1. Potential of ozone for the removal of hazardous micropollutants and related changes in dissolved organic matter composition in a municipal biotreated effluent Bruno Domenjoud 1, Núria Cortés 2, Josep Caixach 2, Santiago Esplugas 1, Sylvie Baig 3 1 University Of Barcelona, Spain 2 IDEA-CSIC, Barcelona, Spain 3 Degrémont SA, France 1

2. OUTLINE  Introduction  New challenge: emerging micropollutant  Regulated micropollutants  Advanced treatment  Experimental  Objectives  Material and methods  Results  Conclusions EA3G-IOA International Conference, April 28-30, Geneva, Switzerland, 2009. 2

3. INTRODUCTION _ New challenge New challenge : Emerging micropollutants  Resistant to conventional treatments  Augmentation of the occurrence in the environment Growth of the environmental and health risks (bio-accumulation with possible severe effects on the receiving organisms) Implementation of advanced treatment at the emission sources: Municipal WWTP European Water Framework Directive (WFD): List of 41 priority and hazardous substances 3

4. EA3G-IOA International Conference, April 28-30, Geneva, Switzerland, 2009. INTRODUCTION _ Regulated micropollutants Micropollutants are metallic or organic and anthropologic substances present at trace level in the environment. WFD: 41 substances listed Priority Hazardous (13): PentaBromoDiphenylEthers (PBDE) Pentachlorobenzene Chloroalcanes C10-C13 Nonylphenols Tributyltin and compounds Hexachlorobenzene Hexachlorobutadiene Hexachlorocyclohexane PAHs Anthracene Endosulfane Cadmium and compounds Mercury and compounds Hazardous (8): DDT, DDD, DDE Aldrine Dieldrine Endrine Isodrine Carbon tetrachloride Perchoroethylene Trichloroethylene Priority (20): DiEthylHexylPhtalates Octylphenols Fluoranthene Alachlor Chlorfenvinphos Chlorpyrifos Diuron Isoproturon Naphtalene Nickels and compounds Lead and compounds 1,2-Dichloroethane Trichloromethane Trichlorobenzenes Pentachlorophenol Dichloromethane Benzene Atrazine Simazine trifluralin 4

5. EA3G-IOA International Conference, April 28-30, Geneva, Switzerland, 2009. INTRODUCTION _ Advanced treatment Advanced treatment for micropollutants removal:  Membrane filtration - Reverse osmosis - Nanofiltration  Activated carbon adsorption  Biological processes with high sludge retention time - N & DN - MBR  Oxidation - Ozonation - AOPs Both concentrated streams and spent media require a proper management Need to evaluate effluent toxicity after treatment (possible bioactivity of by- products) 5 Ozonation Well-known technology, No generation of waste and cpds degradation

6. EA3G-IOA International Conference, April 28-30, Geneva, Switzerland, 2009. EXPERIMENTAL _ Objectives  Specific objectives  Organic micropollutant removal,  Characterization of organic matter bulk fate,  Identification of competitive ozone reactions. Contribute to a better knowledge on technologies able to improve the quality of the water discharged from WWTPs, both considering the conventional parameters and emerging contaminants. 6

7. EXPERIMENTAL _ Material and Methods EA3G-IOA International Conference, April 28-30, Geneva, Switzerland, 2009. 40 mg/L NTP 20 – 60 L/h NTP 20 ºC 1 – 2 L Experimental set up 7

8. EA3G-IOA International Conference, April 28-30, Geneva, Switzerland, 2009. EXPERIMENTAL _ Material and Methods  Chemical Oxygen Demand  Biological Oxygen Demand  Dissolved Organic Carbon  UV-Absorbance at 254 nm  Suspended Solids  Turbidity  Inorganic Carbon  pH  Nitrate and ammonia content Conventional parameters Analytical parameters Micropollutant analysis  VOCs  PAHs  PBDEs  OLCs  Pesticides  Phtalates  Octylphenols//nonylphenols Organic matter fractionation  LC-OCD-ON-UVA 8

9. EA3G-IOA International Conference, April 28-30, Geneva, Switzerland, 2009. EXPERIMENTAL _ Material and Methods 9 LC-OCD-ON-UVA LC-OCD-OND-UVAD stands for Liquid Chromatography (size exclusion) Organic Carbon Detection, Organic Nitrogen Detection and Ultra-Violet Detection. Fractionation: - Primary interaction: molecular weight size exclusion - Secondary interaction: substances’ polarity Retain fraction: highly hydrophobic. Eluted fraction: less hydrophobic. Eluted fraction BiopolymersHumic substances Building BlocksLow Molecular Weight Neutrals Low Molecular Weight Acids BIOPOHSBBLMWNLMWA > 20,000 Da~ 1,000 Da300 ~ 1,000 Da< 350 Da

10. EA3G-IOA International Conference, April 28-30, Geneva, Switzerland, 2009. 10 RESULTS _ Wastewater characterization Municipal secondary wastewater effluent: outlet of a biological treatment BIOFOR C/N®.  Low organic matter content  Poorly biodegradable (BOD 5 /COD) = 0.13  Low inorganic carbon content  Presence of suspended solids  N-NH 3 < 1 mg/L  Moderately aromatic ( 2 < SUVA < 4)

11. EA3G-IOA International Conference, April 28-30, Geneva, Switzerland, 2009. 11 RESULTS _ Wastewater characterization Target and detected micropollutants

12. EA3G-IOA International Conference, April 28-30, Geneva, Switzerland, 2009. 12 RESULTS _ Ozone doses  Micropollutant removal: transferred ozone doses 7, 9 and 180 mg/L  Bulk of organic matter fate: transferred ozone doses 10 and 50 mg/L First kinetic stage Second kinetic stage

13. EA3G-IOA International Conference, April 28-30, Geneva, Switzerland, 2009. 13 RESULTS _ Micropollutant removal

14. EA3G-IOA International Conference, April 28-30, Geneva, Switzerland, 2009. 14 RESULTS _ Micropollutant removal Recalcitrant compounds (removal < 50 %):  PBDE 209  p-p’-DDT  Lindane Non reactive chemical functions towards ozone (aromatic rings deactivated + steric hindrance)

15. EA3G-IOA International Conference, April 28-30, Geneva, Switzerland, 2009. 15 RESULTS _ Organic matter fractionation Raw effluent: Organic carbon repartition

16. EA3G-IOA International Conference, April 28-30, Geneva, Switzerland, 2009. 16 4 % 51 % -1 % 35 % 0 % RESULTS _ Organic matter fractionation Low ozone dose: TOD = 10 mg/L  Slight mineralization (4 %)  Reduction of HPO  HPI unchanged  Reduction of SUVA  No SS reduction

17. EA3G-IOA International Conference, April 28-30, Geneva, Switzerland, 2009. 17 4 % 51 % -1 % 35 % 0 % RESULTS _ Organic matter fractionation Low ozone dose: TOD = 10 mg/L Removal of the aromatic hydrophobic acids compounds

18. EA3G-IOA International Conference, April 28-30, Geneva, Switzerland, 2009. 18 4 % 51 % -1 % - 9 % 36 % -13 % 50 % Dissolution of SS containing mainly compounds defined as HPI by LC-OCD method. High ozone dose: TOD = 50 mg/L RESULTS _ Organic matter fractionation

19. EA3G-IOA International Conference, April 28-30, Geneva, Switzerland, 2009. 19 -14 % - 40 % - 14 % 27 %  Strong reduction of SUVA-HS highlighting HS transformation despite the increase of OC-HS observed.  27 % of OC-BIOPO reduction. High ozone dose: TOD = 50 mg/L RESULTS _ Organic matter fractionation

20. EA3G-IOA International Conference, April 28-30, Geneva, Switzerland, 2009. 20 -14 % - 40 % - 14 % 27 % Oxidation of high molecular weight compounds into more fractioned molecules. High ozone dose: TOD = 50 mg/L RESULTS _ Organic matter fractionation

21. EA3G-IOA International Conference, April 28-30, Geneva, Switzerland, 2009. 21 CONCLUSION

22. EA3G-IOA International Conference, April 28-30, Geneva, Switzerland, 2009. 22 CONCLUSION

23. Potential of ozone for the removal of hazardous micropollutants and related changes in dissolved organic matter composition in a municipal biotreated effluent Bruno Domenjoud 1, Núria Cortés 2, Josep Caixach 2, Santiago Esplugas 1, Sylvie Baig 3 1 University Of Barcelona, Spain 2 IDEA-CSIC, Barcelona, Spain 3 Degrémont SA, France 23 HOPE YOU ENJOYED THE PRESENTATION ! The authors are grateful for the financial support from the Spanish Ministry of Industry (CDTI) within the framework of the Project CENIT: CEN20071039.