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