Photoactivation of oxidative degradation and mineralization of ceftriaxone with excilamp radiation

Among organic compounds resistant to biodegradation, antibiotics are of particular interest because their constantly increasing consumption has resulted in their presence in almost all components of aquatic ecosystems. With the use of advanced oxidation processes, it is possible to achieve conversion not only of target compounds but also of their reaction intermediates, which are often more toxic. Close attention is paid to the use of persulfates as precursors of reactive oxygen species, which are activated via combined methods involving ultraviolet radiation. Modern mercury-free sources include KrCl exilamps emitting quasi-monochromatic radiation. This study is the first to examine the kinetics of oxidation of a β-lactam antibiotic (ceftriaxone) and mineralization of total organic carbon by persulfate under the UVC radiation of a KrCl exilamp. Different oxidative systems were comparatively evaluated. The efficiency of target compound degradation was found to increase in the series {S₂O₈ ^2-} << {UV} < {Fe²⁺/ S₂O₈ ^2-} < {UV/ S₂O₈ ^2-} < {UV/Fe²⁺/ S₂O₈ ^2-}. The total organic carbon was mineralized only in the oxidative systems {UV/Fe²⁺/ S₂O₈ ^2-} > {UV/ S₂O₈ ^2--}. The optimal conditions for complete conversion of ceftriaxone and deep mineralization of total organic carbon (43–60%) in the {UV/Fe²⁺/ S₂O₈ ^2-} system were achieved at a molar ratio of [S₂O₈ ^2-]:[Fe²⁺] = 10. Both sulfate radical anions and hydroxyl radicals were shown to participate in ceftriaxone degradation and mineralization of total organic carbon. The obtained results indicate the viability of using the UVC radiation of a KrCl exilamp in the combined oxidative system {UV/Fe²⁺/ S₂O₈ ^2-} for effective degradation of β-lactam antibiotics.

1. Brillas E., Peralta-Hernández J.M. Antibiotic removal from synthetic and real aqueous matrices by peroxymonosulfatebased advanced oxidation processes. A review of recent development. Chemosphere. 2024;351:141153. DOI: 10.1016/j.chemosphere.2024.141153.

2. Wang X., Dai Y., Li Y., Yin L. Application of advanced oxidation processes for the removal of micro/nanoplastics from water: a review. Chemosphere. 2024;346:140636. DOI: 10.1016/j.chemosphere.2023.140636.

3. Lin W., Liu X., Ding A., Ngo H.H., Zhang R., Nanet J., et al. Advanced oxidation processes (AOPs)-based sludge conditioning for enhanced sludge dewatering and micropollutants removal: a critical review. Journal of Water Process Engineering. 2022;45:102468. DOI: 10.1016/j.jwpe.2021.102468.

4. Wang J., Wang S., Hu C. Advanced treatment of coking wastewater: recent advances and prospects. Chemosphere. 2024;349:140923. DOI: 10.1016/j.chemosphere.2023.140923.

5. Hassani A., Scaria J., Ghanbari F., Nidheesh P.V. Sulfate radicals-based advanced oxidation processes for the degradation of pharmaceuticals and personal care products: a review on relevant activation mechanisms, performance, and perspectives. Environmental Research. 2023;217:114789. DOI: 10.1016/j.envres.2022.114789.

6. Ivantsova N.A., Vetrova M.A., Churina A.A., Andriyanova D.V. Photodestruction of active pharmaceutical substances in the presence of hydrogen peroxide and peroxydisulfate. Proceedings of Universities. Applied Chemistry and Biotechnology. 2023;13(2):206-212. (In Russian). DOI: 10.21285/2227-2925-2023-13-2-206-212. EDN: NOCMUR.

7. Brillas E. A critical review on ibuprofen removal from synthetic waters, natural waters, and real wastewaters by advanced oxidation processes. Chemosphere. 2022;286:131849. DOI: 10.1016/j.chemosphere.2021.131849.

8. Li X., Jie B., Lin H., Deng Z., Qian J., Yang Y., et al. Application of sulfate radicals-based advanced oxidation technology in degradation of trace organic contaminants (TrOCs): recent advances and prospects. Journal of Environmental Management. 2022;308:114664. DOI: 10.1016/j.jenvman.2022.114664.

9. Scaria J., Nidheesh P.V. Comparison of hydroxylradical-based advanced oxidation processes with sulfate radical-based advanced oxidation processes. Current Opinion in Chemical Engineering. 2022;36:100830. DOI: 10.1016/j.coche.2022.100830.

10. Deng Y., Ezyske C.M. Sulfate radical-advanced oxidation process (SR-AOP) for simultaneous removal of refractory organic contaminants and ammonia in landfill leachate. Water Research. 2011;45(18):6189-6194. DOI: 10.1016/j.watres.2011.09.015.

11. Derbalah A., Sakugawa H. Sulfate radical-based advanced oxidation technology to remove pesticides from water a review of the most recent technologies. International Journal of Environmental Research. 2024;18:11. DOI: 10.1007/s41742-023-00561-7.

12. Honarmandrad Z., Sun X., Wang Z., Naushad M., Boczkaj G. Activated persulfate and peroxymonosulfate based advanced oxidation processes (AOPs) for antibiotics degradation – a review. Water Resources and Industry. 2023;29:100194. DOI: 10.1016/j.wri.2022.100194.

13. Brillas E. Progress of antibiotics removal from synthetic and real waters and wastewaters by persulfatebased advanced oxidation processes. Journal of Environmental Chemical Engineering. 2023;11(6):111303. DOI: 10.1016/j.jece.2023.111303.

14. Popova S.A., Matafonova G.G., Batoev V.B. Generation of radicals in ferrous-persulfate system using KrCl excilamp. ChemChemTech. 2019;62(5):118-123. (In Russian). DOI: 10.6060/ivkkt.20196205.5819. EDN: ZINYSD.

15. Tsenter I.M., Alexeev K.D., Popova S.A., GarkushevaN.M., Matafonova G.G., Batoev V.B. Efficiency of ultraviolet excilamps for simultaneous treatment and disinfection of water. ChemChemTech. 2023;66(9):116-122. (In Russian). DOI: 10.6060/ivkkt.20236609.6820. EDN: QNYRLM.

16. Popova S.A., Matafonova G.G., Batoev V.B. Dualwavelength UV degradation of bisphenol A and bezafibrate in aqueous solution using excilamps (222, 282 nm) and LED (365 nm): yes or no synergy? Journal of Environmental Science and Health, Part A. 2023;58(1):39-52. DOI: 10.1080/10934529.2023.2172270.

17. Matafonova G., Batoev V. Recent progress on application of UV excilamps for degradation of organic pollutants and microbial inactivation. Chemosphere. 2012;89(6):637-647. DOI: 10.1016/j.chemosphere.2012.06.012.

18. Welch D., Buonanno M., Grilj V., Shuryak I., Crickmore C., Bigelow A.W. et al. Far-UVC light: a new tool to control the spread of airborne-mediated microbial diseases. Scientific Reports. 2018;8:2752. DOI: 10.1038/s41598-018-21058-w.

19. Zhao J., Payne E.M., Liu B., Shang C., Blatchley E.R., Mitch W.A., et al. Making waves: opportunities and challenges of applying far-UVC radiation in controlling micropollutants in water. Water Research. 2023;241:120169. DOI: 10.1016/j.watres.2023.120169.

20. Yin R., Anderson C.E., Zhao J., Boehm A.B., Mitch W.A. Controlling contaminants using a far-UVC-based advanced oxidation process for potable reuse. Nature Water. 2023;1:555-562. DOI: 10.1038/s44221-023-00094-5.

21. Xu J., Huang C.-H. Enhanced direct photolysis of organic micropollutants by far-UVC light at 222 nm from KrCl* excilamps. Environmental Science & Technology Letters. 2023;10(6):543-548. DOI: 10.1021/acs.estlett.3c00313.

22. Payne E.M., Liu B., Mullen L., Linden K.G. UV 222 nm emission from KrCl* excimer lamps greatly improves advanced oxidation performance in water treatment. Environmental Science & Technology Letters. 2022;9(9):779-785. DOI: 10.1021/acs.estlett.2c00472.

23. Sizykh M.R., Batoeva A.A. Oxidative degradation of azo dyes in combined fenton-like oxidative systems. Zhurnal fizicheskoi khimii. 2019;93(12):1773-1779. (In Russian). DOI: 10.1134/S004445371912029X. EDN: HSSVDR.

24. Li S., Wu Y., Zheng H., Li H., Zheng Y., Nan J., et al. Antibiotics degradation by advanced oxidation process (AOPs): recent advances in ecotoxicity and antibiotic-resistance genes induction of degradation products. Chemosphere. 2023;311:136977. DOI: 10.1016/j.chemosphere.2022.136977.

25. Zhang Y., Zhao Y-G., Maqbool F., Hu Y. Removal of antibiotics pollutants in wastewater by UV-based advanced oxidation processes: influence of water matrix components, processes optimization and application: a review. Journal of Water Process Engineering. 2022;45:102496. DOI: 10.1016/j.jwpe.2021.102496.

26. Canonica S., Meunier L., von Gunten U. Phototransformation of selected pharmaceuticals during UV treatment of drinking water. Water Research. 2008;42(1-2): 121-128. DOI: 10.1016/j.watres.2007.07.026.

27. Sang W., Xu X., Zhan C., Lu W., Jia D., Wang C., et al. Recent advances of antibiotics degradation in different environment by iron-based catalysts activated persulfate: a review. Journal of Water Process Engineering. 2022;49:103075. DOI: 10.1016/j.jwpe.2022.103075.

28. Grčić I., Vujević D., Koprivanac N. Modeling the mineralization and discoloration in colored systems by (US)Fe2+/H2O2/S2O8 2− processes: a proposed degradation pathway. Chemical Engineering Journal. 2010;157:35-44. DOI: 10.1016/j.cej.2009.10.042.

29. Li Y., Shi Y., Huang D., Wu Y., Dong W. Enhanced activation of persulfate by Fe(III) and catechin without light: reaction kinetics, parameters and mechanism. Journal of Hazardous Material. 2021;413:125420. DOI: 10.1016/j.jhazmat.2021.125420.

30. Pan M., Ding J., Duan L., Gao G. Sunlight-driven photo-transformation of bisphenol A by Fe(III) in aqueous solution: Photochemical activity and mechanistic aspects. Chemosphere. 2017;167:353-359. DOI: 10.1016/j.chemosphere.2016.09.144.

31. Ioannidi A., Arvaniti O.S., Nika M.-C., Aalizadeh R., Thomaidis N.S., Mantzavinos D., et al. Removal of drug losartan in environmental aquatic matrices by heatactivated persulfate: kinetics, transformation products and synergistic effects. Chemosphere. 2022;287;131952. DOI: 10.1016/j.chemosphere.2021.131952.

32. Diao Z.H., Wei-Qian., Guo P.-R., Kong L.-J., Pu S.-Y. Photo-assisted degradation of bisphenol A by a novel FeS2@SiO2 microspheres activated persulphate process: synergistic effect, pathway and mechanism. Chemical Engineering Journal. 2018;349:683-693. DOI: 10.1016/j.cej.2018.05.132.

33. Wojnárovits L., Takács E. Rate constants of sulfate radical anion reactions with organic molecules: a review. Chemosphere. 2019;220:1014-1032. DOI: 10.1016/j.chemosphere.2018.12.156.

34. Wojnárovits L., Tóth T., Takács E. Critical evaluation of rate coefficients for hydroxyl radical reactions with antibiotics: a review. Critical Reviews in Environmental Science and Technology. 2018;48:575-613. DOI: 10.1080/10643389.2018.1463066.