Atmospheric chemical reactions of alternatives of polybrominated diphenyl ethers initiated by center dot OH: A case study on triphenyl phosphate

作者：Yu, Qi; Xie, Hong-Bin^*; Chen, Jingwen

来源：Science of the Total Environment, 2016, 571: 1105-1114.

DOI：10.1016/j.scitotenv.2016.07.105

• Triphenyl phosphate
• Atmospheric oxidation
• Mechanism
• Ice surface
• Computational study

Many studies have been performed to evaluate the environmental risk caused by alternative flame retardants (AFRs) of polybrominated diphenyl ethers due to their ubiquitous occurrence in the environment However, as an indispensable component of the environmental risk assessment, the information on atmospheric fate of AFRs is limited although some AFRs have been frequently and highly detected in the atmosphere. Here, a combined quantum chemical method and kinetics modeling were used to investigate atmospheric transformation mechanism and kinetics of AFRs initiated by center dot OH in the presence of O-2, taking triphenyl phosphate (TPhP) as a case. Results show that the pathway involving initial center dot OH addition to phenyl of TPhP to form TPhP-OH adduct, and subsequent reaction of the TPhP-OH adduct with O-2 to finally form phenol phosphate, is the most favorable for the titled reaction. The calculated overall reaction rate constant is 1.6 x 10(-12) cm(3) molecule(-1) s(-1), translating 7.6 days atmospheric lifetime of TPhP. This clarifies that gaseous TPhP has atmospheric persistence. In addition, it was found that ice surface, as a case of ubiquitous water in the atmosphere, has little effect on the kinetics of the rate-determining step in the center dot OH-initiated TPhP reaction.

• 出版日期2016-11-15
• 单位大连理工大学