Are we about to upgrade wastewater treatment for removing organic micropollutants?

Transcription

1 Are we about to upgrade wastewater treatment for removing organic micropollutants? Adriano Joss, Hansruedi Siegrist, Eawag, Switzerland Arne Wick, Michael Schlüsener, Thomas Ternes, BfG, Germany Neptune Workshop, 25 March 2010, Quebec Neptune workshop: Technical Solutions for Nutrient and Micropollutants Removal in WWTPs Eawag: Swiss Federal nstitute of Aquatic Science and Technology Université Laval, Québec, March 25-26, 2010

2 Contents Sorption Biodegradation Transformation products Predicting environmental concentrations Conclusion 01/04/2010 2

3 Removal by sorption on activated sludge Negatively loaded surface F H N N HN Bacteria Adsorption of a bivalent compound (e.g. Norfloxacin) or a positively loaded compound on the surface Tonalide (AHTN) Absorption of a hydrophobic compound (e.g. Tonalide) in the lipophilic membrane Lipophilic cell membrane 01/04/2010 3

4 Sorption of micropollutants Sorbed concentration: C sorbed = K d SS C soluble K d = Sorption coefficient [l/gss] SS = Suspended solids or sludge production [g/l] Sorbed fraction: C sorbed C soluble + C sorbed = K d SS 1 + Kd SS 01/04/2010 4

5 Sorbed share [%] Carbamazepine, Clofibric acid, buprofen Ethinylestradiol Estradiol, Estrone, Ethinylestradiol Diclofenac Norfloxacin Galaxolide, Tonalide Diazepam, Roxithormycin Diclofenac, opromide Galaxolide, Tonalide Norfloxacin Pharmaceuticals Sorption of micropollutants on activated sludge 100 Sludge prod gss m gss m 200 gss m gss m -3 Secondary sludge Primary sludge 01/04/ Sorption coefficient K d,i [L kg SS ]

6 Contents Sorption Biodegradation Transformation products Predicting environmental concentrations Conclusion 01/04/2010 6

7 Full scale sampling Kloten-pfikon (Zurich-North) CAS: PE MBR: 100 PE Altenrhein Lake Constance CAS: PE 01/04/ BioFilter: PE

8 Full scale sampling Kloten-pfikon (Zurich-North) Activated sludge floc CAS: PE MBR: 100 PE Altenrhein 100 mm Lake Constance CAS: PE 01/04/ BioFilter: PE

9 Full scale sampling Kloten-pfikon Zurich-North CAS: PE Submerged biofilm reactor Altenrhein (Bodensee) MBR: 100 PE CAS: PE 01/04/ BioFilter: PE

10 Full scale sampling Kloten-pfikon Zurich-North CAS: PE MBR: 100 PE Altenrhein 50% wastewater to biofilter: h HRT Lake Constance 50% wastewater to CAS: 6 20 h HRT CAS: PE 01/04/ BioFilter: PE

11 Full scale sampling Kloten-pfikon Zurich-North Liquid sample Sludge sample CAS: PE MBR: 100 PE Altenrhein Lake Constance CAS: PE 01/04/ BioFilter: PE

12 Comparison of elimination in MBR, biofilter and conventional plant Elimination in biofilter [%] E1 SPY(1) AZ SPY(2) Elimination in conventional plant [%] E2 01/04/ Ternes and Joss, 2006, WA Publishing ERY CLA TR Elimination in MBR [%] 0 SMX Sludge age Schlammalter con.pl CAS MBR MBR 11d 11d 15d 15d 11d 11d 30d 11d >50d Most compounds: a) different treatment, comparable removal b) only partially removed Elimination in conventional plant [%]

13 01/04/ Batch experiment Test degradation in lab

14 Soluble concentration [µg/l] Soluble concentration [µg/l] [µg/l] Batch experiment with municipal sludge buprofen Diclofenac C t /C 0 Δt Time [d] Relative removal rate constant log Ct log C0 kbiol SS t Reaction rate [μg m -3 Reactor d -1 ] 0.1 Time [d] Blank (CAS) CAS CAS+SS Blank (MBR) MBR MBR+SS Removal (pseudo) first order dct kbiol SS Ct dt Substance conc. [μg m -3 Reaktor] 01/04/ Rate constant [L gss -1 d -1 ] Sludge concentration [gss L -1 ]

15 Modelling removal in the second biological step removal [%] July measured predicted ND 01/04/ psycho-active drugs Model fits most but not all compounds betablockers

16 Modelling removal in the second biological step removal [%] March measured predicted <0% < 0% 01/04/ Model psycho-active fits most drugsbut not all compounds betablockers

17 Contents Sorption Biodegradation Transformation products Predicting environmental concentrations Conclusion 01/04/

18 Removal of atenolol and psychoactive drugs in WWTP Frankfurt [c/c 0 ] Codeine Dihydrocodeine 3 Morphine < LQ Primidone Atenolol Screen Grit primary CD removal Clarifier 1 Denitr Nitrification Clarifier 2 removal clarifier Denitr 01/04/ Primary sludge 1. Biological step (SA: 0.5d; HRT: 0.5h) 2. Biological step (SA:15-20d; HRT: 4-5h) Secondary sludge 4 Receiving water

19 Biological transformation Example: Codeine used as analgesic and cough supressant most widely used opiate in the world opium contains 0.2 to 6% codeine mainly produced from morphine by methylation of the hydroxy group at the aromatic ring up to 90% is removed in WWTPs by primary degradation capsule of the opium poppy (Papaver somniferum L.). formation of transformation products (TPs)? 01/04/

20 Codeine transformation products TP 314, m/z 313 TP 332, m/z 331 TP 316, m/z 315 Codeine TP 300 (1), m/z 299 TP 264, m/z 263 TP 302, m/z /04/ in most cases basic structure unchanged typical reactions observed: double bond shift hydroxylation demethylation

21 opromide: potential aerobic degradation pathways reaction /: oxidation prim./sek. hydroxyl moieties reaction : cleavage of amide-methylen bond reaction V: oxidative decarboxylation reaction V: deacetylation H N H H N H H N H H H H H TP 805 A (1) H H H N H H H opromide TP 819 (3) TP 805 B (2) H N H 2 TP 731 A (7) N H TP 817 A (5) TP 731 B (8) H H V + V H H + V + V N H 2 TP 729 A (4) V V N H H TP 787 A (6) + V V V + V N N H 2 TP 701 A (11) V H TP 759 (9) V H H TP 701 B (10) V V 2 TP 643 (12) 01/04/ Source: Schulz et al. (2008) ES&T

22 Transformation products (TPs) of opromide in WWTP Frankfurt c [µg/l] opr TPs c [µg/l] opr. 2 TPs c [µg/l] TPs 2.0 opr c [µg/l] opr TPs Primary Screen Grit clarifier CD removal Clarifier 1 removal Denitr Nitrification Clarifier Denitr Primary sludge 1. Biological step (SA: 0.5d; HRT: 0.5h) Return sludge Secondary sludge 2. Biological step (SA:15-20d; HRT: 4-5h) Secondary sludge 4 Receiving water 01/04/ Source: Schulz et al., ES&T, 2008

23 Transformation of iodinated contrast media Conc. in µg/l 8 6 (0.5) (1.2) ( ): conc. Σ TP conc. CM omeprol sum of 15 TPs opromide sum of 12 TPs opamidol sum of 9 TPs 4 2 (0.8) dilution (0.7) transformation (261) (1.4) (128) (1.7) (1.1) 0 WWTP effluent surface water groundwater 01/04/

24 Contents Sorption Biodegradation Transformation products Predicting environmental concentrations Conclusion 01/04/

25 Wetland van Cuijk 3 2 1) WWTP influent 2) WWTP effluent 3) Reed bed influent 4) Reed bed effluent 5) Effluent tertiary pond 01/04/

26 Wetland effluent (ng/l) Wetland van Cuijk 4 days hydraulic residence time 0.17 m 3 m-2 d-1 hydraulic loading 10'000 1' /04/ buprofen '000 10'000 Wetland influent (ng/l)

27 Diclofenac: predicted concentrations in Swiss surface waters based on the dilution factor (environmental quality standard: 0.1 µg/l) μg/l μg/l QN * μg/l μg/l μg/l A simple model allows identifying hot spots for advanced treatment assumption consumption: 4 t/a 35% (Dicl. + meta) in wastewater elimination in WWTP: 25% 3 no degradation in surface water rt et al. GWA 11, /04/

28 Conclusions Sorption to sludge: relevant for few compounds Degradation achieves only partial removal First order kinetic does not always fit Transformation products of similar chemical structure often formed Does elimination result in detoxification? Wetlands achieve little micropollutant removal Environmental concentrations: estimation based on consumption and dilution dentify spots for advanced treatment 01/04/

29 Thank you for your attention and the European Commission for financing NEPTUNE, 6 th Framework Programme 01/04/