Eawag - EU Project Neptune

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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

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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

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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

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Full scale sampling Kloten-Opfikon (Zurich-North)

CAS: 55‘000 PE

MBR: 100 PE Altenrhein Lake Constance

CAS: 60‘000 PE

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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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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

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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

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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

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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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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]

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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

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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