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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 Concern a Challenge for Urban Water Management

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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

CEC Symposium Providence, 29/30. July 2007 Thomas A. Ternes, BFG Koblenz

Thank you for your attention

EU projectsPOSEIDON (EVK1-CT-2000-00047) and Neptune (036845)

http://poseidon.bafg.de; http://www.eu-neptune.org