Degradation of organic micropollutants via Advanced Oxidation Process (UV/H 2 O 2 ) 25-09-2009 Josanne Derks Results pilot plant research.

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


research

4

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


research

5

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


research

6

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


research

7

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


research

8

A multitude of compounds and technologies


research

http://wedeco.emea.itt.net/sales/uv/Marketing/UV%20general/Pictures/strahler_image_1300.jpg

http://wedeco.emea.itt.net/sales/ozone/PDO%202000%20%20Aquarno%20Italy/Aquarno_avviamento_ott%2007%20017.jpg

9

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


research

10

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


research

11

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


research

12

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



research

13

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 ↓



research

14

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


research

15

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


research

16

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 %


research

17

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




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





RSF


research

18

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


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


Atrazine

Bromacil

Ibuprofen

NDMA


research

19

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


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


Atrazine

Bromacil

Ibuprofen

NDMA

Degradation of model compounds


research

20

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


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


Atrazine

Bromacil

Ibuprofen

NDMA

EEO = Electrical Energy per Order

P * UV

Q * log (ci/cf)EEO = kWh/m3


research

21Goals - DW production – OMPs in source – Theory – PI – Results – Conclusions – Further

research

22

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


research

23

Degradation of model compounds


research

24

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


research

25

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


research

26

Mean EEO


research

27

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


research

28

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)


research

29

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


research

30

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


research

31


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


research

32


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


research

33

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


research

34

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


research

35

Formation of AOC

?


research

36

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


research

37

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


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


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


Atrazine

Bromacil

Ibuprofen

NDMA


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


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


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


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


Atrazine

Bromacil

Ibuprofen

NDMA


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


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


research

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Degradation of organic micropollutants via Advanced Oxidation Process (UV/H 2 O 2 ) 25-09-2009 Josanne Derks Results pilot plant research.

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