Thesis defence

KINETIC STUDY OF THE

DEGRADATION OF SULFAMETHOXAZOLE BY UV LIGHT
COMBINED WITH H2O2 AND PHOTO-FENTON TREATMENT

21 June 2022

Student: Jankelevitch Sebastien

Promotors: Prof. Dr. Ir. Natalia Villota

Prof. Dr. Ir. Leen Thomassen
Prof. Dr. Josémaria Lomas
1
CONTENTS

01 Context 02 Problem definition and objectives

Pharmaceuticals in the environment Sulfamethoxazole (SMX)

03 Materials and methods 04 Results and discussion

UV/H2O2 and photo-Fenton oxidation Effect of pH, [H2O2] and [Fe2+] on SMX degradation

05 Conclusion

2
1 Context
Pharmaceuticals in the environment: contaminants of emerging concern (CEC)

3
What are contaminants of emerging concern (CECs)?

Negative effect on aquatic

Compound that is increasingly detected
environment or human health

4
Examples of contaminants of emerging concern

5
Figure 1: Number of pharmaceutical substances detected in surface waters, groundwater, or
tap/drinking water (der Beek et al., 2015, p.829).
6
Environmental quality standards directive (EQSD)

7
2 Problem definition and objectives
Sulfamethoxazole under scrutiny

8
Sulfamethoxazole (SMX)
Problems

Increasing concentration Environmental effect

• ng/l or mg/l in surface water [2], • Bacterial imbalance in aquatic
[3] ecosystems [5]
• Increased use [4] • SMX resistant bacteria
• …?

Objectives
• Increase general understanding
of SMX degradation

• Effect of different
parameters on
degradation pathway

• Effect of different
parameters on
degradation kinetics

9
3 Materials and methods
Photocatalytic degradation of sulfamethoxazole (UV/H 2O2 and photo-Fenton)

10
Reaction setup Initiation:
Photocatalytic reactor 𝐻 2 𝑂 2 + 𝑈𝑉 𝑙𝑖𝑔h𝑡 + ¿

𝑃𝑟𝑜𝑑𝑢𝑐𝑡𝑖𝑜𝑛
Propagation:
𝑂𝐻
Figure 2: pH meter Figure 3: Dissolved Figure 4: Cooling system Figure 5: 150 W UV
oxygen meter mercury lamp
Termination:

oxidizes contaminants

Temperature
controller

Take sample every 5 minutes

• Turbidity [NTU]
• Absorbance 455 nm (Color) [AU]
• Absorbance 254 nm (Aromaticity) [AU]
DO- pH- • HPLC separation and absorbance at 260 nm
meter meter ([SMX]) [AU]
Figure 6: Photocatalytic reactor • Ionic chromatography
11
Reaction setup Initiation:
Photocatalytic reactor 𝐻 2 𝑂 2 + 𝑈𝑉 𝑙𝑖𝑔h𝑡 + ¿

𝑃𝑟𝑜𝑑𝑢𝑐𝑡𝑖𝑜𝑛
Propagation:
𝑂𝐻
Figure 2: pH meter Figure 3: Dissolved Figure 4: Cooling system Figure 5: 150 W UV
oxygen meter mercury lamp
Termination:

oxidizes contaminants

Temperature
controller

Take sample every 5 minutes

• Turbidity [NTU]
• Absorbance 455 nm (Color) [AU]
• Absorbance 254 nm (Aromaticity) [AU]
DO- pH- • HPLC separation and absorbance at 260 nm
meter meter ([SMX]) [AU]
Figure 6: Photocatalytic reactor • Ionic chromatography
12
Performed reactions
Varied parameters
Table 1: Performed sulfamethoxazole degradation reactions

Reaction C0 sulfamethoxazole C0 H2O2 C0 Fe2+

pH
number [mg/l] [mM] [mg/l]

1 2.0
2 3.0
3 4.0
100.0 0.0
4 6.0
5 9.0
6 12.0
7 100.0
50.0
8 50.0
2.0
9 25.0
 
10 10.0 3.0
11 5.0  

12 0.5
10.0
13 1.0
 
14 5.0

13
Performed reactions
Varied parameters
Table 1: Performed sulfamethoxazole degradation reactions

Reaction C0 sulfamethoxazole C0 H2O2 C0 Fe2+

pH
number [mg/l] [mM] [mg/l]

1 2.0
2 3.0
3 4.0
4
100.0
6.0
0.0 UV/H2O2
5 9.0 pH vary
6 12.0
7 100.0
50.0
8 50.0
2.0
9 25.0
 
10 10.0 3.0
11 5.0  

12 0.5
10.0
13 1.0
 
14 5.0

14
 Performed reactions
Varied parameters
Table 1: Performed sulfamethoxazole degradation reactions

Reaction C0 sulfamethoxazole C0 H2O2 C0 Fe2+

pH
number [mg/l] [mM] [mg/l]

1 2.0
2 3.0
3 4.0
100.0 0.0
4 6.0
5 9.0
photo-Fenton 6 12.0
7 100.0
50.0
8 50.0
2.0
9 25.0
 
10 10.0 3.0
11 5.0  

12 0.5
10.0
13 1.0
 
14 5.0

15
 Performed reactions
Varied parameters
Table 1: Performed sulfamethoxazole degradation reactions

Reaction C0 sulfamethoxazole C0 H2O2 C0 Fe2+

pH
number [mg/l] [mM] [mg/l]

1 2.0
2 3.0
3 4.0
100.0 0.0
4 6.0
5 9.0
photo-Fenton 6 12.0
7 100.0
50.0
8 50.0
9 25.0
2.0
  [H2O2] vary
10 10.0 3.0
11 5.0  

12 0.5
10.0
[Fe2+] vary 13
 
1.0
14 5.0

16
4
Results and discussion

17
UV/H2O2
Effect of pH on steady-state

One of the methodologies

Figure 7: Color and turbidity measurements at steady state in function of pH Figure 8: Aromaticity and sulfamethoxazole at steady-state in function of pH
18
UV/H2O2
Effect of pH on steady-state

Figure 9: SMX ionization percentage in function of pH Figure 7: Color and turbidity measurements at steady state in function of pH

19
 UV/H2O2
Effect of pH on steady-state

Figure 10: Oxalate and acetate at steady state in function of pH Figure 11: Sulphate and nitrate at steady state in function of pH Figure 7: Color and turbidity measurements at steady state in function of pH

OH
HO
S O
+ S O
-
O + H + SO3
+ O

(SO3 + H2O H2SO4)

Figure 10: Proposed desulfonation of sulfamethoxazole intermediates in acid conditions

20
 UV/H2O2
Kinetic modelling of SMX degradation

Mechanistic model
(1) [SMX]0: Initial measurement of SMX in aqueous solutions(AU)
  kSMX: pseudo-first-order rate constant for degradation of SMX in water (min -1)
(2)
One of the methodologies ; (r2=0.900)

Figure 11: Measured absorbance at 260 nm at various pH and proposed pseudo first- Figure 12: Kinetic constants of pseudo first-order SMX model in function of pH
order kinetic model of SMX degradation. Experimental conditions: [SMX]0=50.0 mg L-1;
[H2O2]0=100.0 mM; [UV]=150W; T=25ºC. 21
 Empirical model
UV/H2O2 (3)
Kinetic modelling of SMX degradation

Mechanistic model (4)

(1)
[SMX]0: Initial measurement of SMX in aqueous solutions(AU)
 
[SMX]∞: SMX in the oxidized samples in the steady state (AU)
(2) kSMX: pseudo-first-order rate constant for degradation of SMX in water (min -1)
One of the methodologies

Figure 11: Measured absorbance at 260 nm at various pH and proposed pseudo first- Figure 13: Measured absorbance at 260 nm at various pH and proposed empirical model of SMX degradation.
order kinetic model of SMX degradation. Experimental conditions: [SMX]0=50.0 mg L-1; Experimental conditions: [SMX]0=50.0 mg L-1; [H2O2]0=100.0 mM; [UV]=150W; T=25ºC.
[H2O2]0=100.0 mM; [UV]=150W; T=25ºC.

; (r2=0.900) ; (r2=0.965) 22
 UV/H2O2
Kinetic modelling of other parameters

1.0 5.0
pH=2.0 pH=3.0 pH=4.0 pH=2.0 pH=3.0 pH=4.0 pH=6.0
0.9 4.5
pH=9.0 pH=12.0 pH=5.0
pH=6.0 pH=9.0 pH=12.0
4.0

[Colour] / [Colour] 0
0.8
[A 254] / [A 254]0

3.5
0.7 3.0

0.6 2.5

2.0
0.5
1.5
0.4
1.0
0 10 20 30 40 50 60 70 80 90 100 110 120
0 20 40 60 80 100 120
Time (min) Time (min)
Figure 14: Empirical model predictions for aromaticity-loss during SMX Figure 15: Empirical model predictions for colour formation during the Figure 7: Colour and turbidity measurements at steady state in
oxidation by UV/H2O2. oxidation of SMX. function of pH

; (r2=0.969) k colo u r =0.001 pH 2 − 0.021 pH +0.114 ; ( r 2 =0.953)

Except pH=4.0:

23
 Photo-Fenton
Kinetic modelling of SMX degradation: effect of Fe2+

Mechanistic model Empirical model

(5) (7)
(6)
(8)
One of the methodologies

Figure 16: SMX degradation during the reaction for reactions with varying [Fe 2+] Figure 17: Empirical model predictions for SMX degradation by photo-Fenton
and second order model reaction with varying [Fe2+]

; (r2=0.976) ; (r2=0.976)
24
 Photo-Fenton
Kinetic modelling of SMX degradation: effect of H2O2

Mechanistic model
(5)
(6)

One of the methodologies

Figure 18: SMX degradation with varying [H2O2] and fitted second-order model Figure 19: Kinetic constant of SMX degradation in function of [H2O2]
 Photo-Fenton Empirical model
Kinetic modelling of color change

Measurements without model Assuming first order for the aromaticity loss this time:

(13)

With,

kC,f : pseudo-first-order rate constant for color formation (min -1)

kC,d : pseudo-first-order rate constant for color degradation (min -1)

kC,a : first-order rate constant for aromaticity degradation (min -1)

Figure 20: Colour formation and degradation for the reactions with varying [Fe 2+] : correlation coefficient between aromaticity absorbance and color

absorbance

26
 Photo-Fenton Empirical model
Kinetic modelling of color change: Effect of
Fe2+

Assuming first order for the aromaticity loss this time:

(13)

With,

kC,f : pseudo-first-order rate constant for color formation (min -1)

kC,d : pseudo-first-order rate constant for color degradation (min -1)

Figure 21: Empirical model predictions for colour changes during the oxidation of SMX by photo-Fenton
kC,a : first-order rate constant for aromaticity degradation (min -1)

; (r2=0.9956) : correlation coefficient between aromaticity absorbance and color

; (r2=0.9918) absorbance

(r2=0.9996) 27
Photo-Fenton
Kinetic modelling of color change: Effect of H2O2

Figure 20: Colour formation and degradation for the reactions with varying [Fe2+]
Figure 22: Colour formation and degradation for the reactions with varying [H2O2]

28
Photo-Fenton
Kinetic modelling of turbidity change

Figure 23: Turbidity formation and degradation for the reactions with varying [Fe2+]
Figure 24:Turbidity formation and degradation for the reactions with varying [Fe2+]

29
5 Conclusion

30
 Percent of ionic form

pH
31
Photo-Fenton
Conclusion

Effect of Fe2+ Effect of H2O2 Intermediates Further research

Linear correlation No effect on kinetics until P-Benzoquinone Identify colour- and

between second order below a certain threshold. could be the cause turbidity forming
kinetic constant and for the brown intermediates with
Fe2+ concentration. Increasing the total H2O2 colour formation HPLC.
makes for a more
Formation and complete degradation. Apply method to other
subsequent degradation Second formation of CECs.
of color and turbidity. turbidity at [H2O2]>25
mM
Muconic acid could be
the cause for the
turbidity formation

32
 Sources
• der Beek, T. A., Weber, F.-A., Bergmann, A., Hickmann, S., Ebert, I., Hein, A., & Küsterz, A. (2015).
PHARMACEUTICALS IN THE ENVIRONMENT-GLOBAL OCCURRENCES AND PERSPECTIVES.
Environmental Toxicology and Chemistry, 35(4), 823–835. https://doi.org/10.1002/etc.3339
• Gao, J., Huang, J., Chen, W., Wang, B., Wang, Y., Deng, S., & Yu, G. (2016). Fate and removal of typical
pharmaceutical and personal care products in a wastewater treatment plant from Beijing: a mass balance
study. Frontiers of Environmental Science & Engineering 2016 10:3, 10(3), 491–501.
https://doi.org/10.1007/S11783-016-0837-Y
• Pera-Titus, M., García-Molina, V., Baños, M. A., Giménez, J., & Esplugas, S. (2004). Degradation of
chlorophenols by means of advanced oxidation processes: A general review. Applied Catalysis B:
Environmental, 47(4), 219–256. https://doi.org/10.1016/j.apcatb.2003.09.010
• Trovó, A. G., Nogueira, R. F. P., Agüera, A., Fernandez-Alba, A. R., Sirtori, C., & Malato, S. (2009).
Degradation of sulfamethoxazole in water by solar photo-Fenton. Chemical and toxicological evaluation.
Water Research, 43(16), 3922–3931. https://doi.org/10.1016/J.WATRES.2009.04.006

33
 Thank you for your attention.
Special thanks for my promotors for their guidance

Questions?

Student: Jankelevitch Sebastien

Promotors: Prof. Dr. Ir. Natalia Villota

Prof. Dr. Ir. Leen Thomassen
Prof. Dr. Josémaria Lomas

34
Industrial
applicability

• AOPs? Alternatives?
• Effect of microbiology
• Treatment setup
• Effluent specifications

Capodaglio, A. G. (2020). Critical perspective on advanced treatment processes for water and
wastewater: AOPs, ARPs, and AORPs. Applied Sciences (Switzerland), 10(13).
https://doi.org/10.3390/APP10134549

35
 Photo-Fenton
Kinetic modelling of aromaticity degradation: effect of Fe2+

Mechanistic model Empirical model

(9)  (11)
(10)  
(12)
One of the methodologies

; (r2=0.968) ; (r2=0.915)
36
 Photo-Fenton
Kinetic modelling of aromaticity degradation: effect of H2O2

Mechanistic model
(9) 
(10)

One of the methodologies

37
Ionic chromatography

38
 Repeatability (Fe 0.5 mg/L) 2+

Colour NTU
0.3 35

0.25 30

25
0.2
20
0.15
15
0.1
10

0.05 5

0 0
0 20 40 60 80 100 120 0 20 40 60 80 100 120

Arom SMX
2.5 3

2 2.5

2
1.5
1.5
1
1

0.5
0.5

0 0
0 20 40 60 80 100 120 0 20 40 60 80 100 120 39
 Repeatability (Fe 2.0 mg/L) 2+

Color NTU
12 10
9
10
8
7
8
6
6 5
4
4
3
2
2
1
0 0
0 20 40 60 80 100 120 0 20 40 60 80 100 120

Arom SMX
2.5 3

2.5
2

2
1.5
1.5
1
1

0.5
0.5

0 0
0 20 40 60 80 100 120 0 20 40 60 80 100 120 40
UV Spectra

8.8M H2O2

41