emerging substances in the aquatic environment

45
Emerging Emerging Substances in Substances in the the Aquatic Aquatic Environment Environment Wick, A. Wick, A. , Prasse, C., Kormos, J., Ternes, T.A. , Prasse, C., Kormos, J., Ternes, T.A. Federal Institute of Hydrology (BfG), Koblenz, Germany Federal Institute of Hydrology (BfG), Koblenz, Germany International Conference on Priority Pollutants in River Basins 26.-27.05.2011, Karlsruhe, Germany

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Page 1: Emerging Substances in the Aquatic Environment

EmergingEmerging Substances in Substances in thethe AquaticAquatic EnvironmentEnvironmentWick, A.Wick, A., Prasse, C., Kormos, J., Ternes, T.A., Prasse, C., Kormos, J., Ternes, T.A.

Federal Institute of Hydrology (BfG), Koblenz, GermanyFederal Institute of Hydrology (BfG), Koblenz, Germany

International Conference on Priority Pollutants in River Basins 26.-27.05.2011, Karlsruhe, Germany

Page 2: Emerging Substances in the Aquatic Environment

~ 100,000 different synthetic organic chemicals have been registered for commercial use in the United States and in Europe

For ~ 30,000 chemicals marketed in the EU, the production volume is >1 t y-1

Knowledge about occurrence, fate and effects in the environment is very scarce

Emerging Micropollutants“Non-regulated organic trace pollutants just recently introduced or newly detected due to advanced analytical technologies” (Richardson, 2007, Anal. Chem.)

New tools for detection in the environment

Importance of organic chemicals in modern societies

LC-QqQ-MS

LC-LTQ-Orbitrap MS

However, …

Page 3: Emerging Substances in the Aquatic Environment

polar pesticidesphenylurea herbicides,

triazines, etc.

chlorobenzenes

chloroalkanes

PAHs

tin organics

HCH

PBDEs

HYDROPHILE

LIPOPHILE

pola

rity

VOLATILE NON-VOLATILEVolatility

Source: Ternes and Joss (2006) IWA Publishing

Organic pollutants according to the WFD, …Selection based on ecotoxicological criteria

WFD

alkylphenolsprimary in solution

primary sorbed

Priority Pollutants

Page 4: Emerging Substances in the Aquatic Environment

polar pesticidesphenylurea herbicides,

triazines, etc.

chlorobenzenes

chloroalkanes

PAHs

tin organics

HCH

PBDEs

VOLATILE NON-VOLATILEvolatility

alkylphenols

antibioticsbenzotriazoles

contrast mediapolyfluorinatedcompounds

psycho-active drugs biocides

estrogenesbetablocker

Priority and Emerging Pollutantspharmaceuticals, personal care products, biocides, perfluorinated compounds, …

Emerging Substances

musk fragrances

primary in solution

primary sorbed

HYDROPHILE

LIPOPHILE

pola

rity

Page 5: Emerging Substances in the Aquatic Environment

Emerging Substances in the Water Cycle

Household

Agriculture

Agricultural land

Industry

Water/Sediment

“Run off“

Drinking Water

Hospital

WWTPs

bank filtration

Waterworks

groundwater

Infiltration

Page 6: Emerging Substances in the Aquatic Environment

Removal processes in WWTPs

influent

effluent

Nitrification(oxic

conditions)

Denitrification(anoxic

conditions)

(bio-)degradationsorption• absorption • adsorption

stripping

Emerging micropollutants are often relatively polar,

non-volatile and persistent

Page 7: Emerging Substances in the Aquatic Environment

WWTPs as point source

00,5

11,5

22,5

33,5

4

sulfameth-oxazole

carbama-zepine ibuprofene

diclofenacatenolol

sotaloldiatrizoate

iopromide

(24%)

(0%)

(96%)

(33%)(84%) (48%)

(0%)

(83%)

18 µg/L

Conc. in µg/L

iodinated X-ray contrast media(ICMs)

betablockeranalgesicsantibiotic anti-epileptic

Source: Ternes et al., 2006, Chemosphere

influent effluent (removal in %)

Page 8: Emerging Substances in the Aquatic Environment

0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9

clofibric acidbezafibratediclofenacnaproxen

metoprololpropranolol

bisoprololsotalol

atenololceliprolol

iopamidoleiopromide

iothalamine aciddiatrizoateiomeprole

roxithromycinerythromycin

sulfamethoxazoletrimethoprim

phenazonecarbamazepine

propyphenazone

Concentration in µg/L

sum: 6 µg/L

Diclofenac

Occurrence of pharmaceuticals in the receiving water

Page 9: Emerging Substances in the Aquatic Environment

Do we have a problem ?

What are the risks of Emerging Substances in the Water Cycle ?

Page 10: Emerging Substances in the Aquatic Environment

0

0.5

1

1.5

2

2.5

3

3.5

control solventcontrol

1 µg/L 5 µg/L 20 µg/L 100 µg/L 500 µg/L

**

***

*

****: p < 0,05 **: p < 0,01 ***: p< 0,001

MAV

Source: Schwaiger et al., Aquatic Toxicol., 2004

NCl

Cl

HHOOC

control

diclofenac

Example: Diclofenac leads to histopathologicalchanges in the kidney of rainbow trouts

LOEC = 5 µg/LNOEC = 1 µg/L-> EQS: 0.1 µg/L

Ecotoxicity of Diclofenac

Page 11: Emerging Substances in the Aquatic Environment

EE2 0.035 ng/L < 1 ng/L (WWTP)

1AA-EQS: Environmental quality standard expressed as annual average concentration

range of annual average concentrations measured in German rivers and streams (BfG)

Diclofenac 100 ng/L 50-500 ng/L

1 AA-EQS

17β-Estradiol 0.53 ng/L 0.5 -270 ng/L

Irgarol 2.5 ng/L < 1 ng/L-19 ng/L

Terbutryn 65 ng/L < 2 ng/L- 35 ng/L

Ibuprofen 10 ng/L 10-600 ng/L

(State of play of Identification of new Priority Substances (26.01.2011))

Candidates of new Priority Substances- currently discussed EQS-values vs. measured concentrations in rivers

Impact on legislation

Page 12: Emerging Substances in the Aquatic Environment

Iodinated X-ray contrast media (ICMs) and their microbial transformation productsantiepileptics (carbamazepine, primidone)lipid lowering agent (clofibric acid)antibiotics (sulfamethoxazole)

Presence in drinking water

Some examples:

diatrizoate: iopamidol: carbamazepine: sulfamethoxazole:

average conc. [ng/L]

16822 4113

maximum conc. [ng/L]

>200180 15070

Page 13: Emerging Substances in the Aquatic Environment

Transformation products (TPs)

influent

effluent

(Bio-)degradation

often more polar high mobility

unknown chem. structure and (eco-)toxcicity,

Transformation Products => „Emerging Substances“

mineralization

Transformation products (TPs)

Page 14: Emerging Substances in the Aquatic Environment

Agriculture

Agricultural landWater/Sediment “Run off“

groundwater

Infiltrationbank filtration

WaterworksDrinking Water

WWTPs

Transformation processes in the Water Cycle

transformation by biochemical processes

transformation by photolysis

transformation by chemical oxidation

Page 15: Emerging Substances in the Aquatic Environment

Current results from three studies:

Source and fate of emerging micropollutants in the aquatic environment

1. antivirals 2. iodinated X-ray contrast media (ICMs)3. opium alkaloids used as analgesics

Current results

Page 16: Emerging Substances in the Aquatic Environment

O

O

H2N

HN

O

O

Oseltamivir

O

OH

H2N

HN

O

O

Oseltamivir carboxylate

application:

• influenza

Antivirals - introduction

swine flue infections

Page 17: Emerging Substances in the Aquatic Environment

application:

• influenza

• herpes

Acyclovir Penciclovir

N

NH

N

N

O

NH2

OOH

N

NH

N

N

O

HO OH

NH2

Antivirals - introduction

Page 18: Emerging Substances in the Aquatic Environment

application:

• influenza

• herpes

• HIV (human immunodeficiency virus)

Stavudine ZidovudineNevirapine

Abacavir Lamivudine

HN

N

N

NH2N

HN

OH

S

O

N

N

NH2

O

HO

N

NH

O

N N O

OHOH

HO N

NH

O

O

O

N

HON

NH

O

O

NN

Antivirals - introduction

Page 19: Emerging Substances in the Aquatic Environment

Duisburg

Dortmund

Ruhr

Neger

ValmeElpe

Wenne

RöhrLenneVolme

Oel

bach

Emscher

Ruhr Ru_06

Ru_12Ru_14

Möhne

Ru_20

Ru_19

Ru_26

Rhin

e

Rhine

Ru_34

Ru_33Ru_32

Ru_31 Ru_30

Ru_29

Ru_28

Ru_27Ru_25

Ru_24

Ru_23Ru_22

Ru_21

Ru_18Ru_17

Ru_16Ru_15 Ru_13

Ru_11Ru_10

Ru_09 Ru_08

Ru_07

Ru_05Ru_04Ru_03Ru_02

Ru_01

0 5 10 15 20 25

Kilometers

Sampling of Ruhr, Rhine and Emscher(September 2009)Rhine

Ruhr

flow direction

Em_01

Rh_02Rh_0

1

Rh_03

Antivirals – Occurrence in rivers

Source: Prasse et al., Environ. Sci. Technol., 2010

Page 20: Emerging Substances in the Aquatic Environment

0

2

4

6

8

10

Em

_01

Rh_

03R

h_02

Rh_

01R

u_30

Ru_

29R

u_28

Ru_

27R

u_26

Ru_

25R

u_24

Ru_

23R

u_22

Ru_

21R

u_20

Ru_

19R

u_18

Ru_

17R

u_16

Ru_

15R

u_14

Ru_

13R

u_12

Ru_

11R

u_10

Ru_

09R

u_08

Ru_

07R

u_06

Ru_

05R

u_04

Ru_

03R

u_02

Ru_

01

OseltamivirOseltamivir carboxylate

Emsc

her

Wen

ne

Lenn

e

Volm

e

17 151505

10152025303540

AcyclovirZidovudine

94

Rhine

0

2

4

6

8

10

Em

_01

Rh_

03R

h_02

Rh_

01R

u_30

Ru_

29R

u_28

Ru_

27R

u_26

Ru_

25R

u_24

Ru_

23R

u_22

Ru_

21R

u_20

Ru_

19R

u_18

Ru_

17R

u_16

Ru_

15R

u_14

Ru_

13R

u_12

Ru_

11R

u_10

Ru_

09R

u_08

Ru_

07R

u_06

Ru_

05R

u_04

Ru_

03R

u_02

Ru_

01

OseltamivirOseltamivir carboxylate

Emsc

her

Wen

ne

Lenn

e

Volm

e

17 1515

0

2

4

6

8

10

Em

_01

Rh_

03R

h_02

Rh_

01R

u_30

Ru_

29R

u_28

Ru_

27R

u_26

Ru_

25R

u_24

Ru_

23R

u_22

Ru_

21R

u_20

Ru_

19R

u_18

Ru_

17R

u_16

Ru_

15R

u_14

Ru_

13R

u_12

Ru_

11R

u_10

Ru_

09R

u_08

Ru_

07R

u_06

Ru_

05R

u_04

Ru_

03R

u_02

Ru_

01

OseltamivirOseltamivir carboxylate

Emsc

her

Wen

ne

Lenn

e

Volm

e

17 1515

0

2

4

6

8

10

Em

_01

Rh_

03R

h_02

Rh_

01R

u_30

Ru_

29R

u_28

Ru_

27R

u_26

Ru_

25R

u_24

Ru_

23R

u_22

Ru_

21R

u_20

Ru_

19R

u_18

Ru_

17R

u_16

Ru_

15R

u_14

Ru_

13R

u_12

Ru_

11R

u_10

Ru_

09R

u_08

Ru_

07R

u_06

Ru_

05R

u_04

Ru_

03R

u_02

Ru_

01

OseltamivirOseltamivir carboxylate

Emsc

her

Wen

ne

Lenn

e

Volm

e

17 151505

10152025303540

AcyclovirZidovudine

94

Rhine

05

10152025303540

AcyclovirZidovudine

94

Rhine

Duisburg

Dortmund

RuhrN

eger

ValmeElpe

Wenne

RöhrLenneVolme

Oel

bach

Emscher

Ruhr Ru_06

Ru_12Ru_14

Möhne

Ru_20

Ru_19

Ru_26

Rhin

e

Rhine

Ru_34

Ru_33Ru_32

Ru_31 Ru_30

Ru_29

Ru_28

Ru_27Ru_25

Ru_24

Ru_23Ru_22

Ru_21

Ru_18Ru_17

Ru_16Ru_15 Ru_13

Ru_11Ru_10

Ru_09 Ru_08

Ru_07

Ru_05Ru_04Ru_03Ru_02

Ru_01

0 5 10 15 20 25

KilometersRh_01

Em

_01

Rh_

03R

h_02

Rh_

01R

u_30

Ru_

29R

u_28

Ru_

27R

u_26

Ru_

25R

u_24

Ru_

23R

u_22

Ru_

21R

u_20

Ru_

19R

u_18

Ru_

17R

u_16

Ru_

15R

u_14

Ru_

13R

u_12

Ru_

11R

u_10

Ru_

09R

u_08

Ru_

07R

u_06

Ru_

05R

u_04

Ru_

03R

u_02

Ru_

01

Em

_01

Rh_

03R

h_02

Rh_

01R

u_30

Ru_

29R

u_28

Ru_

27R

u_26

Ru_

25R

u_24

Ru_

23R

u_22

Ru_

21R

u_20

Ru_

19R

u_18

Ru_

17R

u_16

Ru_

15R

u_14

Ru_

13R

u_12

Ru_

11R

u_10

Ru_

09R

u_08

Ru_

07R

u_06

Ru_

05R

u_04

Ru_

03R

u_02

Ru_

01

Em

_01

Rh_

03R

h_02

Rh_

01R

u_30

Ru_

29R

u_28

Ru_

27R

u_26

Ru_

25R

u_24

Ru_

23R

u_22

Ru_

21R

u_20

Ru_

19R

u_18

Ru_

17R

u_16

Ru_

15R

u_14

Ru_

13R

u_12

Ru_

11R

u_10

Ru_

09R

u_08

Ru_

07R

u_06

Ru_

05R

u_04

Ru_

03R

u_02

Ru_

01

Em

_01

Rh_

03R

h_02

Rh_

01R

u_30

Ru_

29R

u_28

Ru_

27R

u_26

Ru_

25R

u_24

Ru_

23R

u_22

Ru_

21R

u_20

Ru_

19R

u_18

Ru_

17R

u_16

Ru_

15R

u_14

Ru_

13R

u_12

Ru_

11R

u_10

Ru_

09R

u_08

Ru_

07R

u_06

Ru_

05R

u_04

Ru_

03R

u_02

Ru_

01

Concentration [ng L-1]

Em_01

Rh_02

Rh_03

downstream of a WWTP

downstream of a small tributary

AcyclovirZidovudin

Page 21: Emerging Substances in the Aquatic Environment

0

2

4

6

8

10

Em

_01

Rh_

03R

h_02

Rh_

01R

u_30

Ru_

29R

u_28

Ru_

27R

u_26

Ru_

25R

u_24

Ru_

23R

u_22

Ru_

21R

u_20

Ru_

19R

u_18

Ru_

17R

u_16

Ru_

15R

u_14

Ru_

13R

u_12

Ru_

11R

u_10

Ru_

09R

u_08

Ru_

07R

u_06

Ru_

05R

u_04

Ru_

03R

u_02

Ru_

01

OseltamivirOseltamivir carboxylate

Emsc

her

Wen

ne

Lenn

e

Volm

e

17 151505

10152025303540

AcyclovirZidovudine

94

Rhine

0

2

4

6

8

10

Em

_01

Rh_

03R

h_02

Rh_

01R

u_30

Ru_

29R

u_28

Ru_

27R

u_26

Ru_

25R

u_24

Ru_

23R

u_22

Ru_

21R

u_20

Ru_

19R

u_18

Ru_

17R

u_16

Ru_

15R

u_14

Ru_

13R

u_12

Ru_

11R

u_10

Ru_

09R

u_08

Ru_

07R

u_06

Ru_

05R

u_04

Ru_

03R

u_02

Ru_

01

OseltamivirOseltamivir carboxylate

Emsc

her

Wen

ne

Lenn

e

Volm

e

17 1515

0

2

4

6

8

10

Em

_01

Rh_

03R

h_02

Rh_

01R

u_30

Ru_

29R

u_28

Ru_

27R

u_26

Ru_

25R

u_24

Ru_

23R

u_22

Ru_

21R

u_20

Ru_

19R

u_18

Ru_

17R

u_16

Ru_

15R

u_14

Ru_

13R

u_12

Ru_

11R

u_10

Ru_

09R

u_08

Ru_

07R

u_06

Ru_

05R

u_04

Ru_

03R

u_02

Ru_

01

OseltamivirOseltamivir carboxylate

Emsc

her

Wen

ne

Lenn

e

Volm

e

17 1515

0

2

4

6

8

10

Em

_01

Rh_

03R

h_02

Rh_

01R

u_30

Ru_

29R

u_28

Ru_

27R

u_26

Ru_

25R

u_24

Ru_

23R

u_22

Ru_

21R

u_20

Ru_

19R

u_18

Ru_

17R

u_16

Ru_

15R

u_14

Ru_

13R

u_12

Ru_

11R

u_10

Ru_

09R

u_08

Ru_

07R

u_06

Ru_

05R

u_04

Ru_

03R

u_02

Ru_

01

OseltamivirOseltamivir carboxylate

Emsc

her

Wen

ne

Lenn

e

Volm

e

17 151505

10152025303540

AcyclovirZidovudine

94

Rhine

05

10152025303540

AcyclovirZidovudine

94

Rhine

Duisburg

Dortmund

RuhrN

eger

ValmeElpe

Wenne

RöhrLenneVolme

Oel

bach

Emscher

Ruhr Ru_06

Ru_12Ru_14

Möhne

Ru_20

Ru_19

Ru_26

Rhin

e

Rhine

Ru_34

Ru_33Ru_32

Ru_31 Ru_30

Ru_29

Ru_28

Ru_27Ru_25

Ru_24

Ru_23Ru_22

Ru_21

Ru_18Ru_17

Ru_16Ru_15 Ru_13

Ru_11Ru_10

Ru_09 Ru_08

Ru_07

Ru_05Ru_04Ru_03Ru_02

Ru_01

0 5 10 15 20 25

KilometersRh_01

Concentration [ng L-1]

Em_01

Rh_02

Rh_03

AcyclovirZidovudine

OseltamivirOseltamivircarboxylat

AcyclovirZidovudin

OseltamivirOseltamivircarboxylat

Page 22: Emerging Substances in the Aquatic Environment

urine

raw wastewater

treated wastewater

river Ruhr

0.2 - 0.3

0.3

0.7

0.3 - 1.8

river Rhine 12.4-13.8

OP/OC

O

O

H2N

HN

O

O

Oseltamivir (OP)(pro-drug)

O

OH

H2N

HN

O

Ohepatic esterase

Oseltamivir-Carboxylate (OC)active metabolite!

> 75 %

Antivirals – Human metabolites

Page 23: Emerging Substances in the Aquatic Environment

northsea

FRANCE

BELGIUM

GERMANY

Germany

France

Switzerland

Source of Oseltamivir in the river Rhine

Page 24: Emerging Substances in the Aquatic Environment

Concentration [ng L-1]

020406080

100120140160180200

S5 S4 S3 S2 S1Sample location

OseltamivirOseltamivir carboxylate

OP:OC ratio: 13/1

Source of Oseltamivir in the river Rhine

Page 25: Emerging Substances in the Aquatic Environment

International surveillance station

Oseltamivir/ Oseltamivir-Carboxylatenot detected

Discharge from theWWTP Basel

(chemical industry)

Oseltamivir load: 1.8 kg d-1

equivalent to 12,000 patients!

(based on sampling from 07.10.2009)

Source of Oseltamivir in the river Rhine

Page 26: Emerging Substances in the Aquatic Environment

N

NH

N

N

O

OOH

NH2

Acyclovir (ACV)

N

NH

N

N

O

OOH

NH2

Carboxy-Acyclovir(Carboxy-ACV)

O

Oxidation

ACV Carboxy-ACV suminfluent 1990 430 2420effluent 140 2380 2520

Removal 93 % - 453% no

ng/L

Source: Prasse et al., Environ. Sci. Technol., 2011

Transformation of Acyclovir in WWTPs

Page 27: Emerging Substances in the Aquatic Environment

WWTP effluent surface water groundwater(aerobe)

groundwater(anaerobe)

drinking water0

500

1000

1500

2000

2500

3000

ACV

Carboxy-ACV

Acesulfam (conc. x 20)

Concentration[ng/L]

dilutionfurther transformation

Acesulfamused as a tracer for the proportion of WWTP effluent

Fate of Carboxy-Acyclovir

WWTP effluent => Surface water => Groundwater => Drinking Water

Page 28: Emerging Substances in the Aquatic Environment

Current results from three studies:

Source and fate of emerging micropollutants in the aquatic environment

1. antivirals2. iodinated X-ray contrast media (ICMs)3. opium alkaloids used as analgesics

Current results

Page 29: Emerging Substances in the Aquatic Environment

N

O NH

O

NH

CH3

OH

O

I

IIOH

OH

OH

OH

Iopamidol

IomeprolDiatrizoate

O NH

NH

I

II

O

NHOH

OH

O

CH3

OH

OH

OH

NH NH

O

CH3

O

I

II

OH

O

CH3

Used in hospitals and radiological practices200 g/applicationAmount excreted unchanged: > 90% within 24 h

Iodinated X-ray contrast media (ICMs)

Page 30: Emerging Substances in the Aquatic Environment

Source: Kormos et al., Anal. Chem., 2009 and 2010

O NH

NH

I

II

O

NHOH

OH

O

CH3

OH

OH

OH

Iopamidollog KOW: -2.42

Identified TPs of ICMs

O NH

NH

I

II

O

NH2

O

C3

OH

OH

O

TP687

HIopromide: 12 TPs

Iomeprol: 15 TPs

Iohexol: 10 TPsIopamidol: 9 TPs

Number of identified TPs

Diatrizoate: 0 TPs

46 TPs of four ICMs !

reaction I/II: oxidation hydroxyl moietiesreaction III: cleavage of 2-hydroxyl propanoic acidreaction IV: decarboxylationreaction V: deacetylation

Under aerobic conditions only theside chains of ICMs are transformed

Page 31: Emerging Substances in the Aquatic Environment

TP819 TP761

TP805

TP701 TP643

I

III

III

III

IV

V

IIITP791

TP789

TP731

TP701 TP643

TP775

TP629TP599TP657

TP687

TP745

TP717I

IV

III

IV

V

III

IV IV

III, V IV, V

Transformation pathway of iomeprol

I

reaction I/II: oxidation hydroxyl moietiesreaction III: cleavage of 2-hydroxyl propanoic acidreaction IV: decarboxylationreaction V: deacetylation

Source: Kormos et al., Anal. Chem., 2009 and 2010

Page 32: Emerging Substances in the Aquatic Environment

Konz. in µg/L

WWTP effluent Surface water Groundwater (aerobic)0

2

4

6

8

sum TPsIomeprol

sum TPsIopromide

sum TPsIopamidol

(0.8)

(1.7) (1.1)

(1.2)

(1.4) (128)

(0.5)

(0.7)(261)

( ):Conc. Σ TP Conc. ICM

dilution

transformation

WWTP effluent => Surface water => Groundwater

Fate of ICMs in the water cycle

Page 33: Emerging Substances in the Aquatic Environment

0

50

100

150

350

400

450

500

Conc. [ng/L]

WW: water worksWW1: river water, flocculation, ozonation, activated carbon WW2: bank filtration, biol. treatment, sand filtration WW3: groundwater/bank filtrate, activated carbon

200

250

300

IomeprolTP 745TP 701TP 687TP 643TP 629

WW 1 WW 2 WW 3

sum 493 ng/L

sum1661 ng/L

sum 121 ng/L

Occurrence of ICM TPs in drinking water

sum1661 ng/L

Page 34: Emerging Substances in the Aquatic Environment

Current results from three studies:

Source and fate of emerging micropollutants in the aquatic environment

1. antivirals2. iodinated X-ray contrast media (ICMs)3. opium alkaloids used as analgesics

Current results

Page 35: Emerging Substances in the Aquatic Environment

Morphine Codeine Dihydrocodeine

Analgesics and Antitussives

Removal by biotransformation Transformation products (TPs) ?

Different removal efficiencies Distinct transformation pathways ?

Opium alkaloids

> 80% 40-80% 20-50%

Conc. in German WWTP effluents ~ 300 ng L-1 ~ 200 ng L-1 ~ 50 ng L-1

Removal

Source: Wick et al., Wat. Res., 2009

Page 36: Emerging Substances in the Aquatic Environment

17 TPs

(20-40%)

I)

Codeine

unknown

(60-80%)

II)

Codeinone

biol. oxidation

Codeinone as the main precursor

Source: Wick et al., Environ. Sci. Technol., 2011

Page 37: Emerging Substances in the Aquatic Environment

Codeine

Codeinone

(I)(II)

Neopinone

(B)

TP 316(2): 8-Hydroxy-7,8-dihydrocodeinone

(A)

TP 318: 8-Hydroxy-7,8-dihydrocodeine

(II)

(I)?

TP 300(1): Neopine(II)

TP 300(2): Isoneopine(II)

Transformation pathway

56

78

14

(C)TP 314: 14-Hydroxy-

codeinone

TP 316: 14-Hydroxy-codeine

(II)(I)

TP 302: 14-Hydroxy-N-desmethylcodeine

(III)

(A) H2O addition(B) double bond shift(C) hydroxylation

biotic reactions(I) oxidation(II) reduction(III) N-demethylation

abiotic reactions

Page 38: Emerging Substances in the Aquatic Environment

17 TPs

(20-40%)

I)

Codeine

unknown

(60-80%)

II)

Codeinone

biol. oxidation

Codeinone as the main precursor

Wick et al., 2011, Environ. Sci. Technol.

Page 39: Emerging Substances in the Aquatic Environment

Reactivity of Codeinone

other nucleophiles

for instance thiol groups in proteins

TP 316(2)

20 24 28 32 36 40 442.0e7

6.0e7

1.0e8

1.4e8

1.8e8

Inte

nsity

, cps

time, min

codeinoneH2O

Codeinone

- +

cysteinehistidine

lysine

proteins ?

Page 40: Emerging Substances in the Aquatic Environment

Codeine TPs in WWTPs

0

20

40

60

80

100

WWTP I WWTP II WWTP III WWTP IV

∑ TPscodeinoneneopine + Isoneopine14-OH-codeinone14-OH-codeine

concentration [ng L-1]

WWTP effluents

(22%)

(17%)

(18%)

(39%)

(mass balance in %)

Results from batch experiments can be transferred to full-scale WWTPs.

Page 41: Emerging Substances in the Aquatic Environment

Morphinone

belonging to a comparable transformation pathwaycharacterized by biotic and abiotic reactions

9 TPs

biol. oxidation

Morphine 2-Nitromorphine

abiotic

Dihydrocodeine

2-Nitromorphinonebiol. oxidation

6 TPs No furtherreactions

Hydrocodone

Transformation of opium alkaloids

Codeine

Codeinonebiol. oxidation

17 TPs

Page 42: Emerging Substances in the Aquatic Environment

Conclusion - 1

WWTPs important point sources for the discharge of polar emerging substances in the aquatic environment.

The removal of emerging substances in the environment is often linked to the formation of a multitude of transformation products (TPs).

Most TPs are more polar than the parent compounds and are prone to contaminate drinking water.

Transformation pathways are hard to predict – slight differences in the chemical structure have significant effects on the transformation.

Abiotic reactions are not adequately considered during nitrification.

With regard to pharmaceuticals, the ratio of parent compound and human metabolites can be used to identify the input sources.

Page 43: Emerging Substances in the Aquatic Environment

New mitigation strategies are needed to

1) meet the upcoming Environmental Quality Standards (EQS) values of the WFD.

2) minimize the potential impact of unregulated emerging organic micropollutants and their mostly unknown TPs on the aquatic ecosystem and the drinking water quality.

Conclusion - 2

improved source controlproduct labeling

product directives separation of point sources

advanced treatmentozonation

activated carbonnanofiltration, etc

Page 44: Emerging Substances in the Aquatic Environment

Financial support: EU-projects

Keybioeffects, Neptune, Reclaim Water

Thank you for your attention

Page 45: Emerging Substances in the Aquatic Environment

none0.09 –0.300.05 / 0.4–0.7 2)

activated carbon(10-20 mg/L) / + sand filtration

concentrateamount?

0.20 –0.501.5–3.0 / 4.5–9.0

nanofiltration5 – 30 bar

15-30% concentrate0.70 – 1.52.0–5.0 / 6.0–15 1)

reversed osmosis50 bar

toxicologyunknown

0.05 –0.200.1–0.2/0.3-0.6

ozonation/sandfiltration(3-10 mg/L O3)

by-productscosts€·m-3

Energy (electric/primary)

kWh·m-3

1) Busch and Mickols, Desalination, 20042) Primary energy consumption of PAC (no regeneration) 3.5 kg carbon needed for 1 kgPAC: 3.5kgC/kgPAC x 31MJ/kgC / 3.6MJ/kWh = 30kWh/kgPAC

Options for a tertiary treatment