My Doctoral Thesis, titled "Advanced Oxidation Processes applied to mineralize Paracetamol, Chloroxylenol, Ibuprofen and Diclofenac in aqueous medium".

1. Advanced Oxidation Processes applied to
mineralize
Paracetamol, Chloroxylenol, Ibuprofen and
Diclofenac in aqueous medium
Marcel Skoumal
Directors de Tesi: Dr. Pere-Lluís Cabot
Dra. Rosa M. Rodríguez

2. Presentation Structure
- Pharmaceuticals and Personal Care Products in Freshwater
- Studied Pharmaceuticals and Personal Care Products
Introduction
- Advanced Oxidation Processes
- Paracetamol by ozone-based AOPs
- Chloroxylenol by EAOPs
Degradation studies
- Ibuprofen by EAOPs
- Diclofenac by EAOPs
2

3. Freshwater is an irreplaceable resource for life
3

4. - herbicides
- pesticides
- heavy metals
- synthesis by-products...
- ...
Pharmaceuticals and Personal Care Products
4

5. Pharmaceuticals and Personal Care Products (PPCPs)
5

6. How do PPCPs reach the aquatic environment?
• Excretion of pharmaceuticals
• Use of Personal Care Products
• Improper disposal of medicines
• Veterinary use
• Residues from pharmaceutical factories and hospitals
6

7. Pharmaceuticals and Personal Care Products
have been detected here...
...and even here.
7

8. PPCPs are present in the environment.
So, what?
Main concerns:
• Growing number of detected PPCPs
• Uncertain risk of chronic exposure
8

9. Studied PPCPs
• PARACETAMOL
• CHLOROXYLENOL
• IBUPROFEN
• DICLOFENAC
9

10. - Paracetamol
- Chloroxylenol
Studied PPCPs
- Ibuprofen
- Diclofenac
H
N
Paracetamol O
HO
IUPAC name: N-(4-hydroxyphenyl)acetamide
Type: analgesic drug
Consumption: high, common household drug
up to 246 g L-1 (STP influent) and 220 ng L-1 (STP effluent) (a)
Occurrence:
30 ng L-1 (Llobregat river), 22 ng L-1 (Ebro river) (b)
Threats: Unknown effect of chronic exposure to either humans and
aquatic animals
(a) Gómez et al. Chemosphere (2007), 66(6), 993. 10
(b) Pedrouzo et al. J Separ Sci (2007), 30(3), 297.

11. - Paracetamol
- Chloroxylenol
Studied PPCPs
- Ibuprofen
- Diclofenac
Cl
Chloroxylenol
HO
IUPAC name: 4-chloro-3,5-dimethylphenol
Type: antimicrobial
Uses: antimicrobial preservative, disinfectant soaps
over 500 g L-1 (United Kingdom stuaries) (c)
Occurrence:
Threats: bacterial resistance
(c)
Thomas et al. Environ. Toxicol. 11
Pharmacol (1999), 18(3), 401.

12. - Paracetamol
- Chloroxylenol
Studied PPCPs
- Ibuprofen
- Diclofenac
OH
Ibuprofen O
IUPAC name: 2-[4-(2-methylpropyl)phenyl]propanoic acid
Drug type: NSAID
Consumption: very extended, common household drug
up to 370 g L-1 (STP influent), 48 g L-1 (effluent) (d)
Occurrence:
up to 530 ng L-1 in German rivers (e)
Threats: - unknown effect of chronic exposure to humans
- growth slow-down in some aquatic larvae
(d) Santos et al. Environment. Int. (2007), 33(4), 596.
12
(e) Ternes Water Res. (1998), 32(11), 3245.

13. - Paracetamol
- Chloroxylenol
O
Studied PPCPs
- Ibuprofen
- Diclofenac
HO Cl
H
N
Diclofenac
Cl
IUPAC name: 2-[2-(2,6-dichlorophenylamino)phenyl]acetic acid
Drug type: NSAID
Consumption extent: extended, common household drug
810 ng L-1 in German STP effluents, 150 ng L-1 in
Occurrence:
German rivers) (e). Over 140 ng L-1 in Catalan STP
effluents, 41 ng L-1 in Ter river(b).
Threats: - unknown effect of chronic exposure to humans
- kidney damage on fish(f)
(e) Ternes Water Res. (1998), 32(11), 3245.
13
(b) Pedrouzo et al. J Separ Sci (2007), 30(3), 297.
(f) Höger et al. Aquat. Toxicol. (2005), 75(1), 53.

14. Advanced Oxidation Processes (AOPs)
Characteristics:
- Near ambient Temperature & Pressure
- No inherent generation of undesirable side-products
- Generation of Hydroxyl Radicals
Process E° / V
F2(g) + 2 e ⇌ 2 F 2,87
OH(aq) + H+ + e ⇌ H2O(aq) 2,80
O3(g) + 2 H+ + 2 e ⇌ O2 + H2O(aq) 2,07
H2O2(aq) + 2 H+ + 2 e ⇌ 2 H2O(aq) 1,77
O2 + 4 H+ + 4 e ⇌ 2 H2O(aq) 1,23
O2 + 2 H+(aq) + 2 e ⇌ H2O2(aq) 0,70
14

15. Working method
Analysis of global content
of pollutants: TOC
Identification of degradation
intermediates: GC-MS
Treatment cell
(ozonation or electrolysis)
sampling
Analysis of individual
15
pollutants: HPLC

16. - Paracetamol
- Chloroxylenol
Degradation Studies
- Ibuprofen
- Diclofenac
Mineralization of Paracetamol by ozone-based AOPs
Main oxidant species: O3 & OH.
O3: generated from an electrical discharge over
oxygen in the ozonator
the ozone source
16

17. Experimental device for ozonations
tubing for
ozone supply
6W blacklight
blue tube
coolant outlet
coolant inlet
magnetic
stirrer
17

18. - Paracetamol
- Chloroxylenol
Degradation Studies
- Ibuprofen
- Diclofenac
Ozone flow effect
100
flow value
O3 alone
0.7 g O3 h-1
80
TOC / mg L-1
1.0 g O3 h-1
60
40
O3/Fe2+,Cu2+/H2O2/UVA
0.5 g O3 h-1
20
1.0 g O3 h-1
0
0 60 120 180 240 300
t / min
18
Conditions: pH 3.0, 25.0 °C.

19. - Paracetamol
- Chloroxylenol
Degradation Studies
- Ibuprofen
- Diclofenac
Irradiance effect
O3/Fe2+/UVA – 14 cm
100
O3/Fe2+,Cu2+/UVA – 14 cm
80 O3/Fe2+/UVA – 7 cm
TOC / mg L-1
O3/Fe2+,Cu2+/UVA – 7 cm
60
40
20
0
0 60 120 180 240 300
t / min
19
Conditions: 1 g O3 h-1, pH 3.0, 25.0 °C.

20. - Paracetamol
- Chloroxylenol
Degradation Studies
- Ibuprofen
- Diclofenac
Temperature influence
100
O3, 25 °C
O3, 35 °C
80
TOC / mg L-1
60
40
O3/Fe2+,Cu2+,H2O2/UVA
20 O3/Fe2+,Cu2+,H2O2/UVA
0
0 60 120 180 240 300
t / min
20
Conditions: 1 g O3 h-1, pH 3.0.

21. - Paracetamol
- Chloroxylenol
Degradation Studies
- Ibuprofen
- Diclofenac
Study of pH influence
(O3/UVA treatment)
100
O3/UVA, pH 3
O3/UVA, pH 9
80
TOC / mg L-1
60
40
20
0
0 60 120 180 240 300
t / min
21
Conditions: 1 g O3 h-1, 25.0 °C.

22. - Paracetamol
- Chloroxylenol
Degradation Studies
- Ibuprofen
- Diclofenac
Study of pH influence
(O3/Fe2+/ UVA treatment)
100 pH 2
pH 3
Fe2+ + H2O2 → Fe3+ +OH- + OH
80 pH 4
Fe3+ + H2O + h → Fe2+ + H+ + OH
TOC / mg L-1
pH 6
60
40
20
0
0 60 120 180 240 300
t / min
22
Conditions: 1 g O3 h-1, 25.0 °C, 1.0 mM Fe2+.

23. - Paracetamol
- Chloroxylenol
Degradation Studies
- Ibuprofen
- Diclofenac
Testing of several O3-based AOPs
O3
100
O3/Fe2+
O3/Cu2+
80
TOC / mg L-1
O3/UVA
O3/H2O2/UVA
60
O3/Fe2+/UVA
O3/Fe2+,Cu2+/UVA
40
20
0
0 60 120 180 240 300
t / min
Common conditions: 1 g O3 h-1, 25.0 °C, pH 3.0.
23
Cation including treatments contain 1.0 mM Fe2+ and/or 0.25 mM Cu2+.

24. - Paracetamol
- Chloroxylenol
Degradation Studies
- Ibuprofen
- Diclofenac
[H2O2] monitoring during course
of several O3-based AOPs
1.2
O3
1 O3/Fe2+
[H2O2] / mg L-1
O3/Cu2+
0.8 O3/UVA
O3/Fe2+/UVA
0.6
O3/Fe2+,Cu2+/UVA
0.4
0.2
0
0 10 20 30 40 50 60 70
t / min
Common conditions: 1 g O3 h-1, 25.0 °C, pH 3.0.
24
Cation including treatments contain 1.0 mM Fe2+ and/or 0.25 mM Cu2+.

25. - Paracetamol
- Chloroxylenol
Degradation Studies
- Ibuprofen
- Diclofenac
Does OH really work?
O3/Fe2+
Oxamic acid / mg L-1
O3/Fe2+ + tBu
20 O3/Fe2+/UVA
O3/Fe2+/UVA + tBu
O3/Fe2+,Cu2+
O3/Fe2+,Cu2+ + tBu
O3/Fe2+,Cu2+/UVA
15
O3/Fe2+,Cu2+/UVA + tBu
10
0 20 40 60 80
t / min
Conditions: 1 g O3 h-1, 25.0 °C, pH 3.0. 25
Added cation concentrations: 1.0 mM Fe2+ and/or 0.25 mM Cu2+.

26. - Paracetamol
- Chloroxylenol
Degradation Studies
- Ibuprofen
- Diclofenac
Influence of Fe2+ and Cu2+ presence and ratios
on Paracetamol mineralization through O3/UVA treatment
0.25 mM Fe2+
100
1 mM Fe2+
0.25 mM Cu2+
80
1 mM Cu2+
TOC / mg L-1
1 mM Fe2+, 0.25 mM Cu2+
60
x 0.25 mM Fe2+,1 mM Cu2+
0.5 mM Fe2+,0.5 mM Cu2+
40
20
0
0 60 120 180 240 300 360
t / min
26
Conditions: 1 g O3 h-1, 25.0 °C, pH 3.0.

27. - Paracetamol
- Chloroxylenol
Degradation Studies
- Ibuprofen
- Diclofenac
Mineralization of Paracetamol by O3-based AOPs
at different initial concentrations
500
600
400
TOC / mg L-1
TOC / mg L-1
O3/UVA O3/Fe2+/UVA
300 400
200
200
100
0 0
0 120 240 360 480 0 120 240 360 480 600 720 840
t / min t / min
500
600
400
TOC / mg L-1
TOC / mg L-1
O3/Fe2+,Cu2+,H2O2/UVA
O3/Fe2+,Cu2+/UVA 300
400
200
200
100
0 0
0 120 240 360 0 60 120 180 240 300
t / min t / min
Conditions: 1 g O3 h-1, 25.0 °C, pH 3.0. 27
Added cation concentrations: 1.0 mM Fe2+ and/or 0.25 mM Cu2+.

28. - Paracetamol
- Chloroxylenol
Degradation Studies
- Ibuprofen
- Diclofenac
Paracetamol abatement kinetics
under different ozone-based AOPs
180
8 O3
paracetamol / mg L-1
O3/UVA
150
6
O3/Fe2+/UVA
ln[C0/Ct]
120 O3/Fe2+,Cu2+/UVA
4
90 2
0
60 k’ / 10-2 s-1
1.2
0 2 t / min 4 6
1.7
30
1.7
1.6
0
0 2 4 6 8
t / min
28
Conditions: 1 g O3 h-1, 25.0 °C, pH 3.0.
Added cation concentrations: 1.0 mM Fe2+ and/or 0.25 mM Cu2+.

29. - Paracetamol
- Chloroxylenol
Degradation Studies
- Ibuprofen
- Diclofenac
Paracetamol abatement kinetics at different
initial concentrations for O3/Fe2+,Cu2+/UVA treatment
800
5 157 mg L-1
paracetamol / mg L-1
315 mg L-1
4
628 mg L-1
600
ln[C0/Ct] 3
2
400
1
0 k’ / 10-2 s-1
200 1.6
0 2 t / min 4 6
1.1
0.8
0
0 2 4 6 8 10 12
t / min
29
Conditions: 1 g O3 h-1, 25.0 °C, pH 3.0.
Added cation concentrations: 1.0 mM Fe2+ and/or 0.25 mM Cu2+.

30. GC-MS-identified Paracetamol intermediates
acetamide
hydroquinone p-benzoquinone
glycolic acid glyoxylic acid oxalic acid
tartronic acid ketomalonic acid
2-hydroxy-4(N-acetyl)aminophenol
30
maleic acid

31. - Paracetamol
- Chloroxylenol
Degradation Studies
- Ibuprofen
- Diclofenac
Aromatic intermediates of Paracetamol
Hydroquinone
9
[hydroquinone] / mg L-1
O3
8
O3/UVA
7 O3/Fe2+/UVA
6 O3/Fe2+,Cu2+/UVA
5
4
3
2
1
0
0 1 2 3 4 5 6
t / min
Conditions: 1 g O3 h-1, 25.0 °C, pH 3.0. 31
Added cation concentrations: 1.0 mM Fe2+ and/or 0.25 mM Cu2+.

32. - Paracetamol
- Chloroxylenol
Degradation Studies
- Ibuprofen
- Diclofenac
Aromatic intermediates of Paracetamol
p-benzoquinone
12
[p-benzoquinone] / mg L-1
O3
O3/UVA
10
O3/Fe2+/UVA
8 O3/Fe2+,Cu2+/UVA
6
4
2
0
0 2 4 6 8
t / min
Conditions: 1 g O3 h-1, 25.0 °C, pH 3.0. 32
Added cation concentrations: 1.0 mM Fe2+ and/or 0.25 mM Cu2+.

33. - Paracetamol
- Chloroxylenol
Degradation Studies
- Ibuprofen
- Diclofenac
Aliphatic carboxylic acid intermediates of Paracetamol
Oxalic acid
250
[oxalic acid]/ mg L-1
200
O3
150
O3/UVA
O3/Fe2+/UVA
100 O3/Fe2+,Cu2+/UVA
50
0
0 60 120 180 240 300
t / min
Conditions: 1 g O3 h-1, 25.0 °C, pH 3.0. 33
Added cation concentrations: 1.0 mM Fe2+ and/or 0.25 mM Cu2+.

34. - Paracetamol
- Chloroxylenol
Degradation Studies
- Ibuprofen
- Diclofenac
Aliphatic carboxylic acid intermediates of Paracetamol
Oxamic acid
50
O3
[oxamic acid] / mg L-1
O3/UVA
40
O3/Fe2+/UVA
O3/Fe2+,Cu2+/UVA
30
20
10
0
0 60 120 180 240 300
t / min
Conditions: 1 g O3 h-1, 25.0 °C, pH 3.0. 34
Added cation concentrations: 1.0 mM Fe2+ and/or 0.25 mM Cu2+.

35. - Paracetamol
- Chloroxylenol
Degradation Studies
- Ibuprofen
- Diclofenac
Ions arising from Paracetamol mineralization
NH4+
Ammonium ion
10 O3
O3/UVA
8 O3/Fe2+/UVA
NH4+ / mg L-1
O3/Fe2+,Cu2+/UVA
6
4
2
0
0 60 120 180 240 300
t / min
Conditions: 1 g O3 h-1, 25.0 °C, pH 3.0. 35
Added cation concentrations: 1.0 mM Fe2+ and/or 0.25 mM Cu2+.

36. - Paracetamol
- Chloroxylenol
Degradation Studies
- Ibuprofen
- Diclofenac
Ions arising from Paracetamol mineralization
NO3
Nitrate
45
O3
40
O3/UVA
35 O3/Fe2+/UVA
NO3 / mg L-1
O3/Fe2+,Cu2+/UVA
30
25
20
15
10
5
0
0 60 120 180 240 300
t / min
Conditions: 1 g O3 h-1, 25.0 °C, pH 3.0.
36
Added cation concentrations: 1.0 mM Fe2+ and/or 0.25 mM Cu2+.

37. Proposal of a degradation pathway for the mineralization of Paracetamol
acetamide Fe3+ - oxamato
oxamic acid
complexes
CO2
NO3-, NH4+
Cu2+ - oxamato
complexes
glycolic acid glyoxylic acid
2-hydroxy-4(N-acetyl)aminophenol
paracetamol
tartronic acid ketomalonic acid oxalic acid
Fe3+ - oxalato Cu3+ - oxalato
complexes complexes
37
hydroquinone p-benzoquinone maleic acid CO2

38. - Paracetamol
- Chloroxylenol
Degradation Studies
- Ibuprofen
- Diclofenac
Mineralization of Chloroxylenol by EAOPs
38

39. - Paracetamol
- Chloroxylenol
Degradation Studies
- Ibuprofen
- Diclofenac
Chloroxylenol mineralization by ozonation: inefficient
70
O3
60 O3/UVA
O3/Fe2+/UVA
[TOC] / mg L-1
50
40
30
20
10
0
0 60 120 180 240 300
t / min
Conditions: 1 g O3 h-1, 25.0 °C, pH 3.0. 39
Added cation concentrations: 1.0 mM Fe2+ and/or 0.25 mM Cu2+.

40. - Paracetamol
- Chloroxylenol
Degradation Studies
- Ibuprofen
- Diclofenac
Experimental device for electrolyses
40

41. Experimental device for electrolyses
Electrodic configurations for
Electrochemical Advanced Oxidation Processes
Platinum anode
+
Stainless steel cathode:
Pt-AO method
magnetic
stirrer
41

42. Electrodic configurations for
Electrochemical Advanced Oxidation Processes
BDD anode
+
Stainless steel cathode:
BDD-AO method
magnetic
stirrer
42

43. Electrodic configurations for
Electrochemical Advanced Oxidation Processes
Pt anode
+
O2-diffusion cathode :
Pt-EF method
magnetic
stirrer
43

44. Electrodic configurations for
Electrochemical Advanced Oxidation Processes
BDD anode
+
O2-diffusion cathode :
BDD-EF method
magnetic
stirrer
44

45. Electrodic configurations for
Electrochemical Advanced Oxidation Processes
BDD anode
+
O2-diffusion cathode:
BDD-PEF method
magnetic
stirrer
45

46. - Paracetamol
- Chloroxylenol
Degradation Studies
- Ibuprofen
- Diclofenac
Electrolysis of chloroxylenol with platinum and BDD anodes.
70
Pt anode; (Pt-AO treatment
60
BDD anode; (BDD-AO treatment)
50
[TOC] / mg L-1
40
30
20
10
0
0 120 240 360
t / min
Counter electrode: stainless steel cathode, 46
j = 100 mA cm-2, pH 3.0, 25°C

47. - Paracetamol
- Chloroxylenol
Degradation Studies
- Ibuprofen
- Diclofenac
Effect of current density on BDD-AO treatment
70
33 mA cm-2
60
100 mA cm-2
150 mA cm-2
50
[TOC] / mg L-1
40
30
20
10
0
0 120 240 360 480 600
t / min
47
Conditions: pH 3.0, 25°C

48. - Paracetamol
- Chloroxylenol
Degradation Studies
- Ibuprofen
- Diclofenac
Charge (Q) consumption during BDD-AO treatment
at different applied current densities
80
33 mA cm-2
70
100 mA cm-2
60 150 mA cm-2
[TOC] / mg L-1
50
40
30
20
10
0
0 10 20 30
Q / AhL-1
48
Conditions: pH 3.0, 25°C

49. - Paracetamol
- Chloroxylenol
Degradation Studies
- Ibuprofen
- Diclofenac
Charge (Q) consumption during Pt-EF treatment
at different applied current densities
70
33 mA cm-2
60
100 mA cm-2
150 mA cm-2
50
[TOC] / mg L-1
40
30
20
10
0
0 10 20 30
Q / AhL-1
49
Conditions: pH 3.0, 25°C, 1.0 mM Fe2+

50. - Paracetamol
- Chloroxylenol
Degradation Studies
- Ibuprofen
- Diclofenac
Charge (Q) consumption during BDD-EF treatment
at different applied current densities
70
33 mA cm-2
60
100 mA cm-2
[TOC] / mg L-1
150 mA cm-2
50
40
30
20
10
0
0 10 20 30
Q / AhL-1
50
Conditions: pH 3.0, 25°C, 1.0 mM Fe2+

51. - Paracetamol
- Chloroxylenol
Degradation Studies
- Ibuprofen
- Diclofenac
Testing of several EAOPs on chloroxylenol
70
Pt-AO
60 BDD-AO
Pt-EF
50
[TOC] / mg L-1
Pt-PEF
40 BDD-EF
BDD-PEF
30
20
10
0
0 120 240 360 480
t / min
Conditions: j = 33 mA cm-2, pH 3.0, 25°C. 51
1.0 mM Fe2+ in EF-treatments

52. - Paracetamol
- Chloroxylenol
Degradation Studies
- Ibuprofen
- Diclofenac
Abatement of Chloroxylenol
Pt-AO, 33 mA cm-2
100
[Chloroxylenol] / mg L-1
BDD-AO, 33 mA cm-2
BDD-AO, 100 mA cm-2
80
BDD-AO, 133 mA cm-2
60
40
20
0
0 120 240 360 480 600 720
t / min
52
Conditions: pH 3.0, 25.0 °C.

53. - Paracetamol
- Chloroxylenol
Degradation Studies
- Ibuprofen
- Diclofenac
Chloroxylenol abatement kinetics
under different electro-Fenton EAOPs
120
5 Pt-EF
[Chloroxylenol] / mg L-1
Pt-PEF
100 4
BDD-EF
ln[C0/Ct] 3 BDD-PEF
80
2
60
1
40 0
k’ / 10-3 s-1
0 2 4 6 8 10 12
t / min
20 6.2
6.3
0
6.4
0 5 10 15 20 25 6.9
t / min
53
Conditions: j = 33 mA cm-2, pH 3.0, 25.0 °C, 1.0 mM Fe2+

54. GC-MS-identified Chloroxylenol intermediates
2,6-dimethylhydroquinone
2,6-dimethyl-p-benzoquinone
3,5-dimethyl-2-hydroxy-p-benzoquinone
54

55. - Paracetamol
- Chloroxylenol
Degradation Studies
- Ibuprofen
- Diclofenac
Chloroxylenol aromatic intermediates
2,6-dimethyl-p-benzoquinone
[2,6-dimethyl-p-benzoquinone] / mg L-1
40
35
Pt-AO
30 BDD-AO
25
20
15
10
5
0
0 2 4 6 8 10 12 14 16 18
t/h
55
Conditions: j = 33 mA cm-2, pH 3.0, 25.0 °C.

56. - Paracetamol
- Chloroxylenol
Degradation Studies
- Ibuprofen
- Diclofenac
Chloroxylenol intermediates
2,6-dimethyl-p-benzoquinone
[2,6-dimethyl-p-benzoquinone] / mg L-1
10
Pt-EF
9
Pt-PEF
8
BDD-EF
7
BDD-PEF
6
5
4
3
2
1
0
0 5 10 15 20 25
t / min 56
Conditions: j = 33 mA cm-2, pH 3.0, 25.0 °C, 1.0 mM Fe2+

57. - Paracetamol
- Chloroxylenol
Degradation Studies
- Ibuprofen
- Diclofenac
Chloroxylenol intermediates
Pyruvic acid
25
Pt-EF
20 Pt-PEF
[pyruvic acid] / mg L-1
BDD-EF
BDD-PEF
15
10
5
0
0 20 40 60 80
t / min
57
Conditions: j = 33 mA cm-2, pH 3.0, 25.0 °C, 1.0 mM Fe2+

58. - Paracetamol
- Chloroxylenol
Degradation Studies
- Ibuprofen
- Diclofenac
Chloroxylenol intermediates
Acetic acid
35
Pt-EF
Pt-PEF
30
BDD-EF
[acetic acid] / mg L-1
25 BDD-PEF
20
15
10
5
0
0 60 120 180 240 300 360 420
t / min
58
Conditions: j = 33 mA cm-2, pH 3.0, 25.0 °C, 1.0 mM Fe2+

59. - Paracetamol
- Chloroxylenol
Degradation Studies
- Ibuprofen
- Diclofenac
Chloroxylenol intermediates
Oxalic acid
40
35
[oxalic acid] / mg L-1
30
25
20
Pt-EF
15 Pt-PEF
BDD-EF
10
BDD-PEF
5
0
0 60 120 180 240 300 360 420
t / min
59
Conditions: j = 33 mA cm-2, pH 3.0, 25.0 °C, 1.0 mM Fe2+

60. - Paracetamol
- Chloroxylenol
Degradation Studies
- Ibuprofen
- Diclofenac
Ions
Chloride anion, Cl-
25
20 Pt-AO
[Cl-] / mg L-1
BDD-AO
15 Pt-EF
Pt-PEF
BDD-EF
10
BDD-PEF
5
0
0 120 240 360 480
t / min
60
Conditions: j = 33 mA cm-2, pH 3.0, 25.0 °C, 1.0 mM Fe2+

61. Proposed degradation pathway for the mineralization of Chloroxylenol
OH(BDD) , OH(Pt), OH(BDD) , OH(Pt), OH(BDD) , OH(Pt),
OH OH OH
Cl-
chloroxylenol 2,6-dimethylhydroquinone 2,6-dimethyl-p-benzoquinone 3,5-dimethyl-2-hydroxy-
p-benzoquinone
OH(BDD)
OH
OH(BDD)
ketomalonic acid CO2
OH(BDD)
h
oxalic acid Fe3+ OH(BDD)
OH(BDD) , OH(Pt), OH
OH Fe3+ - oxalato
complexes
maleic acid
OH(BDD) h
Fe3+ - acetato
Fe3+
OH(BDD)
complexes
OH
61
pyruvic acid acetic acid

62. - Paracetamol
- Chloroxylenol
Degradation Studies
- Ibuprofen
- Diclofenac
Mineralization of Ibuprofen by EAOPs
62

63. - Paracetamol
- Chloroxylenol
Degradation Studies
- Ibuprofen
- Diclofenac
Electrolysis of Ibuprofen with platinum and BDD anodes.
35
Pt anode; (Pt-AO treatment
30
BDD anode; (BDD-AO treatment)
25
[TOC] / mg L-1
20
15
10
5
0
0 120 240 360 480
t / min
63
Counter electrode: stainless steel cathode,
j = 33 mA cm-2, pH 3.0, 25°C

64. - Paracetamol
- Chloroxylenol
Degradation Studies
- Ibuprofen
- Diclofenac
Electrolysis of Ibuprofen by several BDD-AO treatments
35
BDD-AO
30 BDD-AO/UVA
BDD-AO /Fe2+/UVA
25
[TOC] / mg L-1
BDD-AO at pH 6
20
15
10
5
0
0 120 240 360 480
t / min
j = 33 mA cm-2, 25.0 °C 64
pH 3.0 unless otherwise specified, 1.0 mM Fe2+ when added

65. - Paracetamol
- Chloroxylenol
Degradation Studies
- Ibuprofen
- Diclofenac
Testing of several Electro-Fenton EAOPs on Ibuprofen
35
Pt-EF
30 Pt-PEF
BDD-EF
[TOC] / mg L-1
25 BDD-PEF
Pt-SPEF
20
BDD-SPEF
15
10
5
0
0 120 240 360 480
t / min
65
Conditions: j = 33 mA cm-2, pH 3.0, 25.0 °C, 1.0 mM Fe2+

66. - Paracetamol
- Chloroxylenol
Degradation Studies
- Ibuprofen
- Diclofenac
Testing of several Electro-Fenton EAOPs on Ibuprofen
Mineralization Current Efficiency
35
Pt-EF
30
Pt-PEF
25 BDD-EF
[MCE] / %
BDD-PEF
20
Pt-SPEF
BDD-SPEF
15
10
5
0
0 120 240 360 480
Q / AhL-1
66
Conditions: j = 33 mA cm-2, pH 3.0, 25.0 °C, 1.0 mM Fe2+

67. - Paracetamol
- Chloroxylenol
Degradation Studies
- Ibuprofen
- Diclofenac
Testing of several Fe2+ catalyst concentrations on BDD-PEF
35
0.1 mM
30
0.2 mM
25
[TOC] / mg L-1
0.5 mM
1.0 mM
20
2.0 mM
15
10
5
0
0 120 240 360 480
t / min
67
Conditions: j = 33 mA cm-2, pH 3.0, 25.0 °C.

68. - Paracetamol
- Chloroxylenol
Degradation Studies
- Ibuprofen
- Diclofenac
BDD-PEF treatment on Ibuprofen
pH effect
35
pH 2
30
pH 3
25
[TOC] / mg L-1
pH 4
pH 6
20
15
10
5
0
0 120 240 360 480
t / min
68
Conditions: j = 33 mA cm-2, 25.0 °C, 1.0 mM Fe2+

69. - Paracetamol
- Chloroxylenol
Degradation Studies
- Ibuprofen
- Diclofenac
BDD-PEF treatment on Ibuprofen
current density study
35
3.3 mA cm-2
30
6.6 mA cm-2
25
[TOC] / mg L-1
13.3 mA cm-2
33.3 mA cm-2
20
100 mA cm-2
15
10
5
0
0 60 120 180 240 300 360 420
t/h
69
Conditions: 25.0 °C, pH 3.0, 1.0 mM Fe2+

70. - Paracetamol
- Chloroxylenol
Degradation Studies
- Ibuprofen
- Diclofenac
Ibuprofen abatement kinetics
under Pt and BDD anodic oxidation EAOPs
45
4 Pt-AO
40
[Ibuprofen] / mg L-1
BDD-AO
3
35
ln[C0/Ct]
30 2
25
1
20
k’ / 10-4 s-1
15 0
2.67
10 0 60 120 180 240 300 4.86
t / min
5
0
0 60 120 180 240 300
t / min
70
Conditions: j = 33 mA cm-2, 25.0 °C, pH 3.0, stainless steel cathode.

71. - Paracetamol
- Chloroxylenol
Degradation Studies
- Ibuprofen
- Diclofenac
Ibuprofen abatement kinetics
under different electro-Fenton EAOPs
Pt-EF
45
4 Pt-PEF
40 BDD-EF
[Ibuprofen] / mg L-1
3
35 BDD-PEF
ln[C0/Ct] Pt-SPEF
30 2
BDD-SPEF
25
1
20
15 0
10 0 10 20 30 k’ / 10-3 s-1
t / min
5 1.86
0 2.00
2.06
0 10 20 30 40 50
2.08
t / min
71
Conditions: j = 33 mA cm-2, 25.0 °C, pH 3.0, 1.0 mM Fe2+

72. - Paracetamol
- Chloroxylenol
Degradation Studies
- Ibuprofen
- Diclofenac
Ibuprofen abatement kinetics
at different current intensities under BDD-PEF treatment
45
4
6.6 mA cm-2
40
[Ibuprofen] / mg L-1
13.3 mA cm-2
3
35
33.3 mA cm-2
ln[C0/Ct]
30 2
25
1
20
15 0
k’ / 10-3 s-1
10 0 10 20 30 40 50
t / min 1.32
5
1.52
0
2.08
0 60 120
t / min
72
Conditions: 25.0 °C, pH 3.0, 1.0 mM Fe2+

73. GC-MS-identified Ibuprofen intermediates
2-(4-isobutylphenyl)-2-hydroxypropionic acid 4-isobutylacetophenone 4-isobutylphenol
73
2-[4-(1-hydroxyisobutyl)phenyl]propionic acid 4-ethylbenzaldehyde

74. - Paracetamol
- Chloroxylenol
Degradation Studies
- Ibuprofen
- Diclofenac
Ibuprofen intermediates
4-isobutylacetophenone
[4-isobutylacetophenone] / mg L-1
-1.5
Diclofenac
Pt-EF
Pt-PEF
BDD-EF
1
BDD-PEF
Pt-SPEF
BDD-SPEF
0.5
0
0 20 40 60 80
t / min
74
Conditions: j = 33 mA cm-2, 25.0 °C, pH 3.0, 1.0 mM Fe2+

75. - Paracetamol
- Chloroxylenol
Degradation Studies
- Ibuprofen
- Diclofenac
Ibuprofen intermediates
Oxalic acid
25
[oxalic acid] / mg L-1
20
15
Pt-EF
Pt-PEF
10
BDD-EF
- Diclofenac
BDD-PEF
5 Pt-SPEF
BDD-SPEF
0
0 60 120 180 240 300 360 420
t / min
75
Conditions: j = 33 mA cm-2, 25.0 °C, pH 3.0, 1.0 mM Fe2+