Molecular mechanism of NDMA formation from N,N-dimethylsulfamide during ozonation: quantum chemical insights into a bromide-catalyzed pathway

Environmental Science & Technology
Daniela TrogoloJ Samuel Arey

Abstract

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 ...Continue Reading

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Citations

Aug 16, 2016·Environmental Science & Technology·Liudmyla K SviatenkoJerzy Leszczynski
Dec 17, 2016·Environmental Science & Technology·Daniela Trogolo, J Samuel Arey
Feb 7, 2017·Environmental Science. Processes & Impacts·Hang YuYi Luo
Mar 3, 2018·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·Daisuke Minakata, Erica Coscarelli
Nov 18, 2018·Environmental Science and Pollution Research International·Linlu ShenBaoling Yuan
Jun 8, 2021·Environmental Science & Technology·Benjamin BarriosDaisuke Minakata
Jun 21, 2021·The Science of the Total Environment·Menglan GaoWei Cao
Sep 18, 2018·Environmental Science & Technology·Oliver KnoopTorsten C Schmidt

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