Skip to main content
SpringerLink
Log in

A pilot lab trial for enhanced oxidative transformation of procymidone fungicide and its aniline metabolite using heterogeneous MnO2 catalysts

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

Abstract

In this study, the feasibility of two heterogeneous catalysis (non-Fenton heterogeneous catalysis and catalytic ozonation) was evaluated for the oxidative transformation of the fungicide procymidone and its major metabolite (3,5-dichloroaniline; 3,5-DCA) under a pilot lab experiment. Among the studied treatments, only H2O2 or O3 significantly oxidized procymidone and 3,5-DCA. However, heterogeneous catalysis used with various types of MnO2 catalysts was found to be an effective rapid strategy for transformation of procymidone and its aniline metabolite. Among the studied catalysts, δ-MnO2 performed well in the enhanced oxidative transformation of procymidone and 3,5-DCA in MnO2-mediator system assay. The optimal reaction parameters, such as reaction pH, and initial catalyst concentration were comparatively evaluated. However, heterogeneous catalysis and catalytic ozonation were revealed as the rapid strategy for oxidative transformation of investigated procymidone and 3,5-DCA as compared to single oxidation by peroxide/ozone. Finally, as a novel insight of this investigation, a postulated reaction mechanism underlying the accelerated transformation of aniline metabolites via heterogeneous catalysis was explored. The findings of this study will open new avenues for evaluating heterogeneous catalysis during oxidative transformation of non-phenolic pollutants in both lab trial and field applications. This study can be expanded for use in actual field settings, using environmental samples from contaminated areas exposed to non-phenolic pesticides and their metabolites.

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

Similar content being viewed by others

Data availability

The datasets used and/or analyzed during the current study are available from the corresponding author on reasonable request.

Abbreviations

MMS:

MnO2-mediator system

δ-MMS:

δ-MnO2-mediator system

HPLC-UVD:

High-performance liquid chromatography-ultra-violet detector

SPE:

Solid-phase extraction (using for sample clean up in chromatography)

ROS:

Reactive oxygen species

MOF:

Metal-organic framework

References

  • Bavykina A, Kolobov N, Khan IS et al (2020) Metal-organic frameworks in heterogeneous catalysis: recent progress, new trends, and future perspectives. Chem Rev 120:8468–8535. https://doi.org/10.1021/acs.chemrev.9b00685

    Article  CAS  Google Scholar 

  • Bi X, Huang Y, Liu X et al (2021) Oxidative degradation of aqueous organic contaminants over shape-tunable MnO2 nanomaterials via peroxymonosulfate activation. Sep Purif Technol 275:119141. https://doi.org/10.1016/j.seppur.2021.119141

    Article  CAS  Google Scholar 

  • Choi SW, Park SY (2007) Removal of procymidone by ozonated water. J Environ Sci Int 16(12):1425–1430

  • Cui X, Li W, Ryabchuk P et al (2018) Bridging homogeneous and heterogeneous catalysis by heterogeneous single-metal-site catalysts. Nat Catal 1:385–397

    Article  CAS  Google Scholar 

  • Fang C, Gujarati H, Osinaga F et al (2021) Optimization of the catalytic activity of manganese dioxide (MnO2) nanoparticles for degradation of environmental pollutants. Res Chem Intermed 47:3673–3690. https://doi.org/10.1007/s11164-021-04494-8

    Article  CAS  Google Scholar 

  • Gao Z, Zhang D, Jun YS (2021) Does tert-butyl alcohol really terminate the oxidative activity of •OH in inorganic redox chemistry? Environ Sci Technol 55:10442–10450

    Article  CAS  Google Scholar 

  • Guo Y, Zhang Y, Yu G, Wang Y (2021) Revisiting the role of reactive oxygen species for pollutant abatement during catalytic ozonation: the probe approach versus the scavenger approach. Appl Catal B Environ 280:119418

    Article  CAS  Google Scholar 

  • Huang J, Zhang H (2020) Redox reactions of iron and manganese oxides in complex systems. Front Environ Sci Eng 14. https://doi.org/10.1007/s11783-020-1255-8

  • Huang J, Zhong S, Dai Y et al (2018) Effect of MnO2 phase structure on the oxidative reactivity toward bisphenol A degradation. Environ Sci Technol 52:11309–11318

    Article  CAS  Google Scholar 

  • Hulea V, Dumitriu E, Fajula F (2021) Mild oxidation of organosulfur compounds with H2O2 over metal-containing microporous and mesoporous catalysts. Catalysts 11:1–25

    Article  Google Scholar 

  • Ingle AA, Ansari SZ, Shende DZ et al (2022) Progress and prospective of heterogeneous catalysts for H2O2 production via anthraquinone process. Environ Sci Pollut Res. https://doi.org/10.1007/s11356-022-21354-z

    Article  Google Scholar 

  • Issaka E, AMU-Darko JNO, Yakubu S, et al (2022) Advanced catalytic ozonation for degradation of pharmaceutical pollutants―a review. Chemosphere 289:133208

  • Jeong E-J, Cha Y-J (2012) Reduction in residual pesticides and quercetin yields in onion peel extracts by washing. J Life Sci 22:1665–1671

    Article  Google Scholar 

  • Ji J, Lu X, Chen C et al (2020) Potassium-modulated δ-MnO2 as robust catalysts for formaldehyde oxidation at room temperature. Appl Catal B Environ 260:118210

    Article  CAS  Google Scholar 

  • Khan I, Sadiq M, Khan I, Saeed K (2019) Manganese dioxide nanoparticles/activated carbon composite as efficient UV and visible-light photocatalyst. Environ Sci Pollut Res 26:5140–5154. https://doi.org/10.1007/s11356-018-4055-y

  • Khan MSI, Lee NR, Ahn J et al (2021) Degradation of different pesticides in water by microplasma: the roles of individual radicals and degradation pathways. Environ Sci Pollut Res 28:8296–8309. https://doi.org/10.1007/s11356-020-11127-x

    Article  CAS  Google Scholar 

  • Kim DH, Bokare AD, Koo MS, Choi W (2015) Heterogeneous catalytic oxidation of as(III) on nonferrous metal oxides in the presence of H2O2. Environ Sci Technol 49:3506–3513

    Article  CAS  Google Scholar 

  • Li B, Xu X, Zhu L et al (2010) Catalytic ozonation of industrial wastewater containing chloro and nitro aromatics using modified diatomaceous porous filling. Desalination 254:90–98

    Article  CAS  Google Scholar 

  • Li M, Sun M, Dong H et al (2020) Enhancement of micropollutant degradation in UV/H2O2 process via iron-containing coagulants. Water Res 172:115497

    Article  CAS  Google Scholar 

  • Liu B, Ji J, Zhang B et al (2022) Catalytic ozonation of VOCs at low temperature: a comprehensive review. J Hazard Mater 422:126847

    Article  CAS  Google Scholar 

  • Lozowicka B, Jankowska M, Hrynko I, Kaczynski P (2016) Removal of 16 pesticide residues from strawberries by washing with tap and ozone water, ultrasonic cleaning and boiling. Environ Monit Assess 188:1–19. https://doi.org/10.1007/s10661-015-4850-6

    Article  CAS  Google Scholar 

  • Ming B, Li J, Kang F et al (2012) Microwave-hydrothermal synthesis of birnessite-type MnO2 nanospheres as supercapacitor electrode materials. J Power Sources 198:428–431

    Article  CAS  Google Scholar 

  • Nawaz F, Xie Y, Cao H et al (2015) Catalytic ozonation of 4-nitrophenol over an mesoporous α-MnO2 with resistance to leaching. Catal Today 258:595–601

    Article  CAS  Google Scholar 

  • Pandiselvam R, Kaavya R, Jayanath Y et al (2020) Ozone as a novel emerging technology for the dissipation of pesticide residues in foods–a review. Trends Food Sci Technol 97:38–54. https://doi.org/10.1016/j.tifs.2019.12.017

    Article  CAS  Google Scholar 

  • Perveen R, Nasar A, Inamuddin A et al (2018) Optimization of MnO2-graphene/polythioaniline (MnO2-G/PTA) hybrid nanocomposite for the application of biofuel cell bioanode. Int J Hydrogen Energy 43:15144–15154. https://doi.org/10.1016/j.ijhydene.2018.06.070

    Article  CAS  Google Scholar 

  • Pierri L, Gemenetzi A, Mavrogiorgou A et al (2020) Biochar as supporting material for heterogeneous Mn(II) catalysts: Efficient olefins epoxidation with H2O2. Mol Catal 489:110946. https://doi.org/10.1016/j.mcat.2020.110946

    Article  CAS  Google Scholar 

  • Salla JS, Padoin N, Amorim SM et al (2020) Humic acids adsorption and decomposition on Mn2O3 and α-Al2O3 nanoparticles in aqueous suspensions in the presence of ozone. J Environ Chem Eng 8:102780. https://doi.org/10.1016/j.jece.2018.11.025

    Article  CAS  Google Scholar 

  • Sarker A, Islam T, Bilal M, Kim JE (2022) A pilot study for enhanced transformation of a metabolite 3,5-dichloroaniline derived from dicarboximide fungicides through immobilized laccase mediator system. Environ Sci Pollut Res. https://doi.org/10.1007/s11356-022-19645-6

    Article  Google Scholar 

  • Sarker A, Lee SH, Kwak SY et al (2020) Comparative catalytic degradation of a metabolite 3,5-dichloroaniline derived from dicarboximide fungicide by laccase and MnO2 mediators. Ecotoxicol Environ Saf 196:110561. https://doi.org/10.1016/j.ecoenv.2020.110561

    Article  CAS  Google Scholar 

  • Thomas N, Dionysiou DD, Pillai SC (2021) Heterogeneous Fenton catalysts: a review of recent advances. J Hazard Mater 404:124082

    Article  CAS  Google Scholar 

  • Wang J, Bai Z (2017) Fe-based catalysts for heterogeneous catalytic ozonation of emerging contaminants in water and wastewater. Chem Eng J 312:79–98

    Article  CAS  Google Scholar 

  • Wang J, Chen H (2020) Catalytic ozonation for water and wastewater treatment: recent advances and perspective. Sci Total Environ 704:135249

    Article  CAS  Google Scholar 

  • Wang L, Cheng H (2015) Birnessite (γ-MnO2) mediated degradation of organoarsenic feed additive p-arsanilic acid. Environ Sci Technol 49:3473–3481

    Article  CAS  Google Scholar 

  • Wang Z, Bao J, Du J, et al (2022) Sulfamethoxazole degradation by alpha-MnO2/periodate oxidative system: role of MnO2 crystalline and reactive oxygen species. Environ Sci Pollut Res 44732–44745. https://doi.org/10.1007/s11356-022-18901-z

  • Wang Z, Jia H, Liu Z et al (2021) Greatly enhanced oxidative activity of δ-MnO2 to degrade organic pollutants driven by dominantly exposed −111 facets. J Hazard Mater 413:125285. https://doi.org/10.1016/j.jhazmat.2021.125285

    Article  CAS  Google Scholar 

  • Xie C, Yan D, Li H et al (2020) Defect chemistry in heterogeneous catalysis: recognition, understanding, and utilization. ACS Catal 10:11082–11098

    Article  CAS  Google Scholar 

  • Yang W, Su Z, Xu Z, et al (2020) Comparative study of α-, β-, γ- and δ-MnO2 on toluene oxidation: oxygen vacancies and reaction intermediates. Appl Catal B Environ 260. https://doi.org/10.1016/j.apcatb.2019.118150

  • Yu X, Kamali M, Van Aken P et al (2021) Synergistic effects of the combined use of ozone and sodium percarbonate for the oxidative degradation of dichlorvos. J Water Process Eng 39:101721. https://doi.org/10.1016/j.jwpe.2020.101721

    Article  Google Scholar 

  • Zhang Z, Xiang L, Lin F et al (2021) Catalytic deep degradation of Cl-VOCs with the assistance of ozone at low temperature over MnO2 catalysts. Chem Eng J 426:130814

    Article  CAS  Google Scholar 

  • Zhou ZG, Du HM, Dai Z et al (2019) Degradation of organic pollutants by peroxymonosulfate activated by MnO2 with different crystalline structures: catalytic performances and mechanisms. Chem Eng J 374:170–180

    Article  CAS  Google Scholar 

Download references

Acknowledgements

The authors are grateful to Kyungpook National University, Daegu, Republic of Korea, for proofreading, plagiarism checking, and other technical supports throughout the writing period of the paper

Funding

This research work was supported by the 2021 research fund of Kyungpook National University, Daegu, Republic of Korea.

Author information

Authors and Affiliations

  1. School of Applied Biosciences, Kyungpook National University, Daegu, 41566, Republic of Korea

    Aniruddha Sarker & Jang-Eok Kim

  2. Institute of Biotechnology and Genetic Engineering, Bangabandhu Sheikh Mujibur Rahman Agricultural University, Gazipur, 1706, Bangladesh

    Tofazzal Islam

Authors
  1. Aniruddha Sarker
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Tofazzal Islam
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Jang-Eok Kim
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

All authors contributed to the study conception and design. Material preparation, data collection, and analysis were performed by Aniruddha Sarker, Tofazzal Islam, and Jang-Eok Kim. The first draft of the manuscript was written by Aniruddha Sarker, and all authors commented on previous versions of the manuscript. All authors read and approved the final manuscript.

Corresponding author

Correspondence to Jang-Eok Kim.

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: George Z. Kyzas

Publisher's note

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

Supplementary Information

Below is the link to the electronic supplementary material.

Supplementary file1 (DOCX 1764 KB)

Rights and permissions

Springer Nature or its licensor holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Sarker, A., Islam, T. & Kim, JE. A pilot lab trial for enhanced oxidative transformation of procymidone fungicide and its aniline metabolite using heterogeneous MnO2 catalysts. Environ Sci Pollut Res 30, 3783–3794 (2023). https://doi.org/10.1007/s11356-022-22520-z

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11356-022-22520-z

Keywords

Search

Navigation