1. Department of Plant and Environmental Sciences Are PAH metabolites new emerging soil contaminants? Production, identification, and potential mobility in soil of PAH metabolites Esther Boll Anders Johnsen, GEUS Jan H. Christensen, PLEN, UCPH AnalyticalChemistry Group EnvironmentalChemistry and Physics Department of Plant and Environmental Sciences University of Copenhagen

2. Department of Plant and Environmental Sciences Regulation in soil and groundwater Soilqualitycriteria Groundwater qualitycriteria *Sum of fluoranthene, benzo[b+j+k]fluoranthene, benzo[a]pyrene, dibenzo[a,h]anthracene and ideno[123-c,d]pyrene **Sum of benzo[b+k]fluoranthene, ideno[123-c,d]pyrene, and Benzo(ghi)perylene

3. Department of Plant and Environmental Sciences Background ?

4. Department of Plant and Environmental Sciences Fate of PAHs in soil Bamfort& Singleton (2005)

5. Department of Plant and Environmental Sciences Fate of PAH metabolitesin soil R R R R PAH Cytochrome P450 monooxygenase • Conjugated PAH metabolites are MUCH more polar (compared to parent compounds) • Persistent in the environment (Schmidt et al. 2010) Non-enzymaticrearrangement Epoxidehydrolase H H Areneoxide OH OH Phenol Potential risk of leaching to surface and ground water trans-dihydrodiol Conjugation of a large watersolublemolecule O-glucoside O-gluconoride O-xyloside O-sulfate O-methyl

6. Department of Plant and Environmental Sciences Ourstudy Producemetabolites from un-substituted and alkyl-substitutedPAHs Identification of PAH metabolites Potential mobility of PAH metabolites

7. Department of Plant and Environmental Sciences Production and sample analysis of PAH metabolites SPE UPLC-Flr-q-TOF

8. Department of Plant and Environmental Sciences Identification of PAH metabolites OH

9. Department of Plant and Environmental Sciences Sorption of 14 PAHsmetabolites in threesoils • Adsorption test using a batch equilibrium method based on OECDs guideline no. 106. Soil 29 Soil 1 Soil12

10. Department of Plant and Environmental Sciences Concentration range: 0.08 – 5.10 µg mL-1 Kd Soil 1 Sulfate metabolites Kd Kd 1-methyl pyreneKd = ~2200 Sulfate and carboxylicacid metabolites

11. Department of Plant and Environmental Sciences Riskassessment: JAGG

12. Department of Plant and Environmental Sciences PAH metabolites in the environment Soil 1 Soil 12 Soil: ~ 6 m3 1.8 m Leachates 1 L 2 m Solid phaseextraction UPLC-FLR-Q-TOF

13. Department of Plant and Environmental Sciences PAH metabolites in the environment

14. Department of Plant and Environmental Sciences What do I know now? Conclusion and perspectives • Soil organisms are capable of transforming PAHs to highly polar PAH metabolites. The highly polar PAH metabolites do not or only weakly sorp to soil. • Next step is to find the metabolites in the environment – analytical method development to separate our target compound from the matrix (or even better, to identify the entire UCM of compounds in the leachate) ? ?

15. Department of Plant and Environmental Sciences Questions? Thanks to Niels Døssing Overhue, Orbicon Financial support Copenhagen Recycling Center, RECETO, and University of Copenhagen