Skip to main content
SpringerLink
Log in

Electron beam induced degradation of indomethacin in aqueous solution: kinetics, degradation mechanism, and toxicity assessment

  • Research Article
  • Published:
Environmental Science and Pollution Research Aims and scope Submit manuscript

Abstract

Pharmaceutical compounds were emerging contaminants, and the accumulation of pharmaceutical compounds in the environment increased the risk to humans and ecosystems. In this study, electron beam irradiation was applied to degrade indomethacin (IDM) in aqueous solution. IDM degradation followed pseudo-first-order kinetics and 300 μM IDM could be completely degraded at only 2 kGy. According to the quenching experiment, the dose constant ratios of oxidative radicals (•OH) and reductive radicals (e−aq and •H) could be calculated as k•OH: ke aq and •H=4.79:1. As the concentration of H2O2 increased from 0 to 10 mM, the dose constant increased from 1.883 to 2.582 kGy−1. However, degradation effect would be restrained in the existence of NO−3, NO−2, CO2−3, HCO−3, SO2−, and humic acid due to their competition for the active species. Theoretical calculation revealed the radical attacking sites of IDM molecule and the most probable pathways were proposed with identification of intermediates. The attack of •OH mainly resulted in the cleavage of amide bond, indole ring opening, demethoxylation, and •OH addition. Dechlorination and the reduction of the carbonyl group occurred on IDM molecular through the reduction of e−aq and •H. The intermediates could continue to be degraded to small molecule acid, such as formic acid, acetic acid, and oxalic acid. Furthermore, highly toxic IDM transformed into less toxic products during the irradiation process.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8

Similar content being viewed by others

Data availability

All date generated or analyzed during this study are included in this article and its supplementary information files.

References

  • Abdel Daiem MM, Rivera-Utrilla J, Ocampo-Pérez R, Sánchez-Polo M, López-Peñalver JJ (2013) Treatment of water contaminated with diphenolic acid by gamma radiation in the presence of different compounds. Chemical Engineering Journal 219:371–379

    Article  CAS  Google Scholar 

  • An T, Yang H, Li G, Song W, Cooper WJ, Nie X (2010) Kinetics and mechanism of advanced oxidation processes (AOPs) in degradation of ciprofloxacin in water. Applied Catalysis B: Environmental 94:288–294

    Article  CAS  Google Scholar 

  • An T, Gao Y, Li G, Kamat PV, Peller J, Joyce MV (2014) Kinetics and mechanism of •OH mediated degradation of dimethyl phthalate in aqueous solution: experimental and theoretical studies. Environmental Science & Technology 48:641–648

    Article  CAS  Google Scholar 

  • Archer E, Petrie B, Kasprzyk-Hordern B, Wolfaardt GM (2017) The fate of pharmaceuticals and personal care products (PPCPs), endocrine disrupting contaminants (EDCs), metabolites and illicit drugs in a WWTW and environmental waters. Chemosphere 174:437–446

    Article  CAS  Google Scholar 

  • Buxton GV, Greenstock CL, Helman WP, Ross AB (1988) Critical Review of rate constants for reactions of hydrated electrons, hydrogen atoms and hydroxyl radicals (·OH/·O− in Aqueous Solution). Journal of Physical and Chemical Reference Data 17:513–886

    Article  CAS  Google Scholar 

  • Changotra R, Guin JP, Khader SA, Varshney L, Dhir A (2019) Electron beam induced degradation of ofloxacin in aqueous solution: kinetics, removal mechanism and cytotoxicity assessment. Chemical Engineering Journal 356:973–984

    Article  CAS  Google Scholar 

  • Chen J, Qu R, Pan X, Wang Z (2016) Oxidative degradation of triclosan by potassium permanganate: kinetics, degradation products, reaction mechanism, and toxicity evaluation. Water Research 103:215–223

    Article  CAS  Google Scholar 

  • Chen J, Xu X, Pan X, Yao J, Li C, Qu R, Wang Z (2018) Mechanism insights into the oxidative degradation of decabromodiphenyl ethane by potassium permanganate in acidic conditions. Chemical Engineering Journal 332:267–276

    Article  CAS  Google Scholar 

  • De Vleeschouwer F, Van Speybroeck V, Waroquier M, Geerlings P, De Proft F (2007) Electrophilicity and nucleophilicity index for radicals. Organic Letters 9:2721–2724

    Article  Google Scholar 

  • Del Castillo I, Hernández P, Lafuente A, Rodríguez-Llorente ID, Caviedes MA, Pajuelo E (2012) Self-bioremediation of cork-processing wastewaters by (chloro)phenol-degrading bacteria immobilised onto residual cork particles. Water Research 46:1723–1734

    Article  Google Scholar 

  • Fukui K, Yonezawa T, Shingu H (1952) A Molecular orbital theory of reactivity in aromatic hydrocarbons. The Journal of Chemical Physics 20:722–725

    Article  CAS  Google Scholar 

  • Fukui K, Yonezawa T, Nagata C, Shingu H (1954) Molecular orbital theory of orientation in aromatic, heteroaromatic, and other conjugated molecules. The Journal of Chemical Physics 22:1433–1442

    Article  CAS  Google Scholar 

  • Huang J, Wang Y, Liu G, Chen P, Wang F, Ma J, Li F, Liu H, Lv W (2017) Oxidation of indometacin by ferrate (VI): kinetics, degradation pathways, and toxicity assessment. Environmental Science and Pollution Research 24:10786–10795

    Article  CAS  Google Scholar 

  • Jiménez JJ, Sánchez MI, Pardo R, Muñoz BE (2017) Degradation of indomethacin in river water under stress and non-stress laboratory conditions: degradation products, long-term evolution and adsorption to sediment. Journal of Environmental Sciences 51:13–20

    Article  Google Scholar 

  • Kasprzyk-Hordern B, Dinsdale RM, Guwy AJ (2008) The occurrence of pharmaceuticals, personal care products, endocrine disruptors and illicit drugs in surface water in South Wales, UK. Water Research 42:3498–3518

    Article  CAS  Google Scholar 

  • Li WC (2014) Occurrence, sources, and fate of pharmaceuticals in aquatic environment and soil. Environmental Pollution 187:193–201

    Article  CAS  Google Scholar 

  • Li M, Conrad B, Maus RG, Pitzenberger SM, Subramanian R, Fang X, Kinzer JA, Perpall HJ (2005) A novel oxidative degradation pathway of indomethacin under the stressing by hydrogen peroxide. Tetrahedron Letters 46:3533–3536

    Article  CAS  Google Scholar 

  • Li R, Kong J, Liu H, Chen P, Liu G, Li F, Lv W (2017) A sulfate radical based ferrous-peroxydisulfate oxidative system for indomethacin degradation in aqueous solutions. RSC Advances 7:22802–22809

    Article  CAS  Google Scholar 

  • Li F, Du P, Liu W, Li X, Ji H, Duan J, Zhao D (2018a) Hydrothermal synthesis of graphene grafted titania/titanate nanosheets for photocatalytic degradation of 4-chlorophenol: solar-light-driven photocatalytic activity and computational chemistry analysis. Chemical Engineering Journal 331:685–694

    Article  CAS  Google Scholar 

  • Li R, Kong J, Liu H, Chen P, Su Y, Liu G, Lv W (2018b) Removal of indomethacin using UV–vis/peroxydisulfate: kinetics, toxicity, and transformation pathways. Chemical Engineering Journal 331:809–817

    Article  CAS  Google Scholar 

  • Lian L, Yao B, Hou S, Fang J, Yan S, Song W (2017) Kinetic study of hydroxyl and sulfate radical-mediated oxidation of pharmaceuticals in wastewater effluents. Environmental Science & Technology 51:2954–2962

    Article  CAS  Google Scholar 

  • Lin T, Yu S, Chen W (2016) Occurrence, removal and risk assessment of pharmaceutical and personal care products (PPCPs) in an advanced drinking water treatment plant (ADWTP) around Taihu Lake in China. Chemosphere 152:1–9

    Article  CAS  Google Scholar 

  • Liu Y, Wang J (2013) Degradation of sulfamethazine by gamma irradiation in the presence of hydrogen peroxide. J Hazard Mater 250-251:99–105

    Article  CAS  Google Scholar 

  • Liu N, Wang T, Zheng M, Lei J, Tang L, Hu G, Xu G, Wu M (2015a) Radiation induced degradation of antiepileptic drug primidone in aqueous solution. Chemical Engineering Journal 270:66–72

    Article  CAS  Google Scholar 

  • Liu X, Zhang T, Wang L, Shao Y, Fang L (2015b) Hydrated electron-based degradation of atenolol in aqueous solution. Chemical Engineering Journal 260:740–748

    Article  CAS  Google Scholar 

  • Liu N, Lei Z-D, Wang T, Wang J-J, Zhang X-D, Xu G, Tang L (2016) Radiolysis of carbamazepine aqueous solution using electron beam irradiation combining with hydrogen peroxide: Efficiency and mechanism. Chemical Engineering Journal 295:484–493

    Article  CAS  Google Scholar 

  • Liu H, Yao J, Wang L, Wang X, Qu R, Wang Z (2019) Effective degradation of fenitrothion by zero-valent iron powder (Fe0) activated persulfate in aqueous solution: kinetic study and product identification. Chemical Engineering Journal 358:1479–1488

    Article  CAS  Google Scholar 

  • Lu T, Chen F (2012) Multiwfn: a multifunctional wavefunction analyzer. Journal of Computational Chemistry 33:580–592

    Article  Google Scholar 

  • Luo Y, Guo W, Ngo HH, Nghiem LD, Hai FI, Zhang J, Liang S, Wang XC (2014) A review on the occurrence of micropollutants in the aquatic environment and their fate and removal during wastewater treatment. Science of The Total Environment 473-474:619–641

    Article  CAS  Google Scholar 

  • Lyu G, Shi G, Tang L, Fang H, Wu M (2017) Mechanism of degradation of a nitrogenous heterocycle induced by a reductive radical: decomposition of a sym-triazine ring. Physical Chemistry Chemical Physics 19:9354–9357

    Article  CAS  Google Scholar 

  • Oláh J, Van Alsenoy C, Sannigrahi AB (2002) Condensed fukui functions derived from stockholder charges: assessment of their performance as local reactivity descriptors. The Journal of Physical Chemistry A 106:3885–3890

    Article  Google Scholar 

  • Panorel I, Preis S, Kornev I, Hatakka H, Louhi-Kultanen M (2013) Oxidation of aqueous pharmaceuticals by pulsed corona discharge. Environmental Technology 34:923–930

    Article  CAS  Google Scholar 

  • Parr RG, Yang W (1984) Density functional approach to the frontier-electron theory of chemical reactivity. Journal of the American Chemical Society 106:4049–4050

    Article  CAS  Google Scholar 

  • Rivera-Jaimes JA, Postigo C, Melgoza-Alemán RM, Aceña J, Barceló D, López de Alda M (2018) Study of pharmaceuticals in surface and wastewater from Cuernavaca, Morelos, Mexico: Occurrence and environmental risk assessment. Science of The Total Environment 613-614:1263–1274

    Article  CAS  Google Scholar 

  • Rosal R, Rodríguez A, Perdigón-Melón JA, Petre A, García-Calvo E, Gómez MJ, Agüera A, Fernández-Alba AR (2010) Occurrence of emerging pollutants in urban wastewater and their removal through biological treatment followed by ozonation. Water Research 44:578–588

    Article  CAS  Google Scholar 

  • Sánchez-Polo M, López-Peñalver J, Prados-Joya G, Ferro-García MA, Rivera-Utrilla J (2009) Gamma irradiation of pharmaceutical compounds, nitroimidazoles, as a new alternative for water treatment. Water Research 43:4028–4036

    Article  Google Scholar 

  • Scholz M, Blobaum AL, Marnett LJ, Hey-Hawkins E (2012) Ortho-carbaborane derivatives of indomethacin as cyclooxygenase (COX)-2 selective inhibitors. Bioorganic & medicinal chemistry 20:4830–4837

    Article  CAS  Google Scholar 

  • Secretariat UNECfE (2009) Globally harmonized system of classification and labelling of chemicals (GHS). United Nations Publications

    Google Scholar 

  • Shao H-Y, Wu M-h, Deng F, Xu G, Liu N, Li X, Tang L (2018) Electron beam irradiation induced degradation of antidepressant drug fluoxetine in water matrices. Chemosphere 190:184–190

    Article  CAS  Google Scholar 

  • Subedi B, Du B, Chambliss CK, Koschorreck J, Rüdel H, Quack M, Brooks BW, Usenko S (2012) Occurrence of pharmaceuticals and personal care products in german fish tissue: A National Study. Environmental Science & Technology 46:9047–9054

    Article  CAS  Google Scholar 

  • Sui Q, Huang J, Deng S, Yu G, Fan Q (2010) Occurrence and removal of pharmaceuticals, caffeine and DEET in wastewater treatment plants of Beijing, China. Water Research 44:417–426

    Article  CAS  Google Scholar 

  • Tanoue R, Nomiyama K, Nakamura H, Kim J-W, Isobe T, Shinohara R, Kunisue T, Tanabe S (2015) Uptake and tissue distribution of pharmaceuticals and personal care products in wild fish from treated-wastewater-impacted streams. Environmental Science & Technology 49:11649–11658

    Article  CAS  Google Scholar 

  • Wang J, Chu L (2016) Irradiation treatment of pharmaceutical and personal care products (PPCPs) in water and wastewater: an overview. Radiation Physics and Chemistry 125:56–64

    Article  CAS  Google Scholar 

  • Wang J, Wang S (2016) Removal of pharmaceuticals and personal care products (PPCPs) from wastewater: A review. Journal of environmental management 182:620–640

    Article  CAS  Google Scholar 

  • Wang F, Chen P, Feng Y, Xie Z, Liu Y, Su Y, Zhang Q, Wang Y, Yao K, Lv W, Liu G (2017) Facile synthesis of N-doped carbon dots/g-C3N4 photocatalyst with enhanced visible-light photocatalytic activity for the degradation of indomethacin. Applied Catalysis B: Environmental 207:103–113

    Article  CAS  Google Scholar 

  • Xie H, Hao H, Xu N, Liang X, Gao D, Xu Y, Gao Y, Tao H, Wong M (2019) Pharmaceuticals and personal care products in water, sediments, aquatic organisms, and fish feeds in the Pearl River Delta: occurrence, distribution, potential sources, and health risk assessment. Science of The Total Environment 659:230–239

    Article  CAS  Google Scholar 

  • Xu G, Yao J-z, Tang L, Yang X-y, Zheng M, Wang H, Wu M-h (2015) Electron beam induced degradation of atrazine in aqueous solution. Chemical Engineering Journal 275:374–380

    Article  CAS  Google Scholar 

  • Xu Z, Zhang X, Huang N, Hu H-y (2017) Oxidation of benzalkonium chloride by gamma irradiation: kinetics and decrease in toxicity. Journal of Radioanalytical and Nuclear Chemistry 312:631–637

    Article  CAS  Google Scholar 

  • Yang W, Mortier WJ (1986) The use of global and local molecular parameters for the analysis of the gas-phase basicity of amines. Journal of the American Chemical Society 108:5708–5711

    Article  CAS  Google Scholar 

  • Yang W, Parr RG (1985) Hardness, softness, and the fukui function in the electronic theory of metals and catalysis. Proceedings of the National Academy of Sciences 82:6723–6726

    Article  CAS  Google Scholar 

  • Yang Y, Ok YS, Kim K-H, Kwon EE, Tsang YF (2017) Occurrences and removal of pharmaceuticals and personal care products (PPCPs) in drinking water and water/sewage treatment plants: a review. Science of The Total Environment 596-597:303–320

    Article  CAS  Google Scholar 

  • Yu S, Lee B, Lee M, Cho I-H, Chang S-W (2008) Decomposition and mineralization of cefaclor by ionizing radiation: kinetics and effects of the radical scavengers. Chemosphere 71:2106–2112

    Article  CAS  Google Scholar 

  • Zhang S-J, Jiang H, Li M-J, Yu H-Q, Yin H, Li Q-R (2007) Kinetics and mechanisms of radiolytic degradation of nitrobenzene in aqueous solutions. Environmental Science & Technology 41:1977–1982

    Article  CAS  Google Scholar 

  • Zhang Q, Chen P, Zhuo M, Wang F, Su Y, Chen T, Yao K, Cai Z, Lv W, Liu G (2018) Degradation of indometacin by simulated sunlight activated CDs-loaded BiPO4 photocatalyst: roles of oxidative species. Applied Catalysis B: Environmental 221:129–139

    Article  CAS  Google Scholar 

  • Zhao Y, Kuang J, Zhang S, Li X, Wang B, Huang J, Deng S, Wang Y, Yu G (2017) Ozonation of indomethacin: kinetics, mechanisms and toxicity. Journal of Hazardous Materials 323:460–470

    Article  CAS  Google Scholar 

  • Zheng BG, Zheng Z, Zhang JB, Luo XZ, Wang JQ, Liu Q, Wang LH (2011) Degradation of the emerging contaminant ibuprofen in aqueous solution by gamma irradiation. Desalination 276:379–385

    Article  CAS  Google Scholar 

  • Zhou J, Broodbank N (2014) Sediment-water interactions of pharmaceutical residues in the river environment. Water Research 48:61–70

    Article  CAS  Google Scholar 

  • Zhou JL, Zhang ZL, Banks E, Grover D, Jiang JQ (2009) Pharmaceutical residues in wastewater treatment works effluents and their impact on receiving river water. Journal of Hazardous Materials 166:655–661

    Article  CAS  Google Scholar 

Download references

Funding

This work was financially supported by the National Natural Science Foundation of China (Nos. 11975147, 12075148, 12075146, and 41773121), National Key Research and Development Project (No. 2020YFC1808200), and Project supported by Science and Technology Commission of Shanghai Municipality (20010500300).

Author information

Author notes

  1. Yu Duan and Wei Zhou contributed equally to this work.

Authors and Affiliations

  1. School of Environmental and Chemical Engineering, Shanghai University, 99 Shangda Road, Shanghai, 200444, China

    Yu Duan, Haiyang Shao, Zhibo Zhang & Gang Xu

  2. Key Laboratory of Organic Compound Pollution Control Engineering, Ministry of Education, Shanghai, 200444, PR China

    Wenyan Shi & Gang Xu

  3. Baowu Water Technology Co., Ltd., 550 Keshan Road, Shanghai, 201999, China

    Wei Zhou

Authors
  1. Yu Duan
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Wei Zhou
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Haiyang Shao
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Zhibo Zhang
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Wenyan Shi
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Gang Xu
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

All authors contributed to the study conception and design. Yu Duan: data curation, writing-original draft preparation. Wei Zhou: investigation, writing-reviewing and editing. Haiyang Shao: conceptualization, investigation. Zhibo Zhang: investigation, validation. Wenyan Shi: methodology, investigation. Gang Xu: conceptualization, methodology. All authors read the approved the final manuscript.

Corresponding author

Correspondence to Gang Xu.

Ethics declarations

Ethics approval and consent to participate

Not applicable.

Consent for publication

Not applicable.

Competing interests

The authors declare no competing interests.

Additional information

Responsible Editor: Weiming Zhang

Publisher’s note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Supplementary information

ESM 1

(DOCX 26 kb)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Duan, Y., Zhou, W., Shao, H. et al. Electron beam induced degradation of indomethacin in aqueous solution: kinetics, degradation mechanism, and toxicity assessment. Environ Sci Pollut Res 29, 19283–19294 (2022). https://doi.org/10.1007/s11356-021-16348-2

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11356-021-16348-2

Keywords

Search

Navigation