Occurrence and Elimination of Organic Micro Pollutants in Wastewater Treatment Plants

Transcription

1 International Conference and Exhibition on Water in the Environment envirowater February 2006, Stellenbosch, South Africa Occurrence and Elimination of Organic Micro Pollutants in Wastewater Treatment Plants Christoph B. Hannich, DPU GmbH Thomas Ries, DPU GmbH Harald Friedrich, MUNLV NRW Hans Fahlenkamp, Universität Dortmund LEHRSTUHL UMWELTTECHNIK

2 Reasons for the Research Project European Water Framework Directive (EU-WFD)12/2000, Annex X Water Quality Ordinance NRW (Gewässerqualitätsverordnung) 06/2001 Other Organic Trace Compounds Causing Concerns Pharmaceutical residues Personal care products Lack of Data for Trace Compounds Lack of Knowledge of the Behaviour in the WWTPs

3 Ablauf Zulauf Nonylphenole Octylphenole Bisphenol A DEHP Triclosan HHCB AHTN Monobutylzinn Dibutylzinn Tributylzinn TBEP TPP TnBP TCEP TDCP TCPP Iopamidol Iomeprol Atenolol Sotalol Metoprolol Bezafibrat Ibuprofen Diclofenac Carbamazepin Phenazon Clofibrinsäure Roxithromycin Clarithromycin Estradiol Estron Trimethoprim Sulfamethoxazol Estrogens Antibiotics Prescreening Results Organische Spurenschadstoffe im Abwasser 27µg/L ,5 7 6,5 6 5,5 5 4,5 4 3,5 3 2,5 2 1,5 1 0,5 0 Konzentration [µg/l] Industry chemicals Personal care Products Tinorganics Phosphor organic flame retardants X-ray contrast media β-receptorblocker Analgesics, Antiepileptics, Lipidregulator Influent Effluent

4 Investigated WWTPs Cologne-Stammheim > 1 Mio Population Equivalents Düsseldorf-South > 1 Mio Population Equivalents

5 Investigated WWTPs Düsseldorf-South primary sedimentation activated sludge tank final sedimentation effluent influent filter primary-sludge excess-sludge digested sludge

6 Investigated WWTPs Duesseldorf-South / Mass Flow Balance B D, biological degradation B D, elimination by filtration RE SF VK BB NK FI B D, influent B D, effluent primary sedimentation B D, effluent final sedimentation B D, effluent B D, primary sludge B D, excess sludge B D, sorption B D = daily load RE = screening unit SF = grit chamber VK = primary sedimentation BB = biological reactor NK = final sedimentation FI = filtration = sampling point

7 Investigated WWTPs Cologne-Stammheim influent intermediate sedimentation activated sludge tank, activated sludge tank, A-Stage A-Stufe B-Stage B-Stufe final sedimentation filter effluent excess-sludge, B-Stage excess-sludge, A-Stage digested sludge

8 Synthetic Musk Fragrances Polycyclic and nitroaromatic musk fragrances used as additive in cosmetics and soaps etc. bioaccumulation, possible chronical toxicity, metabolites with higher toxic effects shifting from nitroaromatic to polycyclic musk fragrances musk-xylol musk-keton HHCB (galaxolid) AHTN (tonalid) (decreasing use) (substitutes)

9 ResultsMassFlowBalance Polycyclic Musk Fragrance - AHTN 90 AHTN MB D und E - KW Düsseldorf-Süd PS = primary sludge Wasserweg ÜSS = excess sludge PS ÜSS Abbau BB = biological degradation PS = primary sludge ÜSS = excess sludge Abbau BB = biological degredation Fracht Load [g/d] Elimination: 85 % Sorption as main way of elimination Influent Zulauf Ablauf Effluent Vorklärung primary Ablauf Effluent Nachklärung final Effluent Ablauf filtration Filter sedimentation sedimentation

10 Natural and Synthetic Estrogens To differentiate between natural and synthetic estrogens Possible endocrine effects for animals and humans (e.g. feminisation of fishes) Environmental relevance in spite of the very low concentrations, because of very low effect concentration Effluent concentrations approx. 1 ng/l PNEC ethinylestradiol*: 0,03 ng/l (Predicted No Effect Concentration) * Quelle: Wenzel et. al. 1999

11 ResultsMassFlowBalances Natural Estrogen 17β-Estradiol PS = primary sludge ÜSS = excess sludge Abbau BB = biological degradation Load Fracht [mg/d] Duesseldorf Düsseldorf 17-ß-Estradiol MB E - KW Düsseldorf -Süd Wasserweg PS ÜS Abbau BB Elimination Filter Elimination: > 90 % - Biological degradation - Environmental relevance in spite of the very low concentrations 17-ß-Estradiol MB D + E - GKW Köln-Stammheim Cologne Wasserweg ÜSS A-Stufe ÜSS B-Stufe Abbau A-Stufe Abbau B-Stufe Elimination Filter 0 Zulauf Ablauf Vorklärung Ablauf Nachklärung Ablauf Filter Influent Effluent primary sedimentation Effluent final sedimentation Effluent filtration Fracht [mg/d] Load [mg/d] Zulauf Ablauf Zwischenkl. Ablauf Nachklärung Ablauf Filter Influent Effluent A Stage Effluent B Stage Effluent filtration

12 Results - Mass Flow Balances X-Ray-Contrast Media - Diatrizoate Flame-Retardant - TCEP PS = PS primary = primary sludge sludge ÜSS ÜSS = excess = excess sludge sludge Abbau Abbau BB = BB biological = biological degradation degradation Amidotrizoesäure MB E-F - KW Düsseldorf-Süd Wasserweg PS ÜSS Abbau BB Diatrizoate - Düsseldorf Marginal elimination: 0-40 % Biological degradation Fracht [g/d] Load [g/d] TCEP - Cologne TCEP MB E - GKW Köln-Stammheim Wasserweg ÜSS A-Stufe ÜSS B-Stufe Abbau A-Stufe Abbau B-Stufe Elimination Filter Zulauf Ablauf Vorklärung Ablauf Nachklärung Ablauf Filter Influent Effluent primary sedimentation Effluent final sedimentation Effluent filtration Fracht [g/d] Load [g/d] Zulauf Ablauf Zwischenkl. Ablauf Nachklärung Ablauf Filter Influent Effluent A Stage Effluent B Stage Effluent filtration

13 Pilot plant LUA NRW, Neuss Total volume: 20 m³ Two parallel lines (reference) Different sludge ages Membrane Bioreactor

14 Pilot Plant Investigations Influence of Sludge Age Pharmaceuticals Versuchsreihe B - Pharmaka tts = 14 d tts= 25 d 100% 80% 60% 40% 20% Elimination Gesamtelimination % 0% Atenolol Bisoprolol Sotalol Metoprolol Propanolol Trimethoprim Clarithromycin Roxithromycin Sulfamethoxazol Carbamazepin Bezafibrat Clofibrinsäure Naproxen Diclofenac Ibuprofen Increasing elimination with higher sludge ages

15 Pilot Plant Investigations Effectiveness of Membrane Bioreactor (MBR) Pharmaceuticals Versuchsreihe C - Pharmaka Straße 1(MBR) Straße 2 MBR Conventional treatment 100% 80% 60% 40% 20% Elimination % Gesamtelimination 0% Atenolol Bisoprolol Sotalol Metoprolol Propanolol Trimethoprim Clarithromycin Roxithromycin Sulfamethoxazol Carbamazepin Bezafibrat Clofibrinsäure Naproxen Diclofenac Ibuprofen Different effects in MBR effects of shorter retention time??

16 TBEP Roxithromycin Trimethoprim Phenazon Iopromid BBP TDCP Possible Risk Assessment Düsseldorf Abl. Filter Köln Abl. Filter 1,0E+02 1,0E+01 1,0E+00 1,0E-01 1,0E-02 1,0E-03 1,0E-04 Quotient Ablkonz./Zielwert [-] Effluent / Target Value [-] 1,0E-05 Tributylzinn Sulfamethoxazol Triclosan 17 ß -Estradiol Dibutylzinn Nonylphenol Clarithromycin TnBP Carbamazepin Octylphenol Bisphenol A Clofibrinsäure Monobutylzinn HHCB DEHP TCPP Ibuprofen AHTN Diclofenac TPP DBP TCEP Moschus Keton Naproxen Similar relevance for both WWTPs

17 Conclusion / Future Prospects A multitude of organic trace compounds reaching the WWTPs Elimination between 0 % and 95 % Instead of degradation, only sorption onto sludge for some compounds Risk assessment is not yet finished Residual concentrations exceed partly the existing PNEC For a lot of compounds the toxicity data are incomplete and not final Resulting PNEC values do not include all possible effects on the aquatic environment Low possibilities for optimising the existing biological treatment Providing more efficient elimination technologies (e.g. oxidation, adsorption)

18 Acknowledgements The project is jointly run by the University of Dortmund, Deutsche Projekt Union (Cologne), state enviromental agency (LUA NRW), Stadtentwässerungsbetriebe Köln and Düsseldorf and the Emschergenossenschaft/Lipperverband (Essen). The project is financial supported by the Ministry of Environment, Nature Conservation, Agriculture and Consumer Protection of the State of North Rhine-Westphalia (MUNLV NRW).