Apr 1, 2010 - 100. 120. 100. 120. < LOQ. 0. 20. 40. 60. 80. 4. [c/c. 0. ] 0. 20. 40. 60. 80. 100. 120. 2. Morphine. Atenolol. Primidone. Codeine. Dihydrocodeine.
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 Institute of Aquatic Science and Technology Université Laval, Québec, March 25-26, 2010
Contents Sorption Biodegradation Transformation products Predicting environmental concentrations Conclusion
01/04/2010
2
Removal by sorption on activated sludge Negatively loaded surface O
O
F OH
N
N
HN
Bacteria
Adsorption of a bivalent compound (e.g. Norfloxacin) or a positively loaded compound on the surface
O
Tonalide (AHTN)
Absorption of a hydrophobic compound (e.g. Tonalide) in the lipophilic membrane
Lipophilic cell membrane 01/04/2010
3
Sorption of micropollutants Sorbed concentration: Csorbed = Kd · SS · Csoluble Kd = Sorption coefficient [l/gSS] SS = Suspended solids or sludge production [g/l] Sorbed fraction: Csorbed
Csoluble + Csorbed 01/04/2010
4
=
Kd·SS 1 + Kd·SS
Sorption of micropollutants on activated sludge
Pharmaceuticals
40 30 20 10 0 1 10
01/04/2010
5
2
10
Norfloxacin
400 gSS m-3 300 gSS m-3 200 gSS m-3
Galaxolide, Tonalide
50
Galaxolide, Tonalide
60
Norfloxacin
Sorbed share [%]
70
Ethinylestradiol Estradiol, Estrone, Ethinylestradiol Diclofenac
80
Diclofenac, Iopromide
90
Diazepam, Roxithormycin
100
Carbamazepine, Clofibric acid, Ibuprofen
Sludge prod.
3
10
Sorption coefficient K d,i [L kg-1 ] SS
100 gSS m-3
Secondary sludge
Primary sludge 4
10
5
10
Contents Sorption Biodegradation Transformation products Predicting environmental concentrations Conclusion
01/04/2010
6
Full scale sampling Kloten-Opfikon (Zurich-North)
CAS: 55‘000 PE
MBR: 100 PE Altenrhein Lake Constance
CAS: 60‘000 PE
01/04/2010
7
BioFilter: 60‘000 PE
Full scale sampling Kloten-Opfikon (Zurich-North)
Activated sludge floc
CAS: 55‘000 PE
MBR: 100 PE Altenrhein 100 mm Lake Constance
CAS: 60‘000 PE
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8
BioFilter: 60‘000 PE
Full scale sampling Kloten-Opfikon Zurich-North
CAS: 55‘000 PE
Submerged biofilm reactor Altenrhein
MBR: 100 PE
(Bodensee)
CAS: 60‘000 PE
01/04/2010
9
BioFilter: 60‘000 PE
Full scale sampling Kloten-Opfikon Zurich-North
CAS: 55‘000 PE
MBR: 100 PE Altenrhein 50% wastewater to biofilter: 0.5 – 1.5 h HRT Lake Constance 50% wastewater to CAS: 6 – 20 h HRT
CAS: 60‘000 PE
01/04/2010
10
BioFilter: 60‘000 PE
Full scale sampling Liquid sample Sludge sample
Kloten-Opfikon Zurich-North
CAS: 55‘000 PE
MBR: 100 PE Altenrhein Lake Constance
CAS: 60‘000 PE
01/04/2010
11
BioFilter: 60‘000 PE
Comparison of elimination in MBR, biofilter and conventional plant Elimination in MBR [%]
Elimination in biofilter [%] 100
E2 E1
70
70
60
60
50
SPY(1)
50
SMX
90 ERY CLA TRI 80
90 80
100
40
Sludge age Schlammalter con.pl MBR CAS MBR 11d 15d 11d 15d 11d 30d 11d 30d 11d >50d 11d >50d
40
SPY(2)
30
30
20
AZI
20 10
10
0
0 0
10
20
30
40
50
60
70
80
90 100
compounds: EliminationMost in conventional plant [%] 01/04/2010
12
0
10
20
30
40
50
60
70
80
90 100
Elimination in conventional plant [%]
a) different treatment, comparable removal b) only partially removed Ternes and Joss, 2006, IWA Publishing
Batch experiment Test degradation in lab
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13
Batch experiment with municipal sludge Ibuprofen
Diclofenac
Ct/C0 0.1
Δt
1
0.9
0.8
0.7
0.6
0.5
0.4
0.3
Time [d]
Relative removal rate constant log Ct log C0 kbiol SS t Reaction rate
→ Removal (pseudo) first order dC t kbiol SS Ct dt Substance conc.
[μg·m-3Reactor·d-1]
14
Blank (CAS) CAS CAS+SS Blank (MBR) MBR MBR+SS
0.1
Time [d]
01/04/2010
0.2
0.1
1
0
1
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
1
concentration [µg/L] Solubleconcentration [µg/l] Soluble
10
0
Soluble concentration [µg/l]
10
[μg·m-3Reaktor]
Rate constant
Sludge concentration
[L·gSS-1·d-1]
[gSS·L-1]
Modelling removal in the second biological step removal [%] 100
measured predicted
July 80
60
40
20
0
01/04/2010
15
ND
psycho-active drugs betablockers Model fits most but not all compounds
Modelling removal in the second biological step removal [%] 100
March
measured predicted
80
60
40
20
0
01/04/2010
16