Quantum Chemical Study on ·Cl-Initiated Atmospheric Degradation of Monoethanolamine.
Recent findings on the formation of ·Cl in continental urban areas necessitate the consideration of ·Cl initiated degradation when assessing the fate of volatile organic pollutants. Monoethanolamine (MEA) is considered as a potential atmospheric pollutant since it is a benchmark and widely utilized solvent in a leading CO2 capture technology. Especially, ·Cl may have specific interactions with the N atom of MEA, which could make the MEA + ·Cl reaction have different pathways and products from those of the MEA + ·OH reaction. Hence, ·Cl initiated reactions with MEA were investigated by a quantum chemical method [CCSD(T)/aug-cc-pVTZ//MP2/6-31+G(3df,2p)] and kinetics modeling. Results show that the overall rate constant for ·Cl initiated H-abstraction of MEA is 5 times faster than that initiated by ·OH, and the tropospheric lifetimes of MEA will be overestimated by 6-46% when assuming that [·Cl]/[·OH] = 1-10% if the role of ·Cl is ignored. The MEA + ·Cl reaction exclusively produces MEA-N that finally transforms into several products including mutagenic nitramine and carcinogenic nitrosamine via further reactions with O2/NOx, and the contribution of ·Cl to their formation is about 25-250% of that of ·OH. Thus, it is necessary to consider ·Cl initiated tropospheric degradation of MEA for its risk assessment.
Key Laboratory of Industrial Ecology and Environmental Engineering (Ministry of Education), School of Environmental Science and Technology, Dalian University of Technology , Dalian 116024, China.
Hong-Bin
HB
Xie
Key Laboratory of Industrial Ecology and Environmental Engineering (Ministry of Education), School of Environmental Science and Technology, Dalian University of Technology , Dalian 116024, China.
Fangfang
F
Ma
Key Laboratory of Industrial Ecology and Environmental Engineering (Ministry of Education), School of Environmental Science and Technology, Dalian University of Technology , Dalian 116024, China.
Yuanfang
Y
Wang
State Key Laboratory of Fine Chemicals, Dalian University of Technology , Dalian 116024, China.
Ning
N
He
Key Laboratory of Industrial Ecology and Environmental Engineering (Ministry of Education), School of Environmental Science and Technology, Dalian University of Technology , Dalian 116024, China.
Qi
Q
Yu
Key Laboratory of Industrial Ecology and Environmental Engineering (Ministry of Education), School of Environmental Science and Technology, Dalian University of Technology , Dalian 116024, China.
Jingwen
J
Chen
D000393:Air Pollutants / Q000737:chemistry*; D001673:Biodegradation, Environmental; D002713:Chlorine / Q000737:chemistry; D019856:Ethanolamine / Q000737:chemistry*; D007700:Kinetics; D008956:Models, Chemical; D011789:Quantum Theory
D000393:Air Pollutants; D002713:Chlorine; D019856:Ethanolamine