Abstract
The degradation of paracetamol (PCT) in an aqueous medium using the Fenton and photo-Fenton reactions was investigated. The aim of this research was the development of a kinetic model based on a reaction mechanism, which includes two main intermediates of PCT degradation and the local volumetric rate of photon absorption (LVRPA). Ferrioxalate was used as a catalyst and the working pH was adjusted to 5.5 (natural pH). Experimental work was planned through a D-optimal experimental design and performed in a flat plate reactor irradiated by a solar simulator. Hydrogen peroxide (HP) concentration, reaction temperature, and radiation level were the operating parameters. The photo-Fenton reaction allowed to reach a minimum relative PCT concentration of 2.01% compared to 5.04% achieved with Fenton reaction. Moreover, the photo-Fenton system required a 50% shorter reaction time and lower HP concentration than in dark conditions (90 min and 189 mg L-1 vs. 180 min and 334 mg L-1, respectively). The experimental results were used to estimate the kinetic parameters of the proposed kinetic model employing a nonlinear, multi-parameter regression method. The values obtained from the normalized root-mean-square error (14.52, 1.96, 4.36, 13.16, and 8.72 % for PCT, benzoquinone, hydroquinone, HP, and oxalate, respectively) showed a good agreement between the predicted and experimental data.
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Data availability
The datasets generated and analyzed during the current study are available from the corresponding author on reasonable request.
Abbreviations
- A 1 :
-
Reparametrized Arrhenius pre-exponential factor
- B 1 :
-
Reparametrized Arrhenius parameter
- C :
-
Concentration (mg L-1)
- E :
-
Activation energy (kJ mol-1)
- e a :
-
Local volumetric rate of photon absorption (LVRPA) (Einstein cm-3 s-1)
- k :
-
Kinetic constant (M-1 s-1)
- L :
-
Reactor length (cm)
- q :
-
Net radiation flux (Einstein cm-2 s-1)
- R :
-
Reaction rate (M s-1)
- ℜ :
-
Ideal gas constant (kJ mol-1 K-1)
- T :
-
Temperature
- t :
-
Time (s)
- V :
-
Volume (cm3)
- x :
-
Spatial coordinate (cm)
- α :
-
molar absorptivity (m2 mol-1)
- κ :
-
Volumetric absorption coefficient (m-1)
- Φ :
-
Global quantum yield (mol Einstein-1)
- ϒ :
-
Specific consumption of the oxidizing agent (mg HP/mg PCT)
- (C2O4)2- :
-
Relative to oxalate ion
- BQ:
-
Relative to 1,4-benzoquinone
- exp:
-
Experimental value
- Fe2+(C2O4):
-
Relative to ferrous-oxalate complex
- Fe3+(C2O4)3 3- :
-
Relative to ferric-oxalate complex
- HP:
-
Relative to hydrogen peroxide
- HQ:
-
Relative to hydroquinone
- i :
-
Relative to i-th specie
- irr:
-
Relative to irradiated
- mod:
-
Model value
- PCT:
-
Relative to paracetamol
- R:
-
Relative to photoreactor
- W:
-
Reactor wall property
- λ:
-
Dependence on wavelength
- 0:
-
Initial condition
- irr:
-
Relative to irradiated
- ref:
-
Reference value
- rel:
-
Relative value
- T:
-
Thermal rate
- t:
-
Referred to a characteristic reaction time
- tot:
-
Relative to total treated volume
- 〈 〉V :
-
Volume-averaged value
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Acknowledgments
Bárbara N. Giménez particularly acknowledges Consejo Nacional de Investigaciones Científicas y Técnicas (CONICET) for the PhD scholarship.
Funding
The authors are grateful to Universidad Nacional del Litoral (UNL, CAI+D PJ 50020150100028LI, CAI+D PJ 0020150100093LI, and PICT N° 2018-1415), Consejo Nacional de Investigaciones Científicas y Técnicas (CONICET, PIP 2015-2017 GI), and Agencia Nacional de Promoción Científica y Tecnológica (ANPCyT, PICT N° 2015-2651 and PICT N° 2017-0744) for financial support.
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All persons who meet authorship criteria are listed as authors, and all authors certify that they have participated sufficiently in the work to take public responsibility for the content. BNG, AVS, OMA, and LOC contributed to the study conception and design. BNG, AVS, and LOC performed the experiments and data collection. BNG, AVS, and LOC analyzed all the data and made theoretical calculations. BNG, AVS, and LOC wrote the main manuscript text and prepared the figures and tables. AVS, OMA, and LOC obtained funding for the research. BNG, AVS, OMA, and LOC reviewed the manuscript, made amendments, and contributed with their expertise. All authors read and approved the final manuscript.
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Giménez, B.N., Schenone, A.V., Alfano, O.M. et al. Reaction kinetics formulation with explicit radiation absorption effects of the photo-Fenton degradation of paracetamol under natural pH conditions. Environ Sci Pollut Res 28, 23946–23957 (2021). https://doi.org/10.1007/s11356-020-11993-5
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DOI: https://doi.org/10.1007/s11356-020-11993-5