1

Fate and behavior of pharmaceuticals and EDCs in municipal wastewater treatment

Prof. Dr. Hansruedi Siegrist, EAWAG, Switzerland

20 Years of Research in the Field of EndocrineDisruptors & Pharmaceutical Compounds

Symposium, Berlin, 10 February 2010

Eawag: Das Wasserforschungs-Institut des ETH-Bereichs

2

• Introduction• Elimination processes in WWTP• Transformation products• Additional measures in WWTP• Mass flux study Switzerland• Conclusions

Topics

2

3

Average WWTP effluent concentrationsof selected EDCs

0.1

1.0

10.0

100.0

1000.0

10000.0

17b-E

2EE

2 E1

17a-E

2 E3

Nony

lphen

ol

E1-S

ulfate

Genis

tein

17b-E

2-sulf

ate

Bisph

enol

A

E2-G

lucuro

nide

NP1E

C

Dibuty

l phth

alate

Ave

rage

con

cent

ratio

ns [n

g/l]

Desbrow et al. (1998) Environ. Sci. Technol. 32, 1549; Routledge et al. (1998) Environ. Sci. Tech., 32, 1559; Snyder et al. (2001) Env. Sci. & Technol., 35, 3620; Johnson and Sumpter (2001) Env. Sci. & Techn., 36, 1202; Johnson et al. (2005) Wat. Res., 39, 47.

4

Specific estrogenic potencies of important EDCs in vitro and in vivo

1.E-08

1.E-07

1.E-06

1.E-05

1.E-04

1.E-03

1.E-02

1.E-01

1.E+00

1.E+01

1.E+02

17b-E

2EE

2 E1

17a-E

2 E3

Nony

lphen

ol

E1-S

ulfate

Genis

tein

17b-E

2-sulf

ate

Bisph

enol

A

E2-G

lucuro

nide

NP1E

C

Dibuty

l phth

alate

Estr

adio

l Equ

ival

ente

[ng/

l] In vitro testsIn vivo (vitellogenin)In vivo (water snail)

Johnson A., Sumpter J. (2001) Removal of endocrine disrupting chemicals in activated sludge treatment works. Env. Sci. & Techn., 36, 1202. Oehlmann J. et al. (2006) Bisphenol A induces superfeminization in the ramshorn snail Marisa cornuarietis (Gastropoda: Prosobranchia) at low concentrations. Environ. Health Prosp., 114 (S-1) 127-133.

3

5

Estrogenicity of important EDCsProduct of average concentration and specific estrogenic potency

0.00001

0.0001

0.001

0.01

0.1

1

10

100

17b-E

2EE

2 E1

17a-E

2 E3

Nony

lphen

ol

E1-S

ulfate

Genis

tein

17b-E

2-sulf

ate

Bisph

enol

A

E2-G

lucuro

nide

NP1E

C

Dibuty

l phth

alate

Estr

adio

l equ

ival

ents

[ng/

l]

In vitroIn vivo (vitellogenin)In vivo (water snail)

6

Pharmaceuticals in treated wastewater

Trim

etho

prim

Sulfa

met

hoxa

zole

Rox

ithro

myc

in

Ibup

rofe

n

Dic

lofe

nac

Clo

fibric

acid

Car

bam

azep

ine

Ate

nolo

l

Sota

lol

Met

opro

lol

Prop

rano

lol

Gal

axol

ide

Tona

lide

Iopa

mid

ol

Dia

triz

oate

Iom

epro

l0,0

1.0

2.0

3.0

4.0

5.0

6.0 March

May

September

betablocker

antibiotics

diclofenac

musk fragr.

contrast media

carbamazepine

conc.in µg/L

Ternes et al., Chemosphere 2007 360‘000 Pop. Equiv. WWTP for Nitrification/Denitrification

4

7

EE2 0.03 ng/L < 1 ng/L (WWTPs)

1: Suggested maximum annual average concentration

Annual averagemeasured concentration

in German rivers

Diclofenac 100 ng/L 50-500 ng/L

Environmental quality standards (EQS) of contaminants determined according to WFD

(based on ecotoxicological data)

1AA-EQS-S

Source: Moltmann et al., 2007, German EPA report

Bisphenol A 0.79 ng/L 0.5 ng/L-270 ng/L

8

Elimination processes in biological wastewater treatment

• Stripping (negligible for PPCP’s)• Biological degrad./transformation

• potential post treatment:ozonation , PAC additioncombined with filtration, (minor/no effects: UV, wetland)

• Sorption on particulates (sludge)

sludgedigestion

sludgethickening

drying, incineration,

disposal

screen grid / fat removal

rawsewage

primaryeffluent

sludge dewatering

second.effluent

biogas dewateredsludge

receivingwater

excesssludge

primarysludge

post treatment: filtration, disinfection

primaryclarifier

second.clarifier

biologicaltreatment

5

9

Sorption of trace pollutants

lipophilic cell membrane

Bacterium

negatively loaded surface

HN

N N

F

O O

OH

Adsorption of a bivalent compound(e.g. Norfloxacin) or a positevely

loaded compound on the surfaceO

Tonalide(AHTN)

Absorption of a hydrophobic compound (e.g. Tonalide) in the lipophilic membrane

10

Compound Kd (l gSS-1) sorbed fraction (%)

Diclofenac 0.1 3 1.5 1.5 Ethinylestradiol 0.4 11 6 6

Tonalide 2 / 5 47 23 43

Norfloxacin 2 / 25 38 23 79

Sorption of micropollutants in WWTP

Primary sludge0.15 gSS l-1

Primary clarifier Activated sludge

Raw wastewater0.30 gSS l-1

Secondary sludge0.15 gSS l-1

Sorbed concentration: Csorb = Kd · SP · CdissKd = Sorption constant [l gTSS-1] SP = sludge production [g l-1]

=1+ Kd·SP

Kd·SPCdiss+ Csorb

CsorbSorbed fraction:

6

11

Norfloxacin in WWTP Zurich (600’000 PE)mainly sorbed to sewage sludge

51 ± 4 %Excess sludge: ca. 0.1 gTSS LWW-1

8 ± 1 % Outlet Filter70 ± 10 %

Primary effluent11 ± 2 %

Second. effluent

no biological degradation

73 ± 11 % Digested sludgeca. 0.15 gSS L-1

82 ± 9 % Raw sludge

sorbeddissolved

Inlet (~0.2 gTSS L-1)97 ±10 g d-1 = 100%

Mechanicaltreatment

Flocculation-filtration

Biologicaltreatment

Sludge treatment

70 %30 %

HN

N N

F

O O

OH

+H2N

O-

12

% of the equilibrium concentration in the rising gas bubble

Stripping of volatile compounds

0 20 40 60 80 100

0

1

2

3

4 m

Methane(H = 28)

Perchlorethylen(H = 0.77)

CO2(H = 1.07)

Chloroform (H = 0.13)

Fine bubble aeration

7

13

Stripping of volatile compounds

Stripping efficiency: ηStripping = H·qair / (1 + H·qair) ≈ H·qair

Musk fragrance Tonalide (HTon = 0.005) => ηStripp,Ton = 10·0.005 = 0.05 (-)=> Stripping efficiency low, except for surface aeration and MBR

Due to small Henry coefficient air bubble in equilibrium: Cair = H · Cdiss

Mass balance: Cin = Cdiss + Cdiss·H·qair = Cdiss·(1+H·qair)

Cair· qair = Cdiss· H · qair

qair ≈ 6-15 m3 air m-3 wastewater

1 m3 wastewater Aeration tank: Cdiss(fully mixed)Inlet conc. Cin

Outlet conc. Cdiss

14

Pollutant is only transformed

(no carbon source)

Cometabolism : • Growth only with primary substrate• Enzyme system used for transformation of pollutant

ng/lmg/l μg/lConcentration

Pollutant is mineralized(Carbon- and

energy source)

Substrate growth (Pollutant = Substrate)

Growth limitfor single substrate

Mixed substrate• Primary substrate needed• Enzyme system used for

degradation of pollutant

Biological degradation or transformation

8

15

Biological Degradation / Transformation

Sludge age (SA)

2 - 5 d BezafibrateSulfamethoxazoleIbuprofen

degradable at 15°C and SAmin

5 -15 d EthinylestradiolIopromideRoxithromycinBisphenol A

not degradableSA < 20d Carbamazepine

Diazepam

Bio

logi

cal D

egra

datio

n/Tr

ansf

orm

atio

n

100%

0%

SAminimum

16

H O

OO H

H O

Ternes et al. (1999)

Degradation of 17β-Estradiol and Estronein batch reactor with activated sludge (0.26 g l-1)

Time [Hours]

C/C0 (C0 = 1μg/l)

Kinetic 1. Order: ri = - ki·XTSS·Ci

9

17

First order degr. constants for N-removal plants

0.001

0.01

0.1

1

10

100

1000

Azith

romy

cin

Clar

ithro

myc

in

(Anh

ydro

-)Eryt

hrom

ycin

Roxit

hrom

ycin

N4-A

cetyl

-Sulf

am.

Sulfa

meth

oxaz

ole(a

)

Sulfa

meth

azin

(a)

Diaz

epam

(b)

Carb

amaz

epine

(b)

Acet

ylsali

cylic

acid

(c)

Diclo

fena

c (b)

Feno

prof

enIbu

profe

nInd

ometa

cine

Napr

oxen

Para

cetam

olAT

HDA

MIDi

atriz

oate

Iohex

olIom

epro

lIop

amido

lIop

rom

ide

Iotha

lamic

acid

Ioxith

alam

icac

idEs

tradio

l (d)

Estro

ne(d

)

Ethin

ylestr

adiol

(d)

Beza

fibra

teCl

ofibr

icac

id

Feno

fibric

acid

Gemf

ibroz

ilPi

race

tamTo

nalid

e(a

)

Galax

olide

(a)

Deg

rada

tion

cons

tant

kbi

o[l

g TS

S-1

d-1 ]

Antibiotics

Antid

epre

ssan

tAn

tiepi

lept

ic

Antiphlogistics Iodinated contrast agents Lipid regulators

Noo

tropi

c

Estrogens Frag

ranc

es

> 90% removal

< 10% removal

18

Optimal reactor konfigurationfor first order kinetic

hydraulic retention time (HRT)

Batch reactorCi,HRT/Ci,0 = exp (-ki·XTSS·HRT)

First order kinetic: ri = - ki·XTSS·CiCi/Ci,0

1.0

0

one fully mixed reactorCi,HRT/Ci,0 = (1+ki·XTSS·HRT)-1

Cascade with 3 reactors Ci,HRT/Ci,0 = (1+ki·xTSS·HRT/3)-3

10

19

Mass flux of 17α-Ethinylestradiol (g d-1)at WWTP Wiesbaden (300’000 PE)

Primaryclarifier

Rawwastewater

Secondaryclarifier

Primaryeffluent

Secondaryeffluent

Denit 1 Nitrification

Primary sludge

Digester

Digested sludge

Denit 2

Secondary (excess) sludge

dissolvedadsorbedconjugated (estimation)

internal recirculation and return sludge

< 0.07

11

21

Source: Joss und Siegrist, 2005, Eawag News

Comparison of biological degradation of biofilter and MBR with activated sludge

SchlammalterCAS MBR11d 15d11d 30d11d >50d

Comparison with degradation in biofilter [%]

10 20 30 40 50 60 70 80 90 1000

10

20

30

40

50

60

70

80

90

100

CLAERY

TRISMX

0

Sludge agecon.pl MBR11d 15d11d 30d11d >50d

Degradation in activated sludge plant [%]For nutrient removal

30 40 50 60 70 80 901000

10

20

30

40

50

60

70

80

90

100

E1

E2

AZI

SPY(1)

SPY(2)

10 200

Degradation in activated sludge plant [%]For nutrient removal

Comparison with degradation in MBR [%]

Degradation efficiency similar for plants with similar nutrient removal

22

reaction I/II: oxidation prim./sek. hydroxyl moietiesreaction III: cleavage of amide-methylen bond

reaction IV: oxidative decarboxylation

Potential aerobic degradradation pathwayof Iopromide (contrast media)

reaction V: deacetylation

O

NH OHOH

O N OHOH

I

NH

OO

I

I O

O

O

NH OHOH

O N OHOH

I

NH

OO

I

I

O

O

NH OHOH

O N OHOH

I

NH

OO

I

I O

O

NH OHOH

O N OHOH

I

NH

OO

I

I

Iopromide TP 819 (3)

TP 805 B (2)

TP 805 A (1)O

NH2

O N OHOH

I

NH

OO

I

I O

O

NH OHOH

O NH

I

NH

OO

I

I

O

O

NH OHOH

O N OHO

I

NH

OO

I

I O

O

TP 817 A (5)

O

NH2

O N OHO

I

NH

OO

I

I O

O

NH

O N OHO

I

NH

OO

I

I OOH

O

TP 731 B (8)

TP 731 A (7)

TP 729 A (4)

TP 787 A (6)

O

NH2

O N

I

NH

OO

I

I

OH

O

O

NH

O N

I

NH

OO

I

IOH

O

OH

O

O

NH

O NH

I

NH

OO

I

IOH

O

TP 701 A (11)

TP 759 (9)

TP 701 B (10)

O

NH2

O NH

I

NH

OO

I

I

TP 643 (12)

I I

II

III

III

II

IIIV

III

IV

V

V

V

V

III

III

IV + V

II + IV

II + IV

II + IV

IV + V

V

Source: Schulz et al., ES&T, 2008

12

23

Transformation products of Iopromidein WWTP Frankfurt

Sludge age: 20-22 d, hydraul. retention time (biol): 4-5 h, 1.3 Mill person equivalent

Primarysludge

Gritremoval

Primaryclarifier sec. clarifier 1

Return sludge

Denitr Nitrificationsec. clarifier 2Screen

Secondarysludge

Secondarysludge

2. Biological step(SA:15-20d; HRT: 4-5h)

1. Biological step(SA: 4d; HRT: 0,5h)

Nitrification2

Receivingwater

221 3

4

Denitr

Iopr.TPs

3

0.01.02.03.04.0c [µg/L]

Iopr.TPs

0.01.02.03.04.0 4

c [µg/L]

Source: Schulz et al., ES&T, 2008

Iopr.

1

0.01.02.03.04.0

c [µg/L]Iopr.

TPs

2

0.01.02.03.04.0c [µg/L]

TPs

24

Transformation products of iodatedcontrast media in surface and ground water

Conc. in µg/L

WWTP effluent Surface water Ground water0

2

4

6

8

Sum of 15 TPsIomeprol

Sum of 12 TPsIopromid

Sum of 9 TPsIopamidol

(0.8)

(1.7) (1.1)

(1.2)

(1.4) (128)

(0.5)

(0.7)(261)

( ):Conc. Σ TP Conc. ICM

Dilution

Transformation

Source: Kormos et al., ES&T, in preparation

13

25

H3C

Transformation of CodeinTP 314, m/z 313 14-Hydroxycodeinon

H3C

TP 316, m/z 315 14-Hydroxycodein

Codein

H3C

TP 300 (1), m/z 299 7,8-Dihydro-

8,14-dehydrocodein

TP 302, m/z 301 14-Hydroxy-N-

desmethylcodein

H3C

TP 300(2) ?

Dissertation: Arne Wick(ES&T in preparation)

stabletransformationproduct

This studies have been done in the mg/l range, in practice we have mug/l

26

• Cascade of reactors or SBR

• For critical cases (low dilution in receiving water, ground water infiltration, water reuse,...) additional treatment with chemical and physical processes, e.g.:- partial ozonation, - powder activated carbon addition

Measures at the WWTP

• Increasing the sludge age to 10 -15 days, which meansNitrification and Denitrification

14

27

270 20 40 60 80 100

Atrazin

Mecoprop

Atenolol

Benzotriazol

Methylbenzotriazol

Metoprolol

Sulfamethoxazol

Clarithromycin

Carbamazepin

Sulfapyridin

Trimethoprim

Diclofenac

Eliminiation (%)

966 +/- 271617 +/- 47396 +/- 63

Effect of ozone concentr. on elimination efficiency (0.4-1.0 gO3/gDOC = 2-5 gO3/m3)

Calculation: 100 – 100 *cafter ozonation/ csecondary effluent Ozone in g/kg DOC

O

O

CH3

CH3

O

O

H3C

HOOH

O

H3C

CH3

O

O OH

OCH3

NHO

O

ONNH

SH2N

O

O

Full-scal plant Regensdorf

28

PAC addition to secondary effluent, contacttank and additional sedimentation

Pilot plant EawagAll elimination rates referring to primary effluent

0%

20%

40%

60%

80%

100%

Sulfamethoxazol

Benzotriazol

Atenolol

Diclofenac

Carbamazepin

Clarithromyzin

Mefenaminsäure

5-Methyl-Benzotriazol

Ranitidin

Venlafaxin

DHHPrimidon

Codein

Oxazepam

Iopamidol

Iopromid

Iohexol

Diatrizoat

Ibuprofen

Naproxen

Bezafibrat

10 mgPAC/l without PAC-recycling to biology (Pilot: 8.8 mgDOC/l; Ref: 8.4 mgDOC/l)10 mgPAC/l with PAC-recycling to biology (Pilot: 7.4 mgDOC/l; Ref: 8.9 mgDOC/l)

withoutwith

15

29

Mass flux model SwitzerlandModeling of Diclofenac in Swiss rivers

Elimination in WWTP

Load per WWTP

25%

Behavior in receiving waters 175 μg Ed-1

Consumption, sales data Switzerland

Parent compound to sewer

Load per inhabitant

16%

235 μg d-1

4000 kg a-1

30

Diclofenac

In Fliessgewässerproben gemessen [g/d]

Grö

sse

Ein

zugs

gebi

et [E

]

1 2 5 10 20 50 100 200

1

2

5

10

20

50

100

200

10'000

20'000

50'000

100'000

200'000

500'000

1'000'000

1:1

×2

÷2

Measured loads in rivers [g/d]

Pred

icte

dlo

ads

[g/d

]

Cat

chm

ent s

ize

[# in

hab.

]

Model • Sale DCF: 4000kg/a 1 • *Excretion DCF: 16% unchanged 2• Elimination DCF WWTP: Ø 25% 3 • Degradation DCF in natural water bodies: none (rivers), full elimination (lakes) 41 IMS Health AG (2000+2004) 2 Lienert et al. (20067) 3 Ternes and Joss (2006) 4 Buser et al. (1998)

Diclofenac Prediction versus Measurements

**

16

31[μg/L]

< 0.001

0.001 - 0.01

0.01 - 0.1

0.1 - 1

> 1

no Q95% available

discharge to lake

downstream of125 WWTP**(15% of total pe)

Diclofenac: Concentrations in Swiss rivers(based on consumption data and Q95% river flow)

5 PNECDCF

Similar results for other compounds/effects: Carbamazepin, Sulfamethoxazole, Diazinon, estrogenic activity, …(Ort et al. (2009) Environ. Sci. Technol., 43, 3214–3220)

32

Conclusions

• Micropollutants are eliminated in WWTP mainly by sorption and biological degradation or transformation

• Elimination of a lot of trace pollutants is insufficient even athigh solid retention times (sludge ages)

• Losses to surface water by combined sewer overflows (1-2%) and exfiltration from sewer (3-8%) to groundwater

• Additional measures are required for critical cases (low dilution of wastewater in receiving waters, substantial infiltration to groundwater and reuse of treated wastewater)

• Advanced processes (e.g. ozone and PAC addition) have been successfully tested in pilot and full-scale and are available for an acceptable price in comparison to overall treatment cost.

17

33

Thank you for your attention

The results of this presentation are based on the work in:

EU Neptune project (Contract No 036845, SUSTDEV-2005-3.II.3.2), which was financially supported by grants obtained from the EU Commission within the Energy, Global Change and Ecosystems Program of the Sixth Framework (FP6-2005-Global-4).

EU project Poseidon (EVK1-CT-2000-00047) which was financially supported by grants obtained from the EU Commission within the Fifth Framework Programme and

Swiss national project MicroPollSchweizerische EidgenossenschaftConfédération suisseConfederazione SvizzeraConf ederaziun svizra