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UV-A induced photochemical formation of N-nitrosodimethylamine (NDMA) in the presence of nitrite and dimethylamine

机译:在亚硝酸盐和二甲胺的存在下,UV-A诱导的N-亚硝基二甲胺(NDMA)的光化学形成

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The photochemical nitrosation of dimethylamine (DMA) has been suggested as a possible pathway for the occurrence of N-nitrosodimethylamine (NDMA) in aquatic environments.The aim of this study was to investigate the formation of NDMA from the nitrosation of DMA during nitrite (NO_2~-) photolysis in aqueous solution by varying several of the experimental parameters.NDMA was formed at neutral pH,in the presence of DMA and NO_2~- under UV-A irradiation,and exhibited an increase in concentration with irradiation time.Increasing the concentrations of DMA and NO_2~- led to enhanced NDMA formation.Through experiments employing ~(centre dot) OH scavenger (t-BuOH),~(centre dot)OH was found to play an important role in the production of nitrosating agents during the photolysis of NO_2~-.The optimum pH for the formation of NDMA was around 10.This pH dependence was explained by the dual role of deprotonated DMA as a nucleophile,which enhances the nitrosation reaction between nitrosating agents and DMA,and a hydroxyl radical (~(centre dot)OH) scavenger,which reduces the production of nitrosating agents.A higher concentration of NDMA was obtained under N2 condition due to the lower quantum yield for NDMA photolysis in the absence of oxygen.Various anions,including phosphate ions in the buffer solution,retarded the formation of NDMA,possibly due to degradation of the nitrosating agents.
机译:二甲基胺(DMA)的光化学亚硝化被认为是在水生环境中发生N-亚硝基二甲基胺(NDMA)的可能途径。本研究的目的是研究亚硝酸盐(NO_2)期间DMA的亚硝化形成NDMA的过程。 〜-)通过改变几个实验参数在水溶液中进行光解.NDMA在中性pH下在DMA和NO_2〜-存在下于UV-A照射下形成,并随着照射时间的增加而浓度增加。通过使用〜(中心点)OH清除剂(t-BuOH)的实验,发现〜(中心点)OH在光解过程中亚硝化剂的产生中起重要作用形成NDMA的最适pH约为10。这种pH依赖性是由去质子化DMA作为亲核试剂的双重作用所解释的,这增强了亚硝化剂与亚硝化剂之间的亚硝化反应。 DMA和羟基自由基(〜(中心点OH))清除剂,减少了亚硝化剂的产生。由于在没有氧气的情况下NDMA光解的量子产率较低,因此在N2条件下获得了更高浓度的NDMA。阴离子(包括缓冲液中的磷酸根离子)阻碍了NDMA的形成,这可能是由于亚硝化剂的降解所致。

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