Degradation of organic micropollutants via
Advanced Oxidation Process (UV/H2O2)
25-09-2009
Josanne Derks
Results pilot plant research
2
Contents
• Drinking water production from Meuse water
• OMPs in drinking water source
• Theory of AOP via UV/H2O2
• AOP pilot installation
• Results
• Conclusions
• Further research/planning
Goals - DW production – OMPs in source – Theory – PI – Results – Conclusions – Further
research
3
Goals of AOP research project
Determine the best UV-technology in terms of energy and formation of by-products
LP, MP, DBD lamps
Influence of excessive peroxide on transport pipelines and dune ponds
Removal of by-products by DSF (AOC, nitrite, deg. products)
Determine necessity of GACF or PAC
Removal by-products and excessive peroxide
Removal of only excessive peroxide
Effect conditioning water on efficiency AOP
Goals - DW production – OMPs in source – Theory – PI – Results – Conclusions – Further
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Treatment scheme
Coagulation/sedimentation
Intake Meuse water
Transport
RSF
Transport
Dune infiltration
Recovery
Post-treatment
Distribution
The HagueThe Hague
Transport pipelines
PretreatmentRapid sand filtration
IntakeMicro sieves
Tributary Meuse River Dosing of FeSO4
Post-treatment locations
Goals - DW production – OMPs in source – Theory – PI – Results – Conclusions – Further
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The river Meuse as source for drinking water
FRANCE
GERMANY
LUXEMBOURG
FLANDERS
WALLONIA
THE NETHERLANDS
Chiers
Semois
Sambre
Lesse
Ourthe
Rur
Niers
Dommel
Maastricht
Liège
Namur
Charleroi
Charleville-Mezieres
Goals - DW production – OMPs in source – Theory – PI – Results – Conclusions – Further
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Maximum measured incidental concentration (µg/l) at intake
Diuron 0,15
Glyphosate 0,44
Cafeïne 0,3
Ibuprofen 0,05
Amidotrizoic acid 0,15
Iohexol 0,1
MTBE 1,7
Goals - DW production – OMPs in source – Theory – PI – Results – Conclusions – Further
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Atrazine & Glyfosaat in Maas bij Keizersveer
0
0,2
0,4
0,6
0,8
1
1,2
1989 1991 1994 1997 1999 2002 2005 2008
jaar
con
cen
trat
ie [
µg
/l]
Atrazine
Glyfosaat
Goals - DW production – OMPs in source – Theory – PI – Results – Conclusions – Further
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A multitude of compounds and technologies
Goals - DW production – OMPs in source – Theory – PI – Results – Conclusions – Further
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AOP and Dune infiltration: complementary
AOP Dunes
Quick, fast process Long term process
Chemical oxidation Biological oxidation and reduction,
adsorption
Short circuiting smoothing
Increase of AOC Removal of AOC
Goals - DW production – OMPs in source – Theory – PI – Results – Conclusions – Further
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AOP via UV/H2O2
Combination of two degradation mechanisms:
Photolysis: A0 + hv A*
Radical formation: H2O2 + hv 2 ·OH
Combination: OMP + ·OH + hv deg. product(s) + CO2 + H2O
Goals - DW production – OMPs in source – Theory – PI – Results – Conclusions – Further
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Radical scavengingInfluence water matrix on UV/H2O2
HCO3- + ·OH → HCO3· + OH- k = 8,5 * 106 M-1 s-1
CO32- + ·OH → CO3·- + OH- k = 3,9 * 108 M-1 s-1
pH RSF = ±8
Goals - DW production – OMPs in source – Theory – PI – Results – Conclusions – Further
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NO3- + hv → NO2
- + O
NO2- + ·OH → NO2· + OH- k = 1,0 * 1010 M-1 s-1
Nitrate/nitrite Influent
0,0
2,5
5,0
7,5
10,0
12,5
15,0
17,5
Jan Feb Mar Apr May Jun Jul Aug Sep
Date
Nitr
ate
[m
g/l
NO
3]
-0,0020,0000,0020,0040,0060,0080,0100,0120,0140,0160,0180,020
Nitr
ite
(mg
/l N
O2
)
NO3
NO2
Radical scavengingInfluence water matrix on UV/H2O2
Goals - DW production – OMPs in source – Theory – PI – Results – Conclusions – Further
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H2O2 + ·OH → H2O + H+ + O2-· k = 2,7 * 107 M-1 s-1
RH + ·OH → R· + H2O k = 107 - 1010 M-1 s-1
UV-T↓ → Photolysis ↓ + ·OH-formation ↓
Radical scavengingInfluence water matrix on UV/H2O2
Goals - DW production – OMPs in source – Theory – PI – Results – Conclusions – Further
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UV lamps: Medium pressure vs low pressure
0
5
10
15
20
25
200 210 220 230 240 250 260 270 280 290 300
Wavelenght [nm]
Lam
p e
mis
sio
n L
P a
nd
MP
[W
/m2]
0
0,5
1
1,5
2
2,5
Ab
sorb
ance
H2O
2 an
d w
ater
MP
LP
H2O2
Natural water
X-ray Ultraviolet Visible Light Infrared
VUV UVC UVB UVA
Wavelength (nm)
100 200 280 315 400 780
Goals - DW production – OMPs in source – Theory – PI – Results – Conclusions – Further
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AOP UV/H2O2 pilot installation
Settings installation:
- LP lamps 0,26 kWh/m3
- MP lamps 0,88 kWh/m3
- DBD lamps±0,24 kWh/m3
- 5 m3/hr per reactor
- Influent: pre-treated Meuse water
Model compounds:
- Atrazine (10 µg/l),
- Bromacil (10 µg/l),
- Ibuprofen (20 µg/l),
- NDMA (10 µg/l)
Standard experimental settings:
- UV 100 – 80 – 60%
- H2O2 10 – 5 – 0 mg/l
Goals - DW production – OMPs in source – Theory – PI – Results – Conclusions – Further
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Initial situation reactors
“Coffee test” : investigate the influence of UVT on UV intensity
UV-transmission of coffee solutions in lab test
y = 73,612e-0,0183x
R2 = 0,9997
0
10
20
30
40
50
60
70
80
90
100
0 20 40 60 80 100
120
140
160
180
200
concentration coffee in ppm
UV
-T i
n %
Goals - DW production – OMPs in source – Theory – PI – Results – Conclusions – Further
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Initial situation reactors
Zero measurement LP (12-02-09)
0
100
200
300
400
500
40 50 60 70 80 90 100
Ballast (%)
UV
in
ten
sit
y (
W/m
2)
GACF
RSF
0.000050 vol% coffee
0.000075 vol% coffee
0.000100 vol% coffee
0.000150 vol% coffee
Zero measurement MP (12-02-09)
0
50
100
150
200
250
300
40 50 60 70 80 90 100
Ballast (%)
UV
inte
nsi
ty (
%)
GACF
0.000050 vol% coffee
0.000075 vol% coffee
0.000100 vol% coffee
0.000150 vol% coffee
RSF
Goals - DW production – OMPs in source – Theory – PI – Results – Conclusions – Further
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Influent (09-07-2009) DUPLO
0
2
4
6
8
10
12
14
16
18
100/10 100/5 100/0 80/10 80/5 80/0 60/10 60/5 60/0
Setting [%UV / ppm H2O2]
Co
nce
ntr
atio
nl
[µg
/L]
Atrazine
Bromacil
Ibuprofen
NDMA
LP Effluent (09-07-2009) DUPLO
0
2
4
6
8
10
12
14
16
18
100/10 100/5 100/0 80/10 80/5 80/0 60/10 60/5 60/0
Setting [%UV / ppm H2O2]
Co
nce
ntr
atio
nl
[µg
/L]
Atrazine
Bromacil
Ibuprofen
NDMA
MP Effluent (09-07-2009) DUPLO
0
2
4
6
8
10
12
14
16
18
100/10 100/5 100/0 80/10 80/5 80/0 60/10 60/5 60/0
Setting [%UV / ppm H2O2]
Atrazine
Bromacil
Ibuprofen
NDMA
Goals - DW production – OMPs in source – Theory – PI – Results – Conclusions – Further
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LP Degradation (09-07-2009) DUPLO
0%
10%
20%
30%
40%
50%
60%
70%
80%
90%
100%
100/10 100/5 100/0 80/10 80/5 80/0 60/10 60/5 60/0
Setting [%UV / ppm H2O2]
Deg
rad
atio
n [
%]
Atrazine
Bromacil
Ibuprofen
NDMA
MP Degradation (09-07-2009) DUPLO
0%
10%
20%
30%
40%
50%
60%
70%
80%
90%
100%
100/10 100/5 100/0 80/10 80/5 80/0 60/10 60/5 60/0
Setting [%UV / ppm H2O2]
Atrazine
Bromacil
Ibuprofen
NDMA
Degradation of model compounds
Goals - DW production – OMPs in source – Theory – PI – Results – Conclusions – Further
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LP Electrical Energy per Order (09-07-2009) DUPLO
0
1
2
3
4
5
100/10 100/5 100/0 80/10 80/5 80/0 60/10 60/5 60/0
Setting [%UV / ppm H2O2]
EE
O [
kWh
/m3] Atrazine
Bromacil
Ibuprofen
NDMA
MP Electrical Energy per Order (09-07-2009) DUPLO
0
1
2
3
4
5
100/10 100/5 100/0 80/10 80/5 80/0 60/10 60/5 60/0
Setting [%UV / ppm H2O2]
Atrazine
Bromacil
Ibuprofen
NDMA
EEO = Electrical Energy per Order
P * UV
Q * log (ci/cf)EEO = kWh/m3
Goals - DW production – OMPs in source – Theory – PI – Results – Conclusions – Further
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21Goals - DW production – OMPs in source – Theory – PI – Results – Conclusions – Further
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Degradation of model compoundsDegradation Atrazine (100/10)
0
10
20
30
40
50
60
70
80
90
100
05-0
3-20
09
07-0
4-20
09
20-0
4-20
09
28-0
4-20
09
06-0
5-20
09
19-5
-200
9
2-6-
2009
11-6
-200
9
23-6
-200
9
25-6
-200
9
9-7-
2009
15-7
-200
9
23-7
-200
9
30-7
-200
9
4-8-
2009
13-8
-200
9
20-8
-200
9
26-8
-200
9
3-9-
2009
8-9-
2009
Date
De
gra
da
tio
n (
%)
MD
LD
Degradation Atrazine (100/0)
0
10
20
30
40
50
60
70
80
90
100
05-0
3-20
09
07-0
4-20
09
28-0
4-20
09
06-0
5-20
09
19-5
-200
9
2-6-
2009
11-6
-200
9
23-6
-200
9
25-6
-200
9
9-7-
2009
15-7
-200
9
23-7
-200
9
30-7
-200
9
4-8-
2009
13-8
-200
9
20-8
-200
9
26-8
-200
9
3-9-
2009
8-9-
2009
Date
MD
LD
Degradation NDMA (100/10)
0
10
20
30
40
50
60
70
80
90
100
05-0
3-20
09
07-0
4-20
09
20-0
4-20
09
28-0
4-20
09
06-0
5-20
09
19-5
-200
9
2-6-
2009
11-6
-200
9
23-6
-200
9
25-6
-200
9
9-7-
2009
15-7
-200
9
23-7
-200
9
30-7
-200
9
4-8-
2009
13-8
-200
9
20-8
-200
9
26-8
-200
9
3-9-
2009
8-9-
2009
Date
De
gra
da
tio
n (
%)
MD
LD
Degradation NDMA (100/0)
0
10
20
30
40
50
60
70
80
90
100
05-0
3-20
09
07-0
4-20
09
28-0
4-20
09
06-0
5-20
09
19-5
-200
9
2-6-
2009
11-6
-200
9
23-6
-200
9
25-6
-200
9
9-7-
2009
15-7
-200
9
23-7
-200
9
30-7
-200
9
4-8-
2009
13-8
-200
9
20-8
-200
9
26-8
-200
9
3-9-
2009
8-9-
2009
Date
MD
LD
Goals - DW production – OMPs in source – Theory – PI – Results – Conclusions – Further
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Degradation of model compounds
Goals - DW production – OMPs in source – Theory – PI – Results – Conclusions – Further
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Mean degradation Atrazine
0102030405060708090
100
100/10 100/5 100/0 80/10 80/5 80/0 60/10 60/5 60/0
Setting
Mea
n d
egra
dat
ion
(%
)
LD
MD
Mean degradation NDMA
0102030405060708090
100
100/10 100/5 100/0 80/10 80/5 80/0 60/10 60/5 60/0
Setting
Mea
n d
egra
dat
ion
(%
)
LD
MD
Mean degradation Bromacil
0102030405060708090
100
100/10 100/5 100/0 80/10 80/5 80/0 60/10 60/5 60/0
Setting
LD
MD
Mean degradation Ibuprofen
0102030405060708090
100
100/10 100/5 100/0 80/10 80/5 80/0 60/10 60/5 60/0
Setting
LD
MD
Mean degradation of model compounds
Goals - DW production – OMPs in source – Theory – PI – Results – Conclusions – Further
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EEO Bromacil (100/10)
0
2,5
5
7,5
10
12,5
15
05-0
3-20
09
07-0
4-20
09
20-0
4-20
09
28-0
4-20
09
06-0
5-20
09
19-5
-200
9
2-6-
2009
11-6
-200
9
23-6
-200
9
25-6
-200
9
9-7-
2009
15-7
-200
9
23-7
-200
9
30-7
-200
9
4-8-
2009
13-8
-200
9
20-8
-200
9
26-8
-200
9
3-9-
2009
8-9-
2009
Date
EE
O (
kWh
/m3)
MD
LD
EEO Bromacil (100/0)
0
2,5
5
7,5
10
12,5
15
05-0
3-20
09
07-0
4-20
09
28-0
4-20
09
06-0
5-20
09
19-5
-200
9
2-6-
2009
11-6
-200
9
23-6
-200
9
25-6
-200
9
9-7-
2009
15-7
-200
9
23-7
-200
9
30-7
-200
9
4-8-
2009
13-8
-200
9
20-8
-200
9
26-8
-200
9
3-9-
2009
8-9-
2009
Date
MD
LD
EEO = Electrical Energy per Order
Goals - DW production – OMPs in source – Theory – PI – Results – Conclusions – Further
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Mean EEO
Goals - DW production – OMPs in source – Theory – PI – Results – Conclusions – Further
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Mean EEO Atrazine
0
2
4
6
8
10
12
14
100/10 100/5 100/0 80/10 80/5 80/0 60/10 60/5 60/0
Setting
Mea
n E
EO
(kW
h/m
3)
LD
MD
Mean EEO Bromacil
0
2
4
6
8
10
12
14
100/10 100/5 100/0 80/10 80/5 80/0 60/10 60/5 60/0
Setting
LD
MD
Mean EEO Ibuprofen
0
2
4
6
8
10
12
14
100/10 100/5 100/0 80/10 80/5 80/0 60/10 60/5 60/0
Setting
Mea
n E
EO
(kW
h/m
3)
LD
MD
Mean EEO NDMA
0
2
4
6
8
10
12
14
100/10 100/5 100/0 80/10 80/5 80/0 60/10 60/5 60/0
Setting
LD
MD
Mean EEO
Goals - DW production – OMPs in source – Theory – PI – Results – Conclusions – Further
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Mean EEOMean EEO Atrazine
0,0
0,5
1,0
1,5
2,0
2,5
100/10 100/5 80/10 80/5 60/10 60/5
Setting
Mea
n E
EO
(kW
h/m
3)
LD
MD
Mean EEO Bromacil
0,0
0,5
1,0
1,5
2,0
2,5
100/10 100/5 80/10 80/5 60/10 60/5
Setting
LD
MD
Mean EEO Ibuprofen
0,0
0,5
1,0
1,5
2,0
2,5
100/10 100/5 80/10 80/5 60/10 60/5
Setting
Mea
n E
EO
(kW
h/m
3)
LD
MD
Mean EEO NDMA
0,0
0,5
1,0
1,5
2,0
2,5
100/10 100/5 80/10 80/5 60/10 60/5
Setting
LD
MD
Mean EEO(excluding 0 mg/l H2O2)
Goals - DW production – OMPs in source – Theory – PI – Results – Conclusions – Further
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Nitrite formation
Concentrations NO2 (mg/l) Formation factor (-)
IN EF-LD EF-MD EF-LD EF-MD
100/10 0,0016 0,0044 0,5944 1,32 80,65 100/5 0,0013 0,0102 0,1409 15-jul
100/0 0,0007 0,0112 0,1636 1,68 361,44
100/10 0,0010 0,0131 0,1830 6,77 106,56 100/5 0,0023 0,0105 0,4358 15,92 246,88 4-aug
100/0 0,0007 0,0118 0,4896 12,27 183,85
100/10 0,0008 0,0046 0,1668 3,57 188,47 100/5 0,0837 0,0657 0,5254 15,89 698,49 13-aug
100/0 0,0867 0,0791 0,5915 4,75 207,50
100/10 0,0893 0,1018 0,2078 -0,22 5,27 100/5 0,0016 0,0044 0,5944 -0,09 5,82 3-sep
100/0 0,0013 0,0102 0,1409 0,14 1,33
Goals - DW production – OMPs in source – Theory – PI – Results – Conclusions – Further
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Influence nitrite formation (100/10)
Atrazine (100/10)
70
75
80
85
90
95
4-aug 13-aug
Date
Deg
rad
atio
n (
%)
LD
MD
Bromacil (100/10)
70
75
80
85
90
95
4-aug 13-aug
Date
LD
MD
Ibuprofen (100/10)
70
75
80
85
90
95
4-aug 13-aug
Date
Deg
rad
atio
n (
%)
LD
MD
NDMA (100/10)
70
75
80
85
90
95
4-aug 13-aug
Date
LD
MD
Goals - DW production – OMPs in source – Theory – PI – Results – Conclusions – Further
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Influence nitrite formation (100/5)
Atrazine (100/5)
50
60
70
80
4-aug 13-aug
Date
Deg
rad
atio
n (
%)
LD
MD
Bromacil (100/5)
50
60
70
80
4-aug 13-aug
Date
Deg
rad
atio
n (
%)
LD
MD
Ibuprofen (100/5)
50
60
70
80
4-aug 13-aug
Date
Deg
rad
atio
n (
%)
LD
MD
NDMA (100/5)
80
90
100
4-aug 13-aug
Date
Deg
rad
atio
n (
%)
LD
MD
Goals - DW production – OMPs in source – Theory – PI – Results – Conclusions – Further
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Influence nitrite formation (100/0)
Atrazine (100/0)
30
40
50
60
70
4-aug 13-aug
Date
Deg
rad
atio
n (
%)
LD
MD
Bromacil (100/0)
0
10
20
30
40
4-aug 13-aug
Date
Deg
rad
atio
n (
%)
LD
MD
Ibuprofen (100/0)
0
10
20
30
40
50
4-aug 13-aug
Date
Deg
rad
atio
n (
%)
LD
MD
NDMA (100/0)
70
80
90
100
4-aug 13-aug
Date
Deg
rad
atio
n (
%)
LD
MD
Goals - DW production – OMPs in source – Theory – PI – Results – Conclusions – Further
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Influence of DOC DOC (100/10)
2,8
3
3,2
3,4
3,6
15-jul 13-aug 3-sep
DO
C (
mg
/l C
)UV-IN
UVL-EF
UVM-EF
Atrazine (100/10)
60
65
70
75
80
85
90
15-jul 13-aug 3-sep
Date
Deg
rad
atio
n (
%)
LD
MD
Bromacil (100/10)
60
65
70
75
80
85
90
15-jul 13-aug 3-sep
Date
LD
MD
Goals - DW production – OMPs in source – Theory – PI – Results – Conclusions – Further
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Influence of DOC DOC (100/10)
2,8
3
3,2
3,4
3,6
15-jul 13-aug 3-sep
DO
C (
mg
/l C
)UV-IN
UVL-EF
UVM-EF
Ibuprofen (100/10)
60
65
70
75
80
85
90
15-jul 13-aug 3-sep
Date
Deg
rad
atio
n (
%)
LD
MD
NDMA (100/10)
60
65
70
75
80
85
90
15-jul 13-aug 3-sep
Date
LD
MD
Goals - DW production – OMPs in source – Theory – PI – Results – Conclusions – Further
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Formation of AOC
?
Goals - DW production – OMPs in source – Theory – PI – Results – Conclusions – Further
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Increased UVT via GAC
Influent RSF GACF 8-sep 10-sep UVT % ±78 ±98 pH - 7,91 8,69 Bicarbonate mg/l HCO 140 120 Carbonate mg/l CO3 0 6,05 Ammonium mg/l NH4 0,012 0,005 Ammonium mg/l N 0,009 0,004 Nitrite mg/l NO2 0,005 0,629 Nitrite mg/l N 0,001 0,192 Nitrate mg/l N 2,20 1,15 Nitrate mg/l NO3 9,72 5,08 DOC mg/l C 3,17 0,23
Goals - DW production – OMPs in source – Theory – PI – Results – Conclusions – Further
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Influence increased UVTLP Degradation (8-09-09)
0%
10%
20%
30%
40%
50%
60%
70%
80%
90%
100%
100/10 100/0 80/10 80/0 60/10 60/0
Setting (%UV / ppm H2O2)
De
gra
da
tio
n (
%)
Atrazine
Bromacil
Ibuprofen
NDMA
LP Degradation (10-09-09)
0%
10%
20%
30%
40%
50%
60%
70%
80%
90%
100%
100/10 100/0 80/10 80/0 60/10 60/0
Setting (%UV / ppm H2O2)
Atrazine
Bromacil
Ibuprofen
NDMA
MP Degradation (8-09-09)
0%
10%
20%
30%
40%
50%
60%
70%
80%
90%
100%
100/10 100/0 80/10 80/0 60/10 60/0
Setting (%UV / ppm H2O2)
De
gra
da
tio
n (
%)
Atrazine
Bromacil
Ibuprofen
NDMA
MP Degradation (10-09-09)
0%
10%
20%
30%
40%
50%
60%
70%
80%
90%
100%
100/10 100/0 80/10 80/0 60/10 60/0
Setting (%UV / ppm H2O2)
Atrazine
Bromacil
Ibuprofen
NDMA
Goals - DW production – OMPs in source – Theory – PI – Results – Conclusions – Further
research
38
Influence increased UVTLP EEO (8-09-09)
0
1
2
3
4
5
6
7
100/10 100/0 80/10 80/0 60/10 60/0
Setting (%UV / ppm H2O2)
EE
O (
kWh
/m3) Atrazine
Bromacil
Ibuprofen
NDMA
LP EEO (10-09-09)
0
1
2
3
4
5
6
7
100/10 100/0 80/10 80/0 60/10 60/0
Setting (%UV / ppm H2O2)
Atrazine
Bromacil
Ibuprofen
NDMA
MP EEO (8-09-09)
0
1
2
3
4
5
6
7
100/10 100/0 80/10 80/0 60/10 60/0
Setting (%UV / ppm H2O2)
EE
O (
kWh
/m3) Atrazine
Bromacil
Ibuprofen
NDMA
MP EEO (11-09-09)
0
1
2
3
4
5
6
7
100/10 100/0 80/10 80/0 60/10 60/0
Setting (%UV / ppm H2O2)
Atrazine
Bromacil
Ibuprofen
NDMA
Goals - DW production – OMPs in source – Theory – PI – Results – Conclusions – Further
research
39
Conclusions
Degradation by LP comparable to MP
Average degradation NDMA by LP higher then MP
EEO LP < EEO MP
MP shows higher nitrite formation
MP converts/consumes more DOC
Goals - DW production – OMPs in source – Theory – PI – Results – Conclusions – Further
research
40
Further research topics
Influence water temperature on UV dose
Linearity UV ballast – UV dose
Degradation DOC / formation AOC
Nitrite/nitrate issues
Degradation remaining peroxide
Improvement quality influent water
By- and degradation products
Modelling of degradation
Goals - DW production – OMPs in source – Theory – PI – Results – Conclusions – Further
research
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