany RBSP Identification and Prioritization How to derive RBSP candidate substances? Field-based Monitoring (EDA → non- based target) (→ target) RBSP Modelling-based (production and usage) Monitoring-based (→ target) Suggestion: Identification and prioritization of RBSP based on monitoring • Basis: Toxic Units (TU) for Daphnia (invertebrates), Selenastrum (algae) and Pimephales (fish) • Threshold -3 (→ disappearance of sensitive species) • 3 lines of evidence: • trend (R → 0 - 1) existing data insufficient! • frequency of exceeding (0 - 1) • degree of exceeding (0 - 1)* • Rank = t + f + d (0 - 3) *>1000 1, >100 0.5, >10 0.2, >1 0.1 Monitoring-based (→ target) english name Use sub-class # of sites FR ER GR bis-(2-ethylhexyl)-phtalatenglish name plastisizer Use sub-class908 1.0# of sites 1.0 FR 2.0 ER GR azoxystrobinbis-(2-ethylhexyl)-phtalatfungicide plastisizer 181 0.9 9081.0 1.9 1.0 1.0 2.0 dichlorvos insecticide 105 0.3 1.0 1.3 terbutylazineazoxystrobin herbicide fungicide 921 0.7 1810.5 1.2 0.9 1.0 1.9 diurondichlorvos herbicide insecticide 376 0.7 1050.5 1.2 0.3 1.0 1.3 dioctyltinterbutylazine antifouling compoundsherbicide 138 1.0 9210.2 1.2 0.7 0.5 1.2 tetrabutyltindiuron antifouling compoundsherbicide 77 0.2 3761.0 1.2 0.7 0.5 1.2 chlorfenvinfos insecticide 103 0.1 1.0 1.1 perfluorononanoatedioctyltin surfactant antifouling compounds61 1.0 1380.1 1.1 1.0 0.2 1.2 benzo[e]pyrenetetrabutyltin antifouling compounds38 0.8 0.277 1.0 0.2 1.0 1.2 diazinonchlorfenvinfos insecticide insecticide 124 0.5 1030.5 1.0 0.1 1.0 1.1 perfluorooctanoate emulgator 110 0.7 0.2 0.9 indeno(1,2,3-c,d)pyreneperfluorononanoate surfactant 606 0.7 0.261 0.9 1.0 0.1 1.1 irgarol benzo[e]pyrene herbicide 260 0.4 0.538 0.9 0.8 0.2 1.0 alachlordiazinon herbicide insecticide 226 0.4 1240.5 0.9 0.5 0.5 1.0 linuron herbicide 112 0.7 0.2 0.9 2-hydroxy-atrazineperfluorooctanoate transformation productemulgator 97 0.6 1100.2 0.8 0.7 0.2 0.9 4,4'- DDTindeno(1,2,3-c,d)pyreneinsecticide 550 0.5 6060.2 0.7 0.7 0.2 0.9 benzo[b]fluorantheneirgarol herbicide 721 0.5 2600.2 0.7 0.4 0.5 0.9 terbutryne herbicide 570 0.5 0.2 0.7 metolachloralachlor herbicide herbicide 448 0.5 2260.2 0.7 0.4 0.5 0.9 HHCB (Galaxolide®)linuron fragrance herbicide 789 0.6 1120.1 0.7 0.7 0.2 0.9 perylene2-hydroxy-atrazine pigment transformation38 product 0.6 0.197 0.7 0.6 0.2 0.8 2,4'-DDT transformation product 324 0.4 0.2 0.6 chlorpyrifos4,4'- DDT insecticide insecticide 124 0.1 5500.5 0.6 0.5 0.2 0.7 flufenacetbenzo[b]fluorantheneherbicide 183 0.4 7210.2 0.6 0.5 0.2 0.7 chloridazonterbutryne herbicide herbicide 143 0.4 5700.2 0.6 0.5 0.2 0.7 pirimicarbmetolachlor insecticide herbicide 180 0.4 4480.2 0.6 0.5 0.2 0.7 ametryne herbicide 25 0.5 0.1 0.6 dimethenamidHHCB (Galaxolide®)herbicide fragrance 19 0.4 7890.1 0.5 0.6 0.1 0.7 benzo[k]fluorantheneperylene pigment 666 0.4 0.138 0.5 0.6 0.1 0.7 cyanazine2,4'-DDT herbicide transformation113 product 0.3 3240.2 0.5 0.4 0.2 0.6 chloroxylenol anti-microbial 35 0.3 0.2 0.5 desethylterbutylazinechlorpyrifos transformation productinsecticide 356 0.3 1240.1 0.4 0.1 0.5 0.6 prometrynflufenacet herbicide herbicide 263 0.3 1830.1 0.4 0.4 0.2 0.6 tolclofos-methylchloridazon fungicide herbicide 97 0.2 1430.2 0.4 0.4 0.2 0.6 metoxuron herbicide 106 0.2 0.2 0.4 desphenyl-chloridazonpirimicarb transformation productinsecticide 36 0.3 1800.1 0.4 0.4 0.2 0.6 desisopropylatrazineametryne transformation productherbicide 336 0.2 0.225 0.4 0.5 0.1 0.6 hexazinondimethenamid herbicide herbicide 160 0.2 0.219 0.4 0.4 0.1 0.5 benzo[ghi]perylene 589 0.3 0.1 0.4 4-nonylphenolbenzo[k]fluoranthene (tech) tenside 628 0.3 6660.1 0.4 0.4 0.1 0.5 chlorotoluroncyanazine insecticide herbicide 142 0.3 1130.1 0.4 0.3 0.2 0.5 malathionchloroxylenol insecticide anti-microbial147 0.1 0.235 0.3 0.3 0.2 0.5 chlorphyriphos-ethyldesethylterbutylazineinsecticide transformation624 product 0.2 3560.1 0.3 0.3 0.1 0.4 fluoranthene 792 0.2 0.1 0.3 AHTN (Tonalide®)prometryn fragrance herbicide 480 0.2 2630.1 0.3 0.3 0.1 0.4 dimetachlortolclofos-methyl herbicide fungicide 157 0.2 0.197 0.3 0.2 0.2 0.4 propachlormetoxuron herbicide herbicide 97 0.1 1060.2 0.3 0.2 0.2 0.4 desphenyl-chloridazon transformation product 36 0.3 0.1 0.4 desisopropylatrazine transformation product 336 0.2 0.2 0.4 hexazinon herbicide 160 0.2 0.2 0.4 benzo[ghi]perylene 589 0.3 0.1 0.4 4-nonylphenol (tech) tenside 628 0.3 0.1 0.4 chlorotoluron insecticide 142 0.3 0.1 0.4 malathion insecticide 147 0.1 0.2 0.3 chlorphyriphos-ethyl insecticide 624 0.2 0.1 0.3 fluoranthene 792 0.2 0.1 0.3 AHTN (Tonalide®) fragrance 480 0.2 0.1 0.3 dimetachlor herbicide 157 0.2 0.1 0.3 propachlor herbicide 97 0.1 0.2 0.3 Field-based (→ non-target) Often observed: Predicted effects based on target monitoring measured effects Effect-Directed Analysis (EDA) • Site selection: Effect environmental monitoring + expert contamination knowledge on sites and sinks biological chemical • No a priori knowledge analysis analysis on or selection of compounds required confirmation biological • Applicable to any fractionation matrix (water, analysis sediments, biota, …) toxicant Field-based (→ non-target) EDA in sediments 50 120 40 mutagenicity 100 80 30 60 TA98 20 tumor promotion % of control 40 TA98 with metabolic (inhibition of GJIC) 10 activation 20 number of positive wellsof number 0 0 P2 P3 P4 P5 P6 P7 P8 P9 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 P1 P10 P11 P12 P13 P14 P15 P16 P17 P18 fractions 40 4000 35 3500 30 3000 25 thyroid estrogenicity 2500 20 hormone 2000 15 1500 disturbing 10 % maximum induction 1000 potency 5 pmol T4 eq/g dry sediment dry eq/g T4 pmol 500 0 P 1 P 2 P 3 P 4 P 5 P 6 P 7 P 8 P 9 P P 11P 12P 13P 14P 15P 16P 17P 18P P 10P 0 P1 P2 P3 P4 P5 P6 P7 P8 P9 P11 P12 P13 P14 P15 P16 P17 P18 PCBs, PCDD/Fs, P10 halogenated pesticides PAHs polar compounds typically monitored in sediments most problematic compounds Field-based (→ non-target) Non-regulated compounds identified by EDA studies in sediments (algal toxicity, endocrine disuption, mutagenicity) O O - O O + O N CH3 + O N O O - O nandrolone 2-methylanthra- benzanthrone O dinitropyrenes quinone NH O O N-phenyl-2- tonalide O galoxolide Cl OH naphthylamine O Cl P Cl traseolide O O tris(2-chloroisopropyl) O phosphate Cl Cl Cl triclosan .
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