Upload
others
View
6
Download
0
Embed Size (px)
Citation preview
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
~ 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, …
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
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
Emerging Substances in the Water Cycle
Household
Agriculture
Agricultural land
Industry
Water/Sediment
“Run off“
Drinking Water
Hospital
WWTPs
bank filtration
Waterworks
groundwater
Infiltration
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
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 %)
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
Do we have a problem ?
What are the risks of Emerging Substances in the Water Cycle ?
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
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
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
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)
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
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
O
O
H2N
HN
O
O
Oseltamivir
O
OH
H2N
HN
O
O
Oseltamivir carboxylate
application:
• influenza
Antivirals - introduction
swine flue infections
application:
• influenza
• herpes
Acyclovir Penciclovir
N
NH
N
N
O
NH2
OOH
N
NH
N
N
O
HO OH
NH2
Antivirals - introduction
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
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
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
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
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
northsea
FRANCE
BELGIUM
GERMANY
Germany
France
Switzerland
Source of Oseltamivir in the river Rhine
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
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
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
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
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
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)
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
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
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
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
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
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
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
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
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.
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 ?
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.
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
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.
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
Financial support: EU-projects
Keybioeffects, Neptune, Reclaim Water
Thank you for your attention
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