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CEC Symposium Providence, 29/30. July 2007 Thomas A. Ternes, BFG Koblenz
Thomas Ternes, Adriano Joss, Hansruedi Siegrist
Contaminants of Emerging Concerna Challenge for Urban Water Management
CEC Symposium Providence, 29/30. July 2007 Thomas A. Ternes, BFG Koblenz
HYDROPHILIC
LIPOPHILIC
POLA
RIT
Y
pharmaceuticalsbetablockers, antibiotics,
contrast media,analgesics, antiepileptics,
parasiticides, babiturates, opioides
estrogenes
New emerging compounds
VOLATILE NON VOLATILE
Volatility
from Walter Giger, in Ternes und Joss, IWA Publishing, 2006
musk fragrancesMTBE
phosphoric esterflame retardantsNDMA
corrosion inhibitorse.g. benzotriazole
UV filter
perfluorinatedcompounds (PFOA)
benzene, naphthalenesulfonates
surfactants
CEC Symposium Providence, 29/30. July 2007 Thomas A. Ternes, BFG Koblenz
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 frag.
contrast media
carbamazepine
conc.in µg/L
Ternes et al., Chemosphere 2007360‘000 Pop. Equiv.Nitrification/Denitrification
CEC Symposium Providence, 29/30. July 2007 Thomas A. Ternes, BFG Koblenz
Water/Sediment
Industry
STP
Urban Water cycle
bank filtrate
Waterworks Drinking water
Irrigation (soil/aquifer)
“Run off“
infiltrationgroundwater
CEC Symposium Providence, 29/30. July 2007 Thomas A. Ternes, BFG Koblenz
55 plants of three categoriescat 1: small WW with agriculturecat 2: WW with bank filtrationcat 3: WW with no pharmaceutical source
In 11 of 55 WW sulfamethoxazole was detected (7-66 ng/L): LOQ: 2 ng/L10 WW from cat 2, 1 WW from cat 1
cat 1: 55 waterworks cat 2:
cat 3:
Antibiotic and ICM residues in German drinking water 2003/2004
Mückter et al., Environ. Health Persp., in preparation
H 2N S O 2 N HN O
Iodinated contrast media were detectedup to 218 ng/L (LOQ: 5 ng/L)
Carbamazepine was present up to 150 ng/L
CEC Symposium Providence, 29/30. July 2007 Thomas A. Ternes, BFG Koblenz
Iodinated contrast media (e.g. Iodinated contrast media (e.g. diatrizoatediatrizoate, , iopamidoliopamidol))AntiepilepticsAntiepileptics (e.g. (e.g. carbamazepinecarbamazepine, , primidoneprimidone))Lipid regulators and antiLipid regulators and anti--inflammatoriesinflammatories (e.g. (e.g. clofibricclofibric acid, ibuprofen)acid, ibuprofen)ComplexingComplexing agents (e.g. EDTA, DTPA)agents (e.g. EDTA, DTPA)Aromatic naphthalene Aromatic naphthalene sulfonatessulfonatesPolar pesticides (e.g. Polar pesticides (e.g. atrazineatrazine, , diurondiuron, , glufosinateglufosinate, , glyphosateglyphosate ))MTBE, MTBE, triclosantriclosan, phthalates, tri(2, phthalates, tri(2--chloroethyl)phosphate chloroethyl)phosphate …………. .
Trace contaminants relevant for drinking water
Contaminants of water resources
e.g. Loraine and Pettigrove, 2006; Stackelback et al., 2007
CEC Symposium Providence, 29/30. July 2007 Thomas A. Ternes, BFG Koblenz
EE2 0,03 ng/L < 1 ng/L (STPs)
1) maximum annual average concentration
Annual averagemeasured concentration
in Germany
Diclofenac 100 ng/L 50-500 ng/L
Discharge primarily via wastewater treatment plants
Environmental quality standards (EQS) according WFD
1AA-EQS-V
From Moltmann, Liebig, Knacker, Keller, Scheurer, Ternes, report German EPA
Bisphenol A 0,79 ng/L 0,5 ng/L-270 ng/L
CEC Symposium Providence, 29/30. July 2007 Thomas A. Ternes, BFG Koblenz
Measures at the source
Reduction of the loads entering watewater treatment plants (WWTPs)
Evironmental quality standards (EQS) from water framework directory
If EQS are exceeded (probably for diclofenac, isoproturon, EE2, bisphenol A, …)advanced measures have to be established, in order to guaranty the good
ecological/chemical status of rivers and streams until 2015.
Regulation of chemicals is an appropriate mitigation tool
CEC Symposium Providence, 29/30. July 2007 Thomas A. Ternes, BFG Koblenz
Improved behavior of consumers and producers
public education (consumers, professionals)
ecolabelling of products (PBT-concept, FOA-concept)
adequate disposal (e.g. incineration, recycling)
recycling/disposal of non-used products by industry
chem. industry: exchange/replacement of environmental harmful and drinking water relevant compounds
"Green Chemistry": Production of ready biodegradablecompounds and those which are not relevant for drinking water
CEC Symposium Providence, 29/30. July 2007 Thomas A. Ternes, BFG Koblenz
score(0, 1, 2, 3)
Ecolable for products
Persistency not biodegradable (< 60% in 28d) 3
results
Bioaccumulation log DOW (pH7) = 1,7 2
EcoToxicity LOEC = 1 µg/L 3
example: diclofenac
Sum PBT: 8
score(0, 1, 2, 3)
Flocculation removal < 10 % 3
results
Activated carbon removal > 90 % 0
Ozonation oxidation > 90% 0
Sum FOA: 3
CEC Symposium Providence, 29/30. July 2007 Thomas A. Ternes, BFG Koblenz
Further measures at the source
Treatment of point sources (e.g. hospitals, nursing houses)
Behandlungan der Quelle
Hospitalwastewater
Sewer
WWTP influent
WWTP effluent
Receivingriver (Glatt)
Concentration [µg L-1]
CiprofloxacinNorfloxacin
0.001 0.01 0.1 1 10 100
PNECHospital
wastewater
Sewer
WWTP influent
WWTP effluent
Receivingriver (Glatt)
Concentration [µg L-1]
CiprofloxacinNorfloxacin
0.001 0.01 0.1 1 10 100
PNEC
Alder et al., 2006
CEC Symposium Providence, 29/30. July 2007 Thomas A. Ternes, BFG Koblenz
Excretion of pharmaceuticals: mainly urine
0
10
20
3040
50
60
70
8090
100
Aspi
rinPa
race
tam
olPr
opox
yphe
neTr
amad
olAm
oxici
llinAz
ithro
myc
inCi
prof
loxa
cinCl
arith
rom
ycin
Eryt
hrom
ycin
Met
roni
dazo
leM
upiro
cinSu
lfam
etho
xazo
leTe
tracy
cline
Trim
etho
prim
Met
form
inTr
oglita
zone
Gab
apen
tinPh
enyt
oin
Valp
roat
eAl
lopu
rinol
Cim
etid
ine
Rani
tidin
eIb
upro
fen
Nabu
met
one
Napr
oxen
Aten
olol
Met
opro
lol
Vera
pam
il
Pseu
doep
hedr
ine
Hydr
ochl
orot
hiaz
ide
Tria
mte
rene
Caris
opro
dol
Bupr
opio
nNe
fazo
done
Setra
line
FecesUrine
Antiphlogistics Antibiotics Ant
idia
betic
s
Ant
iepi
lept
ics
Ant
igou
t
Ant
ihis
tam
ins
Ant
iphl
ogis
tics
Bet
ablo
cker
s
Ant
iarr
hyth
mic
Sym
path
omim
etic
s
Ant
idep
ress
ants
Diu
retic
s
Mus
cle
rela
xant
excretion in %Ternes und Joss, IWA Publishing, 2006
CEC Symposium Providence, 29/30. July 2007 Thomas A. Ternes, BFG Koblenz
Further measures: source separation
Urine separation and local urine collection
No-Mixtoilet
STP
Sewer overflow
Combined sewer
Urine collection
nutrients foragriculture
ozone,membrane?
Receivingwater
CEC Symposium Providence, 29/30. July 2007 Thomas A. Ternes, BFG Koblenz
Efficiency of municipal WWTPs
CEC Symposium Providence, 29/30. July 2007 Thomas A. Ternes, BFG Koblenz
Processes eliminating pharmaceuticals in an WWTP
Chemical oxidationStripping during aerationBiological degradation (mineralization, transformation)
Sorption onto particulate matter (e.g. activated sludge)
CEC Symposium Providence, 29/30. July 2007 Thomas A. Ternes, BFG Koblenz
History of biological wastewater treatment
1960
Rücklauf
effluent
excesssludge
Secondaryclarifier
influent
Activatedsludge tank
Sludge age(days)
BOD removal 2 – 4 20 - 401970
1980
1990
2000
tankvolume(L inh-1)
anaerobic anoxic Nitrification
EnhancedbiologicalP-removal
14 - 20 140 - 200
Denitrification
Denitrification Nitrification
10 - 15 100 - 160
PO4precipitation
Nitrification
Nitrification
8 - 12 80 - 140
Fe, Al
Fe, Al
Siegrist, 2006
Enhanced micropollutant removal
CEC Symposium Providence, 29/30. July 2007 Thomas A. Ternes, BFG Koblenz
00,5
11,5
22,5
33,5
4influent effluent
Sulfameth-oxazol
Carbama-zepine Ibuprofen
DiclofenacAtenolol
SotalolDiatrizoate
Iopromide
(24)
(0)
(96)
(33)(84) (48)
(0)
(83)
18µg/L
Removal in the municipal WWTP Braunschweig
concentration in µg/L ( ): removal in %
Ternes et al., Chemosphere, 2007
CEC Symposium Providence, 29/30. July 2007 Thomas A. Ternes, BFG Koblenz
0
5
10
15
20
25
30
35
<0,2 <0,4 <0,8 <1,6 <3,2 <6,4 <13 <26 <52sum of pesiticide concentrations (without diuron)
in µg/l
From Peter Seel, HLUG, Wiesbaden
Average pesticide concentrations in 106 Hessian STPs(April/May, 1999)
numberSTPs
CEC Symposium Providence, 29/30. July 2007 Thomas A. Ternes, BFG Koblenz
Raw wastewater(pH6.6) 0.25 gSS L-1
Sorbed fraction
Secondary sludge(pH7.5) 0.10 gSS L-1
Primary sludge(pH6.6) 0.15 gSS L-1
Primary clarifier Activated sludge system
*Golet et al., Env. Sci. Technol. 2003, 37, 3243-3249
Tonalide (AHTN) 5500/10000 58 45 50Ciprofloxacin* 2000/20000 33 23 72
PPCPs Kd (L/kg) Sorbed fraction in % (100·Kd·SS/(1+Kd SS))
Diclofenac 450 / 50 10 6 0.5Ethinylestradiol 350 / 270 8 5 3
prim./sec.
W
Sd C
CK =
Kd = f (pH, Corg, T, p, µ)
Ternes et al., 2004, Water Res.
CEC Symposium Providence, 29/30. July 2007 Thomas A. Ternes, BFG Koblenz
Lipophilic cell membrane
Bacterium
Negative charges on biomass surface
Ternes et al., 2004, Env.Sci.Technol.photo: Jürg Kappeler
Absorption of hydrophobiccompounds (e.g. tonalide) into
the lipid double layer membraneAHTN
Sorption onto sludge
Adsorption of positively chargedcompounds at the biomass surfaces
or Intake by cells(e.g. ciprofloxacin)
O
H2
N
O
O
N
N
F
CEC Symposium Providence, 29/30. July 2007 Thomas A. Ternes, BFG Koblenz
Sludge age (SA)
2 - 5 d BezafibrateIbuprofen
SAmin degradable
5 -15 d NaproxenEthinylestradiolIopromideRoxithromycin
no biodegradation< 20d Carbamazepine
Diazepam
Bio
logi
cal r
emov
al 100%
0%
SAminimum
The biological removal depends on:- Substance properties (kbiol)- Sludge age (SA)
Kreuzinger et al., 2004, Wat. Sci. Tech.Ternes et al., 2004, Env.Sci.Technol.
Biological degradation - sludge age
CEC Symposium Providence, 29/30. July 2007 Thomas A. Ternes, BFG Koblenz
CAS: 60‘000 PE
BioFilter: 60‘000 PE
CAS: 55‘000 PE
MBR: 100 PE
Kloten-Opfikon(Zurich-North)
Altenrhein(lake Constance)
Liquid sampleSludge sample
Sampling of WWTPs
CEC Symposium Providence, 29/30. July 2007 Thomas A. Ternes, BFG Koblenz
N
NH2O
HOOC
HN
Cl
Cl
20-30 % biodegradationsorption: negligible
biodegradation: negligiblesorption: negligible
Carbamazepine kbiol 0.01 L gSS-1 d-1Diclofenac kbiol <0.1 L gSS-1 d-1
0
20406080
100120
12 12 10 16 33 75 25 21
effluentsorptiondegrad.
MBR0
20
40
60
80
100
Sludge age[d]
12 10 16 33 75 25 21
effluentsorptiondegrad.
Fate in CAS/MBR/BioF
CAS1 CAS2 Biofilter MBRCAS1 CAS2 Biofilter
proportion in % proportion in %
140160
CEC Symposium Providence, 29/30. July 2007 Thomas A. Ternes, BFG Koblenz
O
Galaxolide(HHCB)
O
Tonalide(AHTN)
insignificant biodegradation50% elimination by sorption onto sludge
0
20
40
60
80
100
120
140
0
20
40
60
80
100
120
140
Tonalide kbiol <0.01 L gSS-1 d-1Galaxolide kbiol ≤ 0.03 L gSS-1 d-1
Fate in CAS/MBR/BioFMusk fragrances
12 12 10 16 33 75 25 21MBRCAS1 CAS2 Biofilter
12 12 10 16 33 75 25 21MBRCAS1 CAS2 Biofilter
effluentsorptiondegrad.
effluentsorptiondegrad.
proportion in % proportion in %
CEC Symposium Providence, 29/30. July 2007 Thomas A. Ternes, BFG Koblenz
Advanced measures at/before WWTPs
advancedelimination of
micropollutants
chemical-physical• PAC• GAC
chemical-oxidation• chloration• UV• H2O2 / UV• ozonation
physical• flocculation• precipitation• ion exchanger• membrane filtrat.• sand filtration
biological (-physical)• sand filtration• trickling filter• soil passage• wetland
CEC Symposium Providence, 29/30. July 2007 Thomas A. Ternes, BFG Koblenz
Is ozonation an overall solution?
CEC Symposium Providence, 29/30. July 2007 Thomas A. Ternes, BFG Koblenz
0.01
0.1
1
10
100
1000
104
105
106
O3ClO2Cl2
t1/2
[s]
Huber et al., Water Res., 2005
Oxidation of pharmaceuticals with O3, HOCl, ClO2Half life times t1/2, [ox] = 1 mg/L
EE2CBZ SMXDICFDIAZBEZF IBU IOP ROX
BEZF: BezafibrateCBZ: CarbamazepineDIAZ: DiazepamDICF: DiclofenacEE2: EthinylestradiolIBU: IbuprofenIOP: IopromideSMX: SulfamethoxazoleROX: Roxithromycine
CEC Symposium Providence, 29/30. July 2007 Thomas A. Ternes, BFG Koblenz
O
R1
OH
O
O
OR2
O
O
OCH3
OHO
N
OH
HO
HN
HOOCCl
Cl
CH3
HO
OH
C CH
S
O
O
H2NHN
N O
N
NH2O
Diclofenac
17 α-Ethinylestradiol
CarbamazepineSulfamethoxazole
Roxithromycin
Huber et al., 2003, Env.Sci.Technol.
Crucial moieties for ozone attack
CEC Symposium Providence, 29/30. July 2007 Thomas A. Ternes, BFG Koblenz
Convent. activated sludge (CAS)2 columns (2 x 140 litre) for ozonationcontact time: ~ 8-9 minPharma. dosage: ~ 2 mg/L/withoutOzone doses: 0.5, 1, 2, 3.5, 5, 10, 15 mg/LDOC: 6 - 8 mg/L (Kloten-Opfikon)DOC: 23 mg/L (Braunschweig)
Pharmac.spike mixing
O3addition
Ozonation of effluents: Braunschweig and Kloten-Opfikon
DECLORATION OF EFFLUENT
CEC Symposium Providence, 29/30. July 2007 Thomas A. Ternes, BFG Koblenz
Ozonation of Braunschweig effluent (DOC: 23 mg/L)
Tri
met
hp.
Sulfa
met
h.
Ery
thro
my.
Ery
th-H
2O
Cla
rith
r.
Rox
ithro
m.
Ate
nolo
l
Sota
lol
Met
opro
lol
Prop
ran.
Car
bam
az.
Clo
fibr.
Ibup
rofe
n
Nap
roxe
n
Ket
opro
f.
Dic
lofe
nac
AH
TN
HH
CB
Iopa
mid
ol
Iopr
omid
Dia
triz
oat
concentrat.in µg/L
0.01
0.10
1.00
10.00 effluent5 mg/L ozone
10 mg/L ozone
15 mg/L ozone
ICM
musk fragr.
lipid regulator,antiphlogistics
betablocker
carbamazepine
antibiotics
Ternes et al., 2003, Wat. Res.
CEC Symposium Providence, 29/30. July 2007 Thomas A. Ternes, BFG Koblenz
Huber et al. ES&T 2005
Pilot plant Opfikon: DOC=6-8 mg/LOxidation of selected pharmaceuticals
MB
R
0.0
0.2
0.4
0.6
0.8
1.0
0.5 1 2 3.5 5O3 dose [mg/L]
0
0.5
1
1.5
2
2.5
3
O3
conc
. [m
g L-1
] SP-
MID
O3
O3rela
tive
resi
dual
s (C
/C0)
CA
S
0.0
0.2
0.4
0.6
0.8
1.0
0
0.5
1
1.5
2
2.5
3
O3 c
onc.
[mg
L-1] S
P-M
ID
rela
tive
resi
dual
s (C
/C0)
O3
O3
O3
iopromide (contrast medium) roxithromycin (macrolide)sulfamethoxazole (sulfonam.) EE2 (estrogen)
CEC Symposium Providence, 29/30. July 2007 Thomas A. Ternes, BFG Koblenz
OH
HO
EE2 MW=296
OH
HO
O
HO O
OH
O
HOHO
?
MW=294
MW=278
OH
O
HOHO
O
OH
MW=298
OH
HO
O
HO O
O
OH
MW=314
Identification
LC/MS/MSpartly GC/MSO
HOHO
O
MW=252
O
HO
O
HO O
MW=268
Ozonation: Oxidation products of Ethinylestradiol (EE2)
Huber et al., ES&T 2004
CEC Symposium Providence, 29/30. July 2007 Thomas A. Ternes, BFG Koblenz
[EE2]0=10μM, pH=8 , T= RT, [t-BuOH]=5mM (•OH scavenger)Estrogenic activity as estradiol equivalents (EEQ)
0
0.2
0.4
0.6
0.8
1
0 5 10 15 20 25
O3 [μM]
c/c 0
EEQs
EE2
Reduction of estrogenic activity with increasing ozone dose
YES assay
Huber et al. ES&T 2004
CEC Symposium Providence, 29/30. July 2007 Thomas A. Ternes, BFG Koblenz
N
SO2
S
N
CH3
CH3
CCl2F
Tolylfluamid
Dimethylsulfamide(DMSA)
NDMAO3
Formation of the cancerogenic NDMAby ozonation when DMSA is present
Elucidated by Carsten Schmidt form TZW, Karlsruhe, Germany
http://www.mlr.baden-wuertemberg.de
CEC Symposium Providence, 29/30. July 2007 Thomas A. Ternes, BFG Koblenz
Number resistences of 1 colonySampling site
5 6 7 8 9„Urban“ influent + + - - -„Rural“ influent - - + + -Effluent STP + + + - -Ozone (8 g/m³) - - - - -Ozone (15 g/m³) - - - - -
Cooperation:University Mainz, Kohnen, Schön-Hölz
Resistences 7,8: Amoxicillin, Clavulanic acid, Ciprofloxacin, Erythromycin, Imipenem, Tertacyclin, Sulfamethoxazole/Trimetoprim, Gentamycin (8)
No resistences found: Vancomycin, Linezolide, Synercide
Number of resistences in enteroccoci detected
Br- BrO3-
850 < 15
780 25
µg/L µg/L
850 < 15
CEC Symposium Providence, 29/30. July 2007 Thomas A. Ternes, BFG Koblenz
Is activated carbon an overall solution?
CEC Symposium Providence, 29/30. July 2007 Thomas A. Ternes, BFG Koblenz
Elimination of iodinated contrast media
source: Kapp et al., 2006; Applied University Biberach • ZV Klärwerk Steinhäule, Ulm
Elimination in %
11
7673
48
91
77
> 88 > 87
> 94
44
0102030405060708090
100
Diatrizoate Iomeprol Iopromide Iohexol Iopamidol
dose of PAC: 10 mg/L; n=7
dose of PAC: 20 mg/L; n=2
CEC Symposium Providence, 29/30. July 2007 Thomas A. Ternes, BFG Koblenz
Options for advanced wastewater treatment
none0.10 – 0.20<< 0.05Activated carbon (PAC)
volume of concentrate?0.1 – 0.250.5 – 3
RO/NF low salt5 – 30 bar
up to 50% concentrate0.2 – 0.32 – 4
RO desalinationup to 50 bar
Toxicologyunknown0.05 – 0.150.1 – 0.3Ozonation
By productsCosts€ m-3
EnergykWh m-3
Pilo
ting
resu
ltLi
tera
ture
, lab
sca
le
Feasible costs: ≤ 75 €/person/year(100 m3/(person·year)
CEC Symposium Providence, 29/30. July 2007 Thomas A. Ternes, BFG Koblenz
Options for action
Registration
Chemical Industry
Advanced treatmentWastewater
Treatment atthe source
Involve public
Product labelling and description
Appropriatedisposal
Advanced treatmentDrinking water
„Green Chemistry“
Ozonation, activated carbon, nanofiltration, …
Specific criteria, relevance for drinking
and ground water
Hospital wastewater, other point sources
Replacement of pollutants toxic for the environment or present in drinking water,
producer is responsible for disposalHazardous waste,incineration, reuse
Consumers, professionals
Toxicity(environ., human)Contamination
drinking, groundwaterThreshold values,Quality criteria
Precautionary principleto deal with emerging compounds with unkowntoxicity (e.g. HPV: 0.1 µg/L)
Hazard, relevance for drinking water, QSAR
Promote degradable compounds, avoid compounds reaching
drinking water
….
CEC Symposium Providence, 29/30. July 2007 Thomas A. Ternes, BFG Koblenz
Human Pharmaceuticals,Human Pharmaceuticals,Hormones and FragrancesHormones and Fragrances
Challenge for Urban Water ManagementChallenge for Urban Water Management
EditorsEditorsThomas TernesThomas TernesAdriano JossAdriano Joss
yr-1Consumption and occurrence
Analytical methods
Environmental risk assessment
Human and animal toxicology
Wastewater treatment
Drinking water treatment
Indirect potable water reuse
Source control, source separation
MICROPOL & ECOHAZARD 2009- 6th IWA Specialised Conference
on Assessment and Control of Micropollutants in Water”
June 2009San Francisco