Skip to main content
SpringerLink
Log in

Theoretical studies on the mechanism, kinetics, and degradation pathways of auxin mimic herbicides by •OH radical in aqueous media

  • Original Research
  • Published:
Structural Chemistry Aims and scope Submit manuscript

Abstract

The kinetics and mechanism in the oxidative degradation pathways of the •OH radical reaction with seven auxin mimic aromatic acid-based herbicides were investigated with the help of various theoretical methods. Various global and local reactivity parameters such as ionization energy, molecular hardness, electrophilicity, condensed Fukui function, and total energies were determined to predict the reactivity of these herbicides towards the •OH radical. Geometry optimization was performed at the CAM–B3LYP/6–311 + G(d) level of theory including the solvent effect using the polarizable continuum model (PCM) incorporating the integral equation formalism (IEF) with water as solvent. Single point energies of various species were calculated at ROMP2/aug–cc–pVDZ level of theory for better accuracy. The pKa values for these acid-based herbicides allow them to exist in the deprotonated form in aqueous condition. Hence, the calculations are also performed for the deprotonated form apart from the neutral species. The most reactive site for the •OH radical reaction is predicted and validated for neutral and deprotonated species. Once the most reactive site is known, the reaction rate constants are calculated theoretically by the traditional transition–state theory using one-dimensional tunneling corrections. The solvent effect on the reaction rate constant is implemented through Collins–Kimball formulations.

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

Availability of data and materials

The various parameters of the molecular structure of the current study are available and can be obtained from the corresponding author on reasonable request.

References

  1. Milne GWA (1995) CRC Handbook of Pesticides CRC Press, Taylor & Francis Group, Boca Raton, Florida, USA

  2. Tu M, Hurd C, Randall JM (2001) Weed control methods handbook: tools & techniques for use in natural areas. The Nature Conservancy, All U.S. Government Documents (Utah Regional Depository). Paper 533

  3. Gupta PK (2018) Toxicity of herbicides. In: Gupta RC (ed) Veterinary Toxicol. Elsevier Inc

  4. Cobb A (1992:82–106) Auxin-type herbicides. Herbicides and Plant Physiol. Chapman Hall

  5. Grossmann K (2007) Auxin herbicide action: lifting the veil step by step. Plant Signaling Behav 2:421–423

    Article  Google Scholar 

  6. Todd OE, Figueiredo MRA, Morran S, Soni N, Preston C, Kubeš MF, Napier R, Gaines TA (2020) Synthetic auxin herbicides: finding the lock and key to weed resistance. Plant Sci 300

  7. Tilman D, Cassman KG, Matson PA, Naylor R, Polasky S (2002) Agricultural sustainability and intensive production practices. Nature 418:671

    Article  CAS  PubMed  Google Scholar 

  8. Verma P, Verma P, Sagar R (2013) Variations in N mineralization and herbaceous species diversity due to sites, seasons, and N treatments in a seasonally dry tropical environment of India. For Ecol Manage 297:15–26

    Article  Google Scholar 

  9. Xie H, Wang X, Chen J, Li X, Jia G, Zou Y, Zhang Y, Cui Y (2019) Occurrence, distribution and ecological risks of antibiotics and pesticides in coastal waters around Liaodong Peninsula. China Sci Total Environ 656:946–951

    Article  CAS  PubMed  Google Scholar 

  10. Donald DB, Cessna AJ, Sverko E, Glozier NE (2007) Pesticides in surface drinking-water supplies of the northern Great Plains. Environ Health Perspect 15:1183–1191

    Article  Google Scholar 

  11. Rice PJ, Rice PJ, Arthur EL, Barefoot AC (2007) Advances in pesticide environmental fate and exposure assessments. J Agric Food Chem 55:5367–5376

    Article  CAS  PubMed  Google Scholar 

  12. Verma JP, Jaiswal DK, Sagar R (2014) Pesticide relevance and their microbial degradation: a-state-of-art. Rev Environ Sci Biotechnol 13:429–466

    Article  Google Scholar 

  13. Tomco PL, Duddleston KN, Schultz EJ, Hagedorn B, Stevenson TJ, Seefeldt SS (2016) Field degradation of aminopyralid and clopyralid and microbial community response to application in Alaskan soils. Environ Toxicol Chem 35:485–493

    Article  CAS  PubMed  Google Scholar 

  14. De Lucas A, Rodriguez L, Villasenor J, Fernandez FJ (2007) Influence of industrial discharges on the performance and population of a biological nutrient removal process. Biochem Eng J 34:51–61

    Article  Google Scholar 

  15. Fairchild JF, Feltz KP, Sappington LC, Allert AL, Nelson KJ, Valle J (2009) An ecological risk assessment of the acute and chronic toxicity of the herbicide picloram to the threatened bull trout (Salvelinus confluentus) and the rainbow trout (Onchorhyncus mykiss). Arch Environ Contam Toxicol 56:761–769

    Article  CAS  PubMed  Google Scholar 

  16. Garcia-Becerra FY, Ortiz I (2018) Biodegradation of emerging organic micropollutants in nonconventional biological wastewater treatment: a critical review. Environ Eng Sci 35:1012–1036

    Article  CAS  Google Scholar 

  17. Gaur N, Narasimhulu K, PydiSetty Y (2018) Recent advances in the bioremediation of persistent organic pollutants and its effect on environment. J Clean Prod 198:1602–1631

    Article  CAS  Google Scholar 

  18. Kumar S, Kaushik G, Dar MA, Nimesh S, Lopez-Chuken UJ, Villarreal-Chiu JF (2018) Microbial degradation of organophosphate pesticides: a review. Pedosphere 28:190–208

    Article  CAS  Google Scholar 

  19. Ghanbari F, Moradi M (2017) Application of peroxymonosulfate and its activation methods for degradation of environmental organic pollutants: review. Chem Eng J 310:41–62

    Article  CAS  Google Scholar 

  20. Solis RR, Rivas FJ, Gimeno O, Perez-Bote JL (2016) Photocatalytic ozonation of clopyralid, picloram and triclopyr. Kinetics, toxicity and influence of operational parameters. J Chem Technol Biotechnol 91:51–58

    Article  CAS  Google Scholar 

  21. Šojić DV, Anderluh VB, Orčić DZ, Abramović BF (2009) Photodegradation of clopyralid in TiO2 suspensions: identification of intermediates and reaction pathways. J Hazard Mater 168:94–101

    Article  PubMed  Google Scholar 

  22. Rahman MA, Muneer M (2005) Heterogeneous photocatalytic degradation of picloram, dicamba, and floumeturon in aqueous suspensions of titanium dioxide. J Environ Sci Health Part B Pestic Contam Agric Wastes 40:247–267

    Article  Google Scholar 

  23. Pinna MV, Pusino A (2012) Direct and indirect photolysis of two quinolinecarboxylic herbicides in aqueous systems. Chemosphere 86:655–658

    Article  CAS  PubMed  Google Scholar 

  24. Pareja L, Perez-Parada A, Aguera A, Cesio V, Heinzen H, Fernandez-Alba AR (2012) Photolytic and photocatalytic degradation of quinclorac inultrapure and paddy field water: identification of transformation products. Chemosphere 87:834–844

    Article  Google Scholar 

  25. Djebbar K, Zertal A, Sehili T (2006) Photocatalytic degradation of 2,4- dichlorophenoxyacetic acid and 4- chloro-2-methylphenoxyacetic acid in water by using TiO2. Environ Technol 27:1191–1197

    Article  CAS  PubMed  Google Scholar 

  26. Huang C, Dong C, Tang Z (1993) Advanced chemical oxidation: its present role and potential future in hazardous waste treatment. Waste Manag 13:361–377

    Article  CAS  Google Scholar 

  27. Semitsoglou-Tsiapou S, Templeton MR, Graham NJD, Leal LH, Martijn BJ, Royce A, Kruithof JC (2016) Low pressure UV/H2O2 treatment for the degradation of the pesticides metaldehyde, clopyralid and mecoprop-Kinetics and reaction product formation. Water Res 91:285–294

    Article  CAS  PubMed  Google Scholar 

  28. Sangami S, Manu B (2017) Optimization of Fenton’s oxidation of herbicide dicamba in water using response surface methodology. Appl Water Sci 7:4269–4280

    Article  CAS  Google Scholar 

  29. Glaze WH (1987) Drinking-water treatment with ozone. Environ Sci Technol 21:224–230

    Article  CAS  PubMed  Google Scholar 

  30. Ahmad R, James TK, Rahman A, Holland PT (2003) Dissipation of the herbicide clopyralid in an allophanic soil: laboratory and field studies. J Environ Sci Health Part B Pestic Contam Agric Wastes 683–695

  31. Elliott JA, Cessna AJ, Best KB, Nicholaichuk W, Tollefson LC (1998) Leaching and preferential flow of clopyralid under irrigation: field observations and simulation modeling. J Environ Qual 27:124–131

    Article  CAS  Google Scholar 

  32. Tang L, Zeng GM, Shen GL, Li YP, Zhang Y, Huang DL (2008) Rapid detection of picloram in agricultural field samples using a disposable immunomembrane-based electrochemical sensor. Environ Sci Technol 42:1207–1212

    Article  CAS  PubMed  Google Scholar 

  33. Song X (2014) Dicamba. In: Wexler P (ed) Encyclopedia of toxicology (Third Edition). Elsevier Inc

  34. Sanches-Neto FO, Ramos B, Lastre-Acosta AM, Teixeira ACSC, Carvalho-Silva VH (2021) Aqueous picloram degradation by hydroxyl radicals: unveiling mechanism, kinetics, and ecotoxicity through experimental and theoretical approaches. Chemosphere 278:130401

    Article  CAS  PubMed  Google Scholar 

  35. Ozcan A, Sahin Y, Koparal AS, Oturan MA (2008) Degradation of picloram by the electro-Fenton process. J Hazard Mater 153:718–727

    Article  PubMed  Google Scholar 

  36. Coledam DAC, Sanchez-Montes I, Silva BF, Aquino JM (2018) On the performance of HOCl/Fe2+, HOCl/Fe2+/UVA, and HOCl/UVC processes using in situ electrogenerated active chlorine to mineralize the herbicide picloram. Appl Catal B-Environ 227:170–177

    Article  CAS  Google Scholar 

  37. Ghauch A (2001) Degradation of benomyl, picloram, and dicamba in a conical apparatus by zero-valent iron powder. Chemosphere 43:1109–1117

    Article  CAS  PubMed  Google Scholar 

  38. Contreras MBC, Fourcade F, Assadi A, Amrane A, Fernandez-Morales FJ (2019) Electro Fenton removal of clopyralid in soil washing effluents. Chemosphere 237:124447

    Article  Google Scholar 

  39. Wu M-H, Yang X-Y, Xu G, Liu N, Guo R-Y, Lei J-Q, Tang L (2015) UV-based oxidation processes for removal of clopyralid: optimal conditions, efficiency, and by-products. Environ Eng Sci 32:998–1006

    Article  CAS  Google Scholar 

  40. Tizaoui C, Mezughi K, Bickley R (2011) Heterogeneous photocatalytic removal of the herbicide clopyralid and its comparison with UV/H2O2 and ozone oxidation techniques. Desalination 273:197–204

    Article  CAS  Google Scholar 

  41. Xu G, Liu N, Wu M, Bu T, Zheng M (2013) The photodegradation of clopyralid in aqueous solutions: effects of light sources and water constituents. Ind Eng Chem Res 52

  42. Yang X, Cao X, Zhang L, Wu Y, Zhou L, Xiu G, Ferronato C, Chovelon J-M (2021) Sulfate radical-based oxidation of the aminopyralid and picloram herbicides: the role of amino group on pyridine ring. J Hazard Mater 405:124181

    Article  CAS  PubMed  Google Scholar 

  43. Yang X, Ding X, Zhou L, Fan H-h, Wang X, Ferronato C, Chovelon J-M, Xiu G (2020) New insights into clopyralid degradation by sulfate radical: pyridine ring cleavage pathways. Water Res 171:115378

    Article  CAS  PubMed  Google Scholar 

  44. Zhu J, Ding G, Liu Y, Wang B, Zhang W, Guo M, Geng Q, Cao Y (2015) Ionic liquid forms of clopyralid with increased efficacy against weeds and reduced leaching from soils. Chem Eng J 279:472–477

    Article  CAS  Google Scholar 

  45. Thiam A, Sirés I, Salazar R, Brillas E (2018) On the performance of electrocatalytic anodes for photoelectro-Fenton treatment of synthetic solutions and real water spiked with the herbicide chloramben. J Environ Manage 224:340–349

    Article  CAS  PubMed  Google Scholar 

  46. Guin M, Nayak AN, Gowda NMM (2016) Theoretical study of hydrogen bonded picolinic acid-water complexes. Indian J Chem 55:782–792

    Google Scholar 

  47. Domingo LR, Pérez P, Sáez JA (2013) Understanding the local reactivity in polar organic reactions through electrophilic and nucleophilic Parr functions. RSC Adv 3:1486–1494

    Article  CAS  Google Scholar 

  48. Yanai T, Tew DP, Handy NC (2004) A new hybrid exchange−correlation functional using the coulomb-attenuating method (CAM-B3LYP). Chem Phys Lett 393:51–57

    Article  CAS  Google Scholar 

  49. Parr RG, Yang W (1982) Density functional theory for atoms and molecules. Oxford University Press, New York

    Google Scholar 

  50. Pearson RG (1997) Chemical hardness. John Wiley-VCH, Weinheim

    Book  Google Scholar 

  51. Pearson RG (2005) Chemical hardness and density functional theory. J Chem Sci 117:369–377

    Article  CAS  Google Scholar 

  52. Chandrakumar KRS, Pal S (2002) The concept of density functional theory based descriptors and its relation with the reactivity of molecular systems: a semi-quantitative study. Int J Mol Sci 3:324–337

    Article  CAS  Google Scholar 

  53. Sánchez-Márquez J (2019) Correlations between Fukui indices and reactivity descriptors based on Sanderson’s principle. J Phys Chem A 123:8571–8582

    Article  PubMed  Google Scholar 

  54. Schmidt MW, Baldridge KK, Boatz JA, Elbert ST, Gordon MS, Jensen JH, Koseki S, Matsunaga N, Nguyen KA, Su S et al (1993) General atomic and molecular electronic structure system. J Comput Chem 14:1347−1363

  55. Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR, Scalmani G, Barone V, Mennucci B, Petersson GA et al (2010) Gaussian 09, revision B.01. In: Gaussian, Inc., Wallingford, CT

  56. Carvalho-Silva VH, Aquilanti V, de Oliveira HCB, Mundim KC (2017) Deformed transition-state theory: deviation from Arrhenius behavior and application to bimolecular hydrogen transfer reaction rates in the tunneling regime. J Comput Chem 38:178–188

    Article  CAS  PubMed  Google Scholar 

  57. Collins FC, Kimball GE (1949) Diffusion-controlled reaction rates. J Colloid Sci 4:425–437

    Article  CAS  Google Scholar 

  58. Machado HG, Sanches-Neto FO, Coutinho ND, Mundim KC, Palazzetti F, Carvalho-Silva VH (2019) “Transitivity”: a code for computing kinetic and related parameters in chemical transformations and transport phenomena. Molecules 24:3478

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  59. Dzib E, Cabellos JL, Ortíz-Chi F, Pan S, Galano A, Merino G (2019) Eyringpy: a program for computing rate constants in the gas phase and in solution. Int J Quantum Chem 119:e25686

    Article  Google Scholar 

  60. McKinney JD, Richard A, Waller C, Newman MC, Gerberick F (2000) The practice of structure activity relationships (SAR) in toxicology. Toxicol Sci 56:8–17

    Article  CAS  PubMed  Google Scholar 

  61. Mayo-Bean K, Moran-Bruce K, Meylan W, Ranslow P, Lock M, Nabholz JV, Runnen JV, Cassidy LM, Tunkel J (2017) Estimating toxicity of industrial chemicals to aquatic organisms using the ECOSAR (ECOlogical Structure-Activity Relationship) class program Version 2.0. U.S. Environ Protection Agency

Download references

Acknowledgements

The author thanks Prof. G. Naresh Patwari for some of the calculations performed at IITBombay, Mumbai.

Funding

The work was supported by DAE under Project “26–XII–CR& D–117.03/Advanced Research on Laser–Induced Chemical Reactions.”

Author information

Authors and Affiliations

  1. Radiation & Photochemistry Division, Bhabha Atomic Research Centre, HBNI, Trombay, Mumbai, 400 085, India

    Hari P. Upadhyaya

Authors
  1. Hari P. Upadhyaya
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

As a single-author manuscript, starting from the conceptualization to theoretical calculation, writing, presentation, and figures, everything was handled by the author. For the remaining, it has been duly acknowledged.

Corresponding author

Correspondence to Hari P. Upadhyaya.

Ethics declarations

Conflict of interest

The author declares no competing interests.

Additional information

Publisher's Note

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

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

Upadhyaya, H.P. Theoretical studies on the mechanism, kinetics, and degradation pathways of auxin mimic herbicides by •OH radical in aqueous media. Struct Chem 34, 931–943 (2023). https://doi.org/10.1007/s11224-022-02055-2

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11224-022-02055-2

Keywords

Search

Navigation