Degradation, boosted with Fe 2+  ions, of ethylene glycol in oxygen-saturated aqueous solutions using the H 2 O 2 /UV-C oxidation system: a kinetic study

Timur Fazliev; Mikhail Lyulyukin; Dmitry Yakhvarov; Oleg Sinyashin; Vadim Yakovlev; Denis Kozlov; Dmitry Selishchev

doi:10.15826/chimtech.9192

Degradation, boosted with Fe²⁺ ions, of ethylene glycol in oxygen-saturated aqueous solutions using the H₂O₂/UV-C oxidation system: a kinetic study

Timur Fazliev, Mikhail Lyulyukin, Dmitry Yakhvarov, Oleg Sinyashin, Vadim Yakovlev, Denis Kozlov, Dmitry Selishchev

Abstract

Ethylene glycol (EG) is commonly found as the main organic contaminant in airport runoff water during the cold season due to its use in the composition of de-icing fluids. Despite relatively low acute and chronic toxicity, EG may lead to a rapid growth of undesirable microbial biofilms in water bodies, thus reducing the concentration of dissolved oxygen and suppressing biodiversity. EG degradation using hydrogen peroxide activated with UV‑C light (H₂O₂/UV‑C) is a promising method of solving this problem because H₂O₂ serves as a cheap and green oxidant and provides complete EG mineralization in aqueous solutions. This paper describes the results of the in-depth study on the effect of adding Fe²⁺ ions and saturating the reaction solution with oxygen on EG degradation in the H₂O₂/UV system, showing the synergistic effect of both these factors on boosting the rate of EG removal and the depth of its mineralization. Comprehensive analysis of EG degradation and individual oxidation of key EG intermediates using TOC and HPLC methods revealed the roles of Fe²⁺ ions and dissolved oxygen in the synergistic effect and allowed us to clarify the main pathways of EG degradation in this system.

Keywords

ethylene glycol (EG); wastewater treatment; advanced oxidation processes (AOPs); photodegradation; H2O2/UV-C; photo-Fenton

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References

Joint ACI World-ICAO Passenger Traffic Report, Trends, and Outlook. ACI World [Internet] 2025[cited 2025]. English. Available from: https://aci.aero/2025/01/28/joint-aci-world-icao-passenger-traffic-report-trends-and-outlook/, Accessed on 17 June 2025.

Lai C-H, Chuang K-Y, Chang J-W. Source Apportionment of Volatile Organic Compounds at an International Airport. Aerosol Air Qual Res. 2013;13:689–698. doi:10.4209/aaqr.2012.05.0121

Nunes LM, Zhu Y-G, Stigter TY, Monteiro JP, Teixeira, MR. Environmental Impacts on Soil and Groundwater at Airports: Origin, Contaminants of Concern and Environmental Risks. J Environ Monit. 2011;13:3026–3039. doi:10.1039/C1EM10458F

Sulej AM, Polkowska Ż, Namieśnik J. Analysis of Airport Runoff Waters. Critical Reviews in Analytical Chemistry 2011;41:190–213. doi:10.1080/10408347.2011.588920

Sulej-Suchomska AM, Szumińska D, de la Guardia M, Przybyłowski P, Polkowska Ż. Airport Runoff Water: State-of-the-Art and Future Perspectives. Sustainability. 2024;16:8176. doi:10.3390/su16188176

Masiol M, Harrison RM. Aircraft Engine Exhaust Emissions and Other Airport-Related Contributions to Ambient Air Pollution: A Review. Atmospheric Environment. 2014;95:409–55. doi:10.1016/j.atmosenv.2014.05.070

Dyer KP. Anti-icing fluid residues. SAE Trans. [Internet] 2007[cited 2025];116:618–625. English. Available from https://www.jstor.org/stable/44719495, Accessed on 29 July 2025.

Gray DR. Environmental impact of aircraft deicing. Designing, Constructing, Maintaining, and Financing Today’s Airport Projects. 2012:1–10. doi:10.1061/40646(2003)25

LaFond-Hudson S, Corsi SR, Rutter TD. Apportionment of oxygen demand contributions from aircraft and pavement deicer freezing point depressants in airport runoff, Milwaukee, Wisconsin, 2005–2022. Integr Environ Assess Manag. 2025;21:594–603. doi:10.1093/inteam/vjae047

Zhang W, Zhang J, Chen S. Frost resistance of roller compacted concrete in airport runway subjected to ethylene glycol solution. Anti-Corros Method Mater. 2018;66:40–44. doi:10.1108/ACMM-03-2018-1916

LaKind JS, McKenna EA, Hubner RP, Tardiff RG. A review of the comparative mammalian toxicity of ethylene glycol and propylene glycol. Crit Rev Toxicol. 1999;29:331–65. doi:10.1080/10408449991349230

Cornell JS, Pillard DA, Hernandez MT. Comparative measures of the toxicity of component chemicals in aircraft deicing fluid. Environ Toxicol Chem. 2000;19:1465–72. doi:10.1002/etc.5620190601

Gruden CL, Hernandez M. Anaerobic digestion of aircraft deicing fluid wastes: Interactions and toxicity of corrosion inhibitors and surfactants. Water Environ Res. 2002;74:149–58. doi:10.2175/106143002X139866

Pillard DA, Cornell JS, DuFresne, DL, Hernandez MT. Toxicity of benzotriazole and benzotriazole derivatives to three aquatic species. Water Res. 2001;35:557–60. doi:10.1016/S0043-1354(00)00268-2

Hartwell SI, Jordahl DM, Evans JE, May EB. Toxicity of aircraft de‐icer and anti‐icer solutions to aquatic organisms. Environ Toxicol Chem. 1995;14:1375–86. doi:10.1002/etc.5620140813

Nott MA, Driscoll HE, Takeda M, Vangala M, Corsi SR, Tighe SW. Advanced biofilm analysis in streams receiving organic deicer runoff. PLoS ONE. 2020;15:e0227567. doi:10.1371/journal.pone.0227567

Exton B, Hassard F, Medina-Vaya A, Grabowski RC. Undesirable river biofilms: The composition, environmental drivers, and occurrence of sewage fungus. Ecol Indic. 2024;161:111949. doi:10.1016/j.ecolind.2024.111949

Corsi SR, Geis SW, Loyo-Rosales JE, Rice CP, Sheesley RJ, Failey GG, et al. Characterization of aircraft deicer and anti-icer components and toxicity in airport snowbanks and snowmelt runoff. Environ Sci Technol. 2006;40:3195–202. doi:10.1021/es052028m

Barash S, Covington J, Tamulonis C. Preliminary data summary airport deicing operations (revised). Washington: United States Environmental Protection Agency; 2000. 447 p.

Johnson EP. Aircraft de-icer: Recycling can cut carbon emissions in half. Environ Impact Assess Rev. 2012;32:156–64. doi:10.1016/j.eiar.2011.08.001

Bausmith DS, Neufeld RD. Soil biodegradation of propylene glycol based aircraft deicing fluids. Water Environ Res. 1999;71(4):459–64. doi:10.2175/106143097X121997

Lucas R, Earl ER, Babatunde AO, Bockelmann-Evans BN. Constructed wetlands for stormwater management in the UK: A concise review. Civ Eng Environ Syst. 2015;32:251–68. doi:10.1080/10286608.2014.958472

Schoenberg T, Veltman S, Switzenbaum M. Kinetics of anaerobic degradation of glycol-based Type I aircraft deicing fluids. Biodegradation. 2001;12:59–67. doi:10.1023/A:1011961214180

Adeola S, Revitt M, Shutes B, Garelick H, Jones H, Jones C. Constructed wetland control of BOD levels in airport runoff. Int J Phytoremed. 2009;1:1–10. doi:10.1080/15226510802363220

Aguinaco A, Pocostales JP, García-Araya JF, Beltrán FJ. Decomposition of hydrogen peroxide in the presence of activated carbons with different characteristics. J Chem Technol Biotechnol. 2011;86(4):595–600. doi:10.1002/jctb.2560

Khalil LB, Girgis BS, Tawfik TAM. Decomposition of H2O2 on activated carbon obtained from olive stones. J Chem Technol Biotechnol. 2001;76(11):1132–40. doi:10.1002/jctb.481

Armstrong DA, Huie RE, Koppenol WH, Lymar SV, Merényi G, Neta P, et al. Standard electrode potentials involving radicals in aqueous solution: Inorganic radicals (IUPAC Technical Report). Pure Appl Chem. 2015;87:1139–50. doi:10.1515/pac-2014-0502

Kulišťáková A. Removal of pharmaceutical micropollutants from real wastewater matrices by means of photochemical advanced oxidation processes – A review. J Water Process Eng. 2023;53:103727. doi:10.1016/j.jwpe.2023.103727

Liu P, Wu Z, Abramova AV, Cravotto G. Sonochemical processes for the degradation of antibiotics in aqueous solutions: A review. Ultrason Sonochem. 2021;74:105566. doi:10.1016/j.ultsonch.2021.105566

Wang Y, Liu M, Miao Q, Wu P, He J, Liu C, et al. Rapid green degradation of ethylene glycol-based antifreeze wastewater via a coupled photolytic and photocatalytic double-pathway mechanism. J Water Process Eng. 2025;71:107191. doi:10.1016/j.jwpe.2025.107191

Yuan Q, Qu S, Li R, Huo ZY, Gao Y, Luo Y. Degradation of antibiotics by electrochemical advanced oxidation processes (EAOPs): Performance, mechanisms, and perspectives. Sci Total Environ. 2023;856:159092. doi:10.1016/j.scitotenv.2022.159092

Shokri A, Fard MS. A critical review in Fenton-like approach for the removal of pollutants in the aqueous environment. Environ Chall. 2022;7:100534. doi:10.1016/j.envc.2022.100534

Fazliev T, Lyulyukin M, Kozlov D, Selishchev D. Kinetic aspects of ethylene glycol degradation using UV-C activated hydrogen peroxide (H2O2/UV-C). Molecules. 2025;30:49. doi:10.3390/molecules30010049

Liu Z, Hosseinzadeh S, Wardenier N, Verheust Y, Chys M, Hulle SV. Combining ozone with UV and H2O2 for the degradation of micropollutants from different origins: Lab-scale analysis and optimization. Environ Technol. 2019;40:3773–82. doi:10.1080/09593330.2018.1491630

Ghaly MY, Härtel G, Mayer R, Haseneder R. Photochemical oxidation of p-chlorophenol by UV/H2O2 and photo-Fenton process. A comparative study. Waste Manag. 2001;21:41–7. doi:10.1016/S0956-053X(00)00070-2

McGinnis DB, Adams DV, Middlebrooks JE. Degradation of Ethylene Glycol Using Fenton’s Reagent and UV. Chemosphere 2001, 45, 101–108. doi:10.1016/S0045-6535(00)00597-X.

Priyadarshini M, Ahmad A, Das I, Ghangrekar MM, Dutta BK. Efficacious degradation of ethylene glycol by ultraviolet activated persulphate: Reaction kinetics, transformation mechanisms, energy demand, and toxicity assessment. Environ Sci Pollut Res. 2023;30:85071–86. doi:10.1007/s11356-023-27596-9

Wang J, Wang S. Effect of inorganic anions on the performance of advanced oxidation processes for degradation of organic contaminants. Chem Eng J. 2021;411:128392. doi:10.1016/j.cej.2020.128392

Machado F, Teixeira ACSC, Ruotolo LAM. Critical review of Fenton and photo-Fenton wastewater treatment processes over the last two decades. Int J Environ Sci Technol. 2023;20:13995–4032. doi:10.1007/s13762-023-05015-3

Lee C, Seo J, Pham AL-T. The Photo-Fenton System. In Springer Handbook of Inorganic Photochemistry; Bahnemann, D., Patrocinio, A.O.T., Eds.; Springer International Publishing: Cham, 2022. pp. 1719–1734

Tokumura M, Morito R, Hatayama R, Kawase Y. Iron redox cycling in hydroxyl radical generation during the photo-Fenton oxidative degradation: Dynamic change of hydroxyl radical concentration. Appl Catal B Environ. 2011;106:565–76. doi:10.1016/j.apcatb.2011.06.017

Carra I, García Sánchez JL, Casas López JL, Malato S, Sánchez Pérez JA. Phenomenological study and application of the combined influence of iron concentration and irradiance on the photo-Fenton process to remove micropollutants. Sci Total Environ. 2014;478:123–32. doi:10.1016/j.scitotenv.2014.01.066

Hermosilla D, Cortijo M, Huang CP. Optimizing the treatment of landfill leachate by conventional Fenton and photo-Fenton processes. Sci Total Environ. 2009;407:3473–81. doi:10.1016/j.scitotenv.2009.02.009

Khatri N, Tyagi S, Rawtani D. Recent strategies for the removal of iron from water: A review. J Water Process Eng. 2017;19:291–304. doi:10.1016/j.jwpe.2017.08.015

Fakhfekh R, Chabanon E, Mangin D, Amar RB, Charcosset C. Removal of iron using an oxidation and ceramic microfiltration hybrid process for drinking water treatment. Desalin Water Treat. 2017;66:210–20. doi:10.5004/dwt.2017.20225

Modin H, Persson KM, Andersson A, van Praagh M. Removal of metals from landfill leachate by sorption to activated carbon, bone meal and iron fines. J Hazard Mater. 2011;189:749–54. doi:10.1016/j.jhazmat.2011.03.001

Chaturvedi S, Dave PN. Removal of iron for safe drinking water. Desalination. 2012;303:1–11. doi:10.1016/j.desal.2012.07.003

Sui X, Zhou Y, Zhang F, Chen J, Zhu Z, Yu XY. Deciphering the aqueous chemistry of glyoxal oxidation with hydrogen peroxide using molecular imaging. Phys Chem Chem Phys. 2017;19:20357–66. doi:10.1039/C7CP02071F

Sui X, Xu B, Yu J, Kostko O, Ahmed M, Yu XY. Studying interfacial dark reactions of glyoxal and hydrogen peroxide using vacuum ultraviolet single photon ionization mass spectrometry. Atmosphere. 2021;12:338. doi:10.3390/atmos12030338

Eugene AJ, Xia SS, Guzman MI. Aqueous photochemistry of glyoxylic acid. J Phys Chem A. 2016;120:3817–26. doi:10.1021/acs.jpca.6b00225

Zhang F, Yu X, Chen J, Zhu Z, Yu XY. Dark air–liquid interfacial chemistry of glyoxal and hydrogen peroxide. Clim Atmos Sci. 2019;2:28. doi:10.1038/s41612-019-0085-5

Santoss L, Lima Poli A, Schmitt Cavalheiro C, Neumann M. The UV/H2O2 - photodegradation of poly(ethyleneglycol) and model compounds. J Braz Chem Soc. 2009;20(8):14647–72. doi:10.1590/S0103-50532009000800012

Fazliev TR, Bukhtiyarov AV, Selishchev DS. Photocatalytic formation of hydrogen peroxide in aqueous suspensions of titanium dioxide supported with palladium. Kinet Catal. 2024;65:672–81. doi:10.1134/S0023158424602432

Payne JH, Lemon GF Jr. The oxidation of aldehydes with hydrogen peroxide. J Am Chem Soc. 1941;63:226–8. doi:10.1021/ja01846a053

Magneron I, Mellouki A, Le Bras G, Moortgat GK, Horowitz A, Wirtz K. Photolysis and OH-initiated oxidation of glycolaldehyde under atmospheric conditions. J Phys Chem A. 2005;109:4552–61. doi:10.1021/jp044346y

Zuo Y, Hoigne J. Photochemical decomposition of oxalic, glyoxalic and pyruvic acid catalysed by iron in atmospheric waters. Atmos Environ. 1994;28:1231–9. doi:10.1016/1352-2310(94)90270-4

Santambrogio M, Perrucci G, Trueba M, Trasatti SP, Casaletto MP. Effect of major degradation products of ethylene glycol aqueous solutions on steel corrosion. Electrochim Acta. 2016;203:439–50. doi:10.1016/j.electacta.2016.03.144

Jeong J, Yoon J. pH effect on OH radical production in photo/ferrioxalate system. Water Res. 2005;39:2893–900. doi:10.1016/j.watres.2005.05.014

Aristova NA, Karpel Vel Leitner N, Piskarev IM. Degradation of formic acid in different oxidative processes. High Energy Chem. 2002;36:197–202. doi:10.1023/A:1015385103605

Vel Leitner NK, Dore M. Hydroxyl radical induced decomposition of aliphatic acids in oxygenated and deoxygenated aqueous solutions. J Photochem Photobiol A. 1996;99:137–43. doi:10.1016/S1010-6030(96)04360-2

Ahile UJ, Wuana RA, Itodo AU, Sha’Ato R, Dantas RF. Stability of iron chelates during photo-Fenton process: The role of pH, hydroxyl radical attack and temperature. J Water Process Eng. 2020;36:101320. doi:10.1016/j.jwpe.2020.101320

Vallés I, Santos-Juanes L, Amat AM, Moreno-Andrés J, Arques A. Effect of salinity on UVA-Vis light driven photo-Fenton process at acidic and circumneutral pH. Water. 2021;13:1315. doi:10.3390/w13091315

Rozas O, Contreras D, Mondaca MA, Pérez-Moya M, Mansilla HD. Experimental design of Fenton and photo-Fenton reactions for the treatment of ampicillin solutions. J Hazard Mater. 2010;177:1025–30. doi:10.1016/j.jhazmat.2010.01.023

Duesterberg CK, Mylon SE, Waite TD. pH effects on iron-catalyzed oxidation using Fenton’s reagent. Environ Sci Technol. 2008;42:8522–7. doi:10.1021/es801720d

Puzyn T, Mostrag A. Organic Pollutants Ten Years After the Stockholm Convention: Environmental and Analytical Update. InTech: Rijeka; 2012. 472 p.

Laurence GS, Thornton AT. Kinetics of oxidation of transition-metal ions by halogen radical anions. Part III. The oxidation of manganese(II) by dibromide and dichloride ions generated by flash photolysis. J Chem Soc Dalton Trans. 1973:1637–44. doi:10.1039/DT9730001637

DOI: https://doi.org/10.15826/chimtech.9192

Copyright (c) 2025 Timur Fazliev, Mikhail Lyulyukin, Dmitry Yakhvarov, Oleg Sinyashin, Vadim Yakovlev, Denis Kozlov, Dmitry Selishchev

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