OH-initiated degradation of 1,2,3-trimethylbenzene in the atmosphere and wastewater: Mechanisms, kinetics, and ecotoxicity

1,2,3-Trimethylbenzene (1,2,3-TMB) is an important volatile organic compound (VOC) present in petroleum wastewa-ter and the atmosphere. This compound can be degraded by OH radicals via abstraction, addition and substitution mechanisms. Results show that the addition mechanism is dominant and H-abstraction is subdominant, while methyl abstraction and substitution mechanisms are negligible in the gas and aqueous phases. Moreover, H-abstraction prod-ucts undergo further reactions with O2, NO, NO2, H2O, and OH radicals in the atmosphere. Time-dependent density functional theory (TDDFT) calculations show that the degraded products, including 2,3,4-trimethylphenyl-nitroperoxoite, 1,2,3-trimethyl-4-nitrobenzene, 1,2,3-trimethyl-5-nitrobenzene, 2,6-dimethylbenzyl nitroperoxoite, 2,3-dimethylphenyl nitroperoxoite, 2,6-dimethylbenzaldehyde, and 2,3-dimethylbenzaldehyde, can photolyze under the sunlight. Kinetically, the calculated total rate constant is 5.57 x 10-11 cm3 molecule-1 center dot s-1 at 1 atm and 298 K, which is consistent with available experimental values measured in the atmosphere. In addition, the calculated total reaction rate constant in water is close to that in the gas phase. In terms of ecotoxicity, all degradation products are less toxic than the initial reactant to fish, green algae and daphnia. For mammals represented by rats, 1,2,3-TMB and its products are moderately toxic, except for 2,3-dimethylphenol and 2,6-dimethylphenol, which are slightly toxic.

Automated summary

1,2,3-Trimethylbenzene is an important volatile organic compound found in petroleum wastewater and the atmosphere. It can be degraded by OH radicals through abstraction, addition, and substitution mechanisms. The dominant mechanism is addition, while H-abstraction and substitution mechanisms are negligible. The degraded products can photolyze under sunlight and have lower ecotoxicity than the initial reactant.