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论文类型：期刊论文

发表时间：2017-05-02

发表刊物：ENVIRONMENTAL SCIENCE & TECHNOLOGY

收录刊物：SCIE、EI、PubMed

卷号：51

期号：9

页面范围：5043-5051

ISSN号：0013-936X

摘要：Tris(2-chloroisopropyl) phosphate (TCPP), a widely used organophosphate flame retardant, has been recognized as an important atmospheric pollutant. It is notable that TCPP has potential for long-range atmospheric transport. However, its atmospheric fate is unknown, restricting its environmental risk assessment. Herein we performed quantum chemical calculations to investigate the atmospheric transformation mechanisms and kinetics of TCPP initiated by center dot OH in the presence of O-2/NO/NO2, and the effects of ubiquitous water on these reactions. Results show the H-abstraction pathways are the most favorable for the titled reaction. The calculated gaseous rate constant and lifetime at 298 K are 1.7 X 10(-10) cm(3)molecule(-1) s(-1) and 1.7 h, respectively. However, when considering atmospheric water, the corresponding lifetime is about 0.5-20.2 days. This study reveals for the first time that water has a negative role in the center dot OH-initiated degradation of TCPP by modifying the stabilities of prereactive complexes and transition states via forming hydrogen bonds, which unveils one underlying mechanism for the observed persistence of TCPP in the atmosphere. Water also influences secondary reaction pathways of selected TCPP radicals formed from the primary H-abstraction. These results demonstrate the importance of water in the evaluation of the atmospheric fate of newly synthesized chemicals and emerging pollutants.