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Mechanism and kinetics of diuron oxidation by hydroxyl radical addition reaction

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Abstract

Diuron is a phenyl urea herbicide used to control weeds in agricultural lands. The degradation of diuron in the atmosphere takes place dominantly via reaction with OH radicals. In this work, the OH addition reaction of diuron has been studied by using density functional theory methods M06-2X, ωB97X-D and MPWB1K with 6-31G(d,p) basis set. The calculated thermochemical parameters show that OH addition reaction occurs favourably at C2 position of diuron. The rate constant is calculated for the favourable initial reaction pathway by using canonical variational transition state theory with small curvature tunnelling (SCT) correction over the temperature range of 200–1000 K. The reaction of initially formed diuron-OH adduct intermediate with O2 leads to the formation of peroxy radical intermediate. The reaction of peroxy radical intermediate with HO2 and NOx (x = 1, 2) radicals is studied in detail. The results obtained from time-dependent density functional theory (TDDFT) calculations show that the intermediates and products formed from oxidation of diuron can be easily photolyzed in the sunlight. This study provides thermodynamical and kinetic data for the atmospheric oxidation of diuron by OH radical addition reaction and demonstrates the atmospheric chemistry of diuron and its derivatives.

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Funding

The authors received funding from UGC and the Department of Science and Technology (DST), India, to establish high-performance computing facility under the SAP and PURSE programs.

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Authors and Affiliations

  1. Department of Physics, Bharathiar University, Coimbatore, Tamil Nadu, 641046, India

    Gunasekaran Manonmani & Kittusamy Senthilkumar

  2. National Institute of Science, Technology, and Development Studies, CSIR, New Delhi, 110012, India

    Lakshmanan Sandhiya

Authors
  1. Gunasekaran Manonmani
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  2. Lakshmanan Sandhiya
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  3. Kittusamy Senthilkumar
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Correspondence to Kittusamy Senthilkumar.

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ESM 1

Cartesian coordinates of the transition state structures involved in the studied reactions calculated at M06-2X/6-31G(d,p) level of theory are summarized in Table S1. The calculated relative energy (∆E, kcal/mol), enthalpy (∆H298, kcal/mol) and Gibbs free energy (∆G298, kcal/mol) for the initial OH addition reaction of diuron are given in Table S2. Relative energy (∆E, kcal/mol), enthalpy (∆H, kcal/mol) and Gibbs free energy (∆G, kcal/mol) of the reactive species involved in the initial OH addition reactions of diuron by OH radical in aqueous medium obtained at M06-2X/6-31G(d,p) level of theory are given in Table S3. The rate constant for the initial reactions calculated using CVT, TST and TST (SCT) methods are summarized in Table S4. The relative energy (∆E), enthalpy (∆H298) and Gibbs free energy (∆G298) of the reactive species involved in the reaction of intermediate, I4 with O2 are given in Table S5. The relative energy (∆E), enthalpy (∆H298) and Gibbs free energy (∆G298) of all the reactive species involved in the subsequent reactions of intermediate, I7 are given in Table S6. The relative energy (∆E), enthalpy (∆H298) and Gibbs free energy (∆G298) of all the reactive species involved in the subsequent reactions of intermediate, I8 are given in Table S7. The optimized geometry of reactant complexes, intermediates and products involved in the OH addition reaction of diuron are shown in Fig. S1. The structure of reactant complexes, intermediates and product for the reaction of I4 with O2 are shown in Fig. S2. The optimized structure of intermediates, products involved in the subsequent reactions of intermediate, I12 are shown in Fig. S3. The optimized structure of intermediates and products involved in the subsequent reactions of intermediate, I8 are shown in Fig. S4. (DOCX 934 kb)

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Manonmani, G., Sandhiya, L. & Senthilkumar, K. Mechanism and kinetics of diuron oxidation by hydroxyl radical addition reaction. Environ Sci Pollut Res 27, 12080–12095 (2020). https://doi.org/10.1007/s11356-020-07806-4

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