Molecular Mechanism of NDMA Formation from N,N-Dimethylsulfamide During Ozonation: Quantum Chemical Insights into a Bromide-Catalyzed Pathway
| Autor: | Urs von Gunten, Brijesh Kumar Mishra, J. Samuel Arey, Michèle B. Heeb, Daniela Trogolo |
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| Rok vydání: | 2015 |
| Předmět: |
Bromides
Halogenation Inorganic chemistry Reaction intermediate 010501 environmental sciences 010402 general chemistry Photochemistry 01 natural sciences Catalysis Dimethylnitrosamine Water Purification chemistry.chemical_compound Ozone Deprotonation Reaction rate constant Bromide Hypobromous acid Environmental Chemistry Molecule 0105 earth and related environmental sciences Sulfonamides Bromates Chemistry Drinking Water fungi General Chemistry 0104 chemical sciences Kinetics 13. Climate action Nitrosyl bromide Oxidation-Reduction Water Pollutants Chemical |
| Zdroj: | Environmental Science & Technology. 49:4163-4175 |
| ISSN: | 1520-5851 0013-936X |
| DOI: | 10.1021/es504407h |
| Popis: | During ozonation of drinking water, the fungicide metabolite N,N-dimethylsulfamide (DMS) can be transformed into a highly toxic product, N-nitrosodimethylamine (NDMA). We used quantum chemical computations and stopped-flow experiments to evaluate a chemical mechanism proposed previously to describe this transformation. Stopped-flow experiments indicate a pK(a) = 10.4 for DMS. Experiments show that hypobromous acid (HOBr), generated by ozone oxidation of naturally occurring bromide, brominates the deprotonated DMS(-) anion with a near-diffusion controlled rate constant (7.1 ± 0.6 × 10(8) M(-1) s(-1)), forming Br-DMS(-) anion. According to quantum chemical calculations, Br-DMS has a pK(a) ∼ 9.0 and thus remains partially deprotonated at neutral pH. The anionic Br-DMS(-) bromamine can react with ozone with a high rate constant (10(5 ± 2.5) M(-1) s(-1)), forming the reaction intermediate (BrNO)(SO2)N(CH3)2(-). This intermediate resembles a loosely bound complex between an electrophilic nitrosyl bromide (BrNO) molecule and an electron-rich dimethylaminosulfinate ((SO2)N(CH3)2(-)) fragment, based on inspection of computed natural charges and geometric parameters. This fragile complex undergoes immediate (10(10 ± 2.5) s(-1)) reaction by two branches: an exothermic channel that produces NDMA, and an entropy-driven channel giving non-NDMA products. Computational results bring new insights into the electronic nature, chemical equilibria, and kinetics of the elementary reactions of this pathway, enabled by computed energies of structures that are not possible to access experimentally. |
| Databáze: | OpenAIRE |
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