enviroWater, 20 - 22 February – Stellenbosch, South Africa

Occurrence and Elimination of Organic Micro Pollutants in Wastewater Treatment Plants

Christoph B. Hannich, DPU GmbHThomas Ries, DPU GmbH

Harald Friedrich, MUNLV NRWHans Fahlenkamp, Universität Dortmund

International Conference and Exhibition on Water in the EnvironmentenviroWater – 20 - 22 February 2006, Stellenbosch, South Africa

LEHRSTUHL UMWELTTECHNIK

enviroWater, 20 - 22 February – Stellenbosch, South Africa

Reasons for the Research Project

• European Water Framework Directive (EU-WFD)12/2000, Annex X

• Water Quality Ordinance NRW (Gewässerqualitätsverordnung) 06/2001

• Other Organic Trace Compounds Causing Concerns

Pharmaceuticalresidues

Personal care products

• Lack of Data for Trace Compounds

• Lack of Knowledge of the Behaviour in the WWTPs

enviroWater, 20 - 22 February – Stellenbosch, South Africa

Non

ylph

enol

eO

ctyl

phen

ole

Bisp

heno

l AD

EH

PTr

iclo

san

HH

CB

AH

TNM

onob

utyl

zinn

Dib

utyl

zinn

Trib

utyl

zinn

TBE

P

TPP

TnB

PTC

EP

TDC

PTC

PPIo

pam

idol

Iom

epro

lAt

enol

olS

otal

ol

Met

opro

lol

Beza

fibra

tIb

upro

fen

Dic

lofe

nac

Car

bam

azep

inPh

enaz

onC

lofib

rinsä

ure

Cla

rithr

omyc

inR

oxith

rom

ycin

Trim

etho

prim

Sulfa

met

hoxa

zol

Estra

diol

E

stro

n

AblaufZulauf

27µg/L 20 34 17

00,5

11,5

22,5

33,5

44,5

5

5,5

6

6,5

7

7,5

8

Kon

zent

ratio

n [µ

g/L]

Organische Spurenschadstoffe im Abwasser

Industry

chem

icals

Personal

care

Products

Tinorgan

icsPhosp

hor org

anic

flame ret

ardan

ts

X-ray co

ntrast

media

β-Rec

eptor-

blocker

Analges

ics,

Antiepile

ptics,

Lipidregulat

orAntib

iotics

Estrogen

s

Prescreening Results

Influent

Effluent

enviroWater, 20 - 22 February – Stellenbosch, South Africa

Investigated WWTPs

Cologne-Stammheim

Düsseldorf-South

> 1 Mio Population Equivalents

> 1 Mio Population Equivalents

enviroWater, 20 - 22 February – Stellenbosch, South Africa

Investigated WWTPs –Düsseldorf-South

influent

digestedsludge

primary-sludge excess-sludge

effluent

final sedimentation

primarysedimentation

activated sludgetank

filter

enviroWater, 20 - 22 February – Stellenbosch, South Africa

BD, sorption

BD, elimination by filtration

BD, influent

BD, primary sludge

BD, effluent primary sedimentation

BD, excess sludge

RE SF VK BB NK

BD, effluentfinal sedimentation

FI

BD, biological degradation

BD, effluent

BD = daily loadRE = screening unitSF = grit chamber VK = primary sedimentationBB = biological reactorNK = final sedimentationFI = filtration

= sampling pointBD, sorption

BD, elimination by filtration

BD, influent

BD, primary sludge

BD, effluent primary sedimentation

BD, excess sludge

RE SF VK BB NK

BD, effluentfinal sedimentation

FI

BD, biological degradation

BD, effluent

BD = daily loadRE = screening unitSF = grit chamber VK = primary sedimentationBB = biological reactorNK = final sedimentationFI = filtration

= sampling point

Investigated WWTPs –Duesseldorf-South / Mass Flow Balance

enviroWater, 20 - 22 February – Stellenbosch, South Africa

Investigated WWTPs –Cologne-Stammheim

influent

effluent

digestedsludge

intermediatesedimentation

A-Stufe B-Stufe

excess-sludge, A-Stage

activated sludge tank, A-Stage

final sedimentation

activated sludge tank, B-Stage

filter

excess-sludge, B-Stage

enviroWater, 20 - 22 February – Stellenbosch, South Africa

Synthetic Musk Fragrances

• Polycyclic and nitroaromatic musk fragrances– used as additive in cosmetics and soaps etc.– bioaccumulation, possible chronical toxicity, metabolites with higher toxic

effects– shifting from nitroaromatic to polycyclic musk fragrances

musk-xylol musk-keton HHCB (galaxolid) AHTN (tonalid)

(decreasing use) (substitutes)

enviroWater, 20 - 22 February – Stellenbosch, South Africa

PS = primary sludge ÜSS = excess sludge Abbau BB = biological degredation

AHTN MB D und E - KW Düsseldorf-Süd

0

10

20

30

40

50

60

70

80

90

Zulauf Ablauf Vorklärung Ablauf Nachklärung Ablauf Filter

Frac

ht [g

/d]

Wasserweg PS ÜSS Abbau BB

Influent Effluent primarysedimentation

Effluent final sedimentation

Effluent filtration

Load

[g/d

]

Results Mass Flow Balance Polycyclic Musk Fragrance - AHTN

Elimination: 85 %

Sorption as main way of elimination

PS = primary sludge ÜSS = excess sludge Abbau BB = biological degradation

enviroWater, 20 - 22 February – Stellenbosch, South Africa

Natural and Synthetic Estrogens

– To differentiate between natural and synthetic estrogens

– Possible endocrine effects for animals and humans (e.g. feminisation of fishes)

– Environmental relevance in spite of the very low concentrations, because of very low effect concentration

– Effluent concentrations approx. 1 ng/L

– PNEC ethinylestradiol*: 0,03 ng/L(Predicted No Effect Concentration)

* Quelle: Wenzel et. al. 1999

enviroWater, 20 - 22 February – Stellenbosch, South Africa

17-ß-Estradiol MB D + E - GKW Köln-Stammheim

0

500

1.000

1.500

2.000

2.500

3.000

3.500

4.000

4.500

5.000

Zulauf Ablauf Zwischenkl. Ablauf Nachklärung Ablauf Filter

Frac

ht [m

g/d]

Wasserweg ÜSS A-Stufe ÜSS B-Stufe Abbau A-Stufe Abbau B-Stufe Elimination Filter

Influent Effluent A Stage

Effluent B Stage

Effluentfiltration

Cologne

17-ß-Estradiol MB E - KW Düsseldorf -Süd

0

200

400

600

800

1000

1200

Zulauf Ablauf Vorklärung Ablauf Nachklärung Ablauf Filter

Frac

ht [m

g/d]

Wasserweg PS ÜS Abbau BB Elimination Filter

Duesseldorf

Influent Effluentprimary

sedimentation

Effluent final sedimentation

Effluentfiltration

PS = primary sludge ÜSS = excess sludge Abbau BB = biological degradation

Results Mass Flow BalancesNatural Estrogen – 17β-Estradiol

- Elimination: > 90 %

- Biological degradation

- Environmental relevance in spite of thevery low concentrations

Düsseldorf

Load

[mg/

d]

Load

[mg/

d]

enviroWater, 20 - 22 February – Stellenbosch, South Africa

Amidotrizoesäure MB E-F - KW Düsseldorf-Süd

0

100

200

300

400

500

600

700

800

900

1000

Zulauf Ablauf Vorklärung Ablauf Nachklärung Ablauf Filter

Frac

ht [g

/d]

Wasserweg PS ÜSS Abbau BB

Influent Effluentprimary

sedimentation

Effluent final sedimentation

Effluentfiltration

Load

[g/d

]

TCEP MB E - GKW Köln-Stammheim

0

20

40

60

80

100

120

140

Zulauf Ablauf Zwischenkl. Ablauf Nachklärung Ablauf Filter

Frac

ht [g

/d]

Wasserweg ÜSS A-Stufe ÜSS B-Stufe Abbau A-Stufe Abbau B-Stufe Elimination Filter

TCEP - Cologne

Influent Effluent A Stage

Effluent B Stage

Effluentfiltration

Load

[g/d

]

Results - Mass Flow BalancesX-Ray-Contrast Media - Diatrizoate

Flame-Retardant - TCEP

Marginal elimination: 0- 40 %

Biological degradation

PS = primary sludge ÜSS = excess sludge Abbau BB = biological degradation

Diatrizoate - Düsseldorf

PS = primary sludge ÜSS = excess sludge Abbau BB = biological degradation

enviroWater, 20 - 22 February – Stellenbosch, South Africa

Pilot plant LUA NRW, Neuss

Total volume: 20 m³

Two parallel lines (reference)

Different sludge ages

Membrane Bioreactor

enviroWater, 20 - 22 February – Stellenbosch, South Africa

Pilot Plant InvestigationsInfluence of Sludge Age

Versuchsreihe B - Pharmaka

0%

20%

40%

60%

80%

100%

Atenolo

lBiso

prolol

Sotalol

Metopro

lolProp

anolo

lTrim

ethop

rimClar

ithrom

ycin

Roxith

romyc

in

Sulfam

ethox

azol

Carbam

azep

inBez

afibra

tClof

ibrins

äure

Naprox

enDiclo

fenac

Ibupro

fen

Ges

amte

limin

atio

n

tts = 14 d tts= 25 d

PharmaceuticalsEl

imin

atio

n %

Increasing elimination with higher sludge ages

enviroWater, 20 - 22 February – Stellenbosch, South Africa

Pilot Plant InvestigationsEffectiveness of Membrane Bioreactor (MBR)

Versuchsreihe C - Pharmaka

0%

20%

40%

60%

80%

100%

Atenolol

Bisopro

lolSotal

olMeto

prolol

Propan

ololTrim

ethoprim

Clarith

romyc

inRoxit

hromyc

in

Sulfameth

oxazo

lCarb

amaz

epin

Bezafi

bratClofib

rinsä

ureNap

roxe

nDicl

ofenac

Ibuprofen

Ges

amte

limin

atio

n

Straße 1(MBR) Straße 2

PharmaceuticalsEl

imin

atio

n %

Different effects in MBR – effects of shorter retention time ??

MBR Conventional treatment

enviroWater, 20 - 22 February – Stellenbosch, South Africa

Possible Risk Assessment

1,0E-05

1,0E-04

1,0E-03

1,0E-02

1,0E-01

1,0E+00

1,0E+01

1,0E+02

Tributyl

zinn

Sulfameth

oxazo

lTric

losan

17 ß -E

strad

iolDibutyl

zinn

Nonylphen

ol

Clarith

romyc

inTnBP

Carbam

azep

in

Octylphen

ol

Bisphen

ol A

Clofibrin

säure

Monobutylzin

nHHCBDEHPTCPP

Ibuprofen

AHTNDicl

ofenac TPP

DBPTCEP

Moschus K

eton

Napro

xen

BBPTDCPTBEP

Roxithro

mycin

Trimeth

oprimPhen

azon

Iopromid

Quo

tient

Abl

konz

./Zie

lwer

t [-]

Düsseldorf Abl. Filter Köln Abl. FilterEf

fluen

t/ T

arge

tVal

ue[-]

Similar relevance for both WWTPs

enviroWater, 20 - 22 February – Stellenbosch, South Africa

Conclusion / Future Prospects

• A multitude of organic trace compounds reaching the WWTPs

• Elimination between 0 % and 95 %

• Instead of degradation, only sorption onto sludge for some compounds

• Risk assessment is not yet finished– Residual concentrations exceed partly the existing PNEC– For a lot of compounds the toxicity data are incomplete and not final– Resulting PNEC values do not include all possible effects on the aquatic environment

• Low possibilities for optimising the existing biological treatmentProviding more efficient elimination technologies(e.g. oxidation, adsorption)

enviroWater, 20 - 22 February – Stellenbosch, South Africa

Acknowledgements

The project is jointly run by the University of Dortmund, Deutsche Projekt Union (Cologne), state enviromental agency(LUA NRW), Stadtentwässerungsbetriebe Köln and Düsseldorf

and the Emschergenossenschaft/Lipperverband (Essen).

The project is financial supported by the Ministry of Environment, Nature Conservation, Agriculture and Consumer Protection of

the State of North Rhine-Westphalia (MUNLV NRW).