The bacteriostatic antibiotics, sulfamethoxazole (SMX) and trimethoprim (TMP), have frequently been found in wastewater and surface water, which raises the concerns about their ecotoxicological effects. The indirect photochemical transformation has been proven to be an efficient way to degrade SMX and TMP. In this study, the reaction mechanisms of the degradation by SMX and TMF by OH radicals were investigated by theoretical calculations. Corresponding rate constants were determined and the eco-toxicity of SMX and TMP and its degradations products were predicted using theoretical models. The results indicate that the most favorable pathways for the transformation of SMX and TMP are both •OH-addition reaction of benzene ring site with lowest Gibbs free energy barriers (6.86 and 6.21 kcal mol⁻¹). It was found that the overall reaction rate constants of •OH-initial reaction of SMX and TMP are 1.28 × 10⁸ M⁻¹ s⁻¹ and 6.21 × 10⁸ M⁻¹ s⁻¹ at 298 K, respectively. When comparing the eco-toxicity of transformation products with parent SMX and TMP, it can be concluded that the acute and chronic toxicities of the degraded products are reduced, but some products remain harmful for organisms, especially for daphnid (toxic or very toxic level). This study can give greater insight into the degradation of SMX and TMP by •OH through theoretical calculations in aquatic environment.

Effect of H₂O and NH₃ on the synergistic oxidation reaction of SO₂ and NO₂ is investigated by theoretical calculation using the molecule system SO₂-2NO₂-nH₂O (n = 0, 1, 2, 3) and SO₂-2NO₂-nH₂O-mNH₃ (n = 0, 1, 2; m = 1, 2). Calculated results show that SO₂ is oxidized to SO₃ by N₂O₄ intermediate. The additional H₂O in the systems can reduce the energy barrier of oxidation step. The increasing number of H₂O molecules in the systems enhances the effect and promotes the production of HONO. When the proportion of H₂O to NH₃ is 1:1, with NH₃ included in the system, the energy barrier is lower than two pure H₂O molecules in the oxidation step. The present study indicates that the H₂O and NH₃ have thermodynamic effects on promoting the oxidation reaction of SO₂ and NO₂, and NH₃ has a more significant role in stabilizing product complexes. In these hydrolysis reactions, nethermost barrier energy (0.29 kcal/mol) can be found in the system SO₂-2NO₂-H₂O. It is obvious that the production of HONO is energetically favorable. A new reaction mechanism about SO₂ oxidation in the atmosphere is proposed, which can provide guidance for the further study of aerosol surface reactions.