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论文类型：期刊论文

发表时间：2018-09-04

发表刊物：ENVIRONMENTAL SCIENCE & TECHNOLOGY

收录刊物：PubMed、SCIE

卷号：52

期号：17

页面范围：9801-9809

ISSN号：0013-936X

摘要：Chlorine radicals (center dot Cl) initiated amine oxidation plays an important role for the formation of carcinogenic nitrosamine in the atmosphere. Piperazine (PZ) is considered as a potential atmospheric pollutant since it is an alternative solvent to monoethanolamine (MEA), a benchmark solvent in a leading CO2 capture technology. Here, we employed quantum chemical methods and kinetics modeling to investigate center dot Cl-initiated atmospheric oxidation of PZ, particularly concerning the potential of PZ to form nitrosamine compared to MEA. Results showed that the center dot Cl-initiated PZ reaction exclusively leads to N-center radicals (PZ-N) that mainly react with NO to produce nitrosamine in their further reaction with O-2/NO. Together with the PZ + center dot OH reaction, the PZ-N yield from PZ oxidation is still lower than that of the corresponding MEA reactions. However, the nitrosamine yield of PZ is higher than the reported value for MEA when [NO] is <5 ppb, a concentration commonly encountered in a polluted urban atmosphere. The unexpected high nitrosamine yield from PZ compared to MEA results from a more favorable reaction of N-center radicals with NO compared to O-2. These findings show that the yield of N-center radicals cannot directly be used as a metric for the yield of the corresponding carcinogenic nitrosamine.