Subcritical water oxidation of diethyl phthalate using H2O2 and K2S2O8 as oxidizing agents: application of Box-Behnken design

Abstract

Phthalates are known for their harmful effects on human health, including being carcinogenic, toxic, and causing endocrine disruption. Therefore, removing phthalates from aquatic environments is an important issue for researchers. This study aims to compare the efficiency of hydrogen peroxide (HP) and potassium persulfate (PS) oxidants in degrading diethyl phthalate using the oxidant-assisted subcritical water oxidation method. Additionally, the study statistically examines the effect of operational parameters (temperature, oxidant concentration, and treatment time) on diethyl phthalate degradation using the Box-Behnken design. Results indicated that temperature was the primary parameter affecting diethyl phthalate degradation, with both oxidants fitting a quadratic model. The highest total organic carbon (TOC) removal rate (100%) was achieved when potassium persulfate was used as the oxidant in the oxidation experiments. When hydrogen peroxide was used as the oxidant, the maximum TOC removal efficiency was determined to be 87%.

Keywords

• Advanced Oxidation Processes
• Subcritical water oxidation
• Response Surface Methodology
• Box-Behnken Design
• Endocrine disrupting chemicals

Ethical Statement

All the data supporting this study's findings are available in this manuscript.

Thanks

I would like to thank Prof. Dr. Belgin GÖZMEN for their support. This work was supported by Mersin University Research Fund (Project No: BAP 2015-TP3-1072).

References

1. Wang Z., Shao Y., Gao N., Lu N., An N. (2018). Degradation of diethyl phthalate (DEP) by UV/persulfate: An experiment and simulation study of contributions by hydroxyl and sulfate radicals. Chemosphere, 193:602-610.
2. Bensalah, N., Dbira, S., Bedoui, A. (2019). Mechanistic and kinetic studies of the degrada-tion of diethyl phthalate (DEP) by homogeneous and heterogeneous Fenton oxidation. Environ-mental Nanotechnology, Monitoring & Management, 11:100224.
3. Li, H., Miao, X., Zhang, J., Du, J., Xu, S., Tang, J., Zhang, Y. (2020). DFT studies on the reaction mechanism and kinetics of dibutyl phthalate initiated by hydroxyl and sulfate radicals: Prediction of the most reactive sites. Chemical Engineering Journal, 381:122680.
4. Arrigo, F., Imppellitteri, F., Piccoione, G., Faggio, C. (2023). Phthalates and their effects on human health: Focus on erythrocytes and the reproductive system. Comparative Biochemistry and Physiology Part C: Toxicology & Pharmacology, 270:109645.
5. Paluselli, A., Fauvelle, V., Galgani, F., Sempere, R. (2019). Phthalate Release from Plastic Fragments and Degradation in Seawater. Environmental Science and Technology, 53:166-175.
6. Ghosh, S., Sahu, M. (2022). Phthalate pollution and remediation strategies: A review. Journal of Hazardous Materials Advances, 6:100065.
7. Mahbub, P., Duke, M. (2023). Scalability of advanced oxidation processes (AOPs) in in-dustrial applications: A review. Journal of Environmental Management, 345:118861.
8. Dong, C., Fang, W., Yi, Q., Zhang, J. (2022). A comprehensive review on reactive oxygen species (ROS) in advanced oxidation processes (AOPs). Chemosphere, 308:136205.

9. Hu, M., Chen, M., Li, Z., et al. (2024). Mechanism of catalytic subcritical water oxidation of m-nitroaniline and nitrogen conversion by CuCo2O4 catalyst. Chemical Engineering Journal, 490:151757.
10. Yabalak, E., Ozay, Y., Dizge, N. (2021). Water recovery from textile bath wastewater using combined subcritical water oxidation and nanofiltration. Journal of Cleaner Production, 290:125207.
11. Görmez, Ö., Akay, S., Gözmen, B., Kayan, B., Kalderis, D. (2022). Degradation of emerging contaminant coumarin based on anodic oxidation, electro-Fenton and subcritical water oxidation processes. Environmental Research, 208:112736.
12. Aparna, Kumar, V., Nautiyal, R. (2024). Isolation and chemical characterization of ligno-cellulosic fiber from Pueraria montana using Box-Behnken design for weed management. In-ternational Journal of Biological Macromolecules, 268:131479.
13. Sezer, M., Isgoren, M., Veli, S., Topkaya, E., Arslan, A. (2024). Removal of microplastics in food packaging industry wastewaters with electrocoagulation process: Optimization by Box-Behnken design. Chemosphere, 352:141314.
14. Yabalak, E., Görmez, Ö., Gizir, A. M. (2018). Subcritical water oxidation of propham by H2O2 using response surface methodology (RSM). Journal of Environmental Science and Health, Part B. 53(5):334–339.
15. Chaker, H., Ameur, N., Saidi-Bndahou, K., Djennas, M., Foumentin, S. (2021). Modeling and Box-Behnken design optimization of photocatalytic parameters for efficient removal of dye by lanthanum-doped mesoporous TiO2. Journal of Environmental Chemical Engineering, 9:104584.
16. Yabalak, E., Döndaş, H. A., Gizir, A.M. (2017). Subcritical water oxidation of 6-aminopenicillanic acid and cloxacillin using H2O2, K2S2O8, and O2. Journal of Environmental Science and Health, Part A, 52(3):210-220.
17. Kayan, B., Akay, S., Kulaksız, E., Gözmen, B., Kalderis, D. (2017). Acid Red 1 and Acid Red 114 decolorization in H2O2 -modified subcritical water: process optimization and application on a textile wastewater. Desalination Water Treatment, 59:248-26.
18. Görmez, Ö., Çalhan Doğan, S., Gözmen, B. (2022). Degradation of isoniazid by anodic oxidation and subcritical water oxidation methods: Application of Box-Behnken design. Journal of Environmental Science and Health, Part C, 40(1):1-26.
19. Li, N., Wu, S., Dai, H., Cheng, Z., Peng, W., Yan, B., Chen, G., Wang, S., Duan, X. (2022). Thermal activation of persulfates for organic wastewater purification: Heating modes, mechanism and influencing factors. Chemical Engineering Journal, 450:137976.
20. Ji, Y., Fan, Y., Liu, K., Kong, D., Lu, J. (2015). Thermo activated persulfate oxidation of antibiotic sulfamethoxazole and structurally related compounds. Water Research, 87:1-9.
21. Luo, R., Wang, C., Yao, Y., Qi, J., Li, J. (2022). Insights into the relationship of reactive oxygen species and anions in persulfate-based advanced oxidation processes for saline organic wastewater treatment. Environmental Science: Water Research and Technology, 8:465-483.