Effects of Atmospheric Water on ·OH-initiated Oxidation of Organophosphate Flame Retardants: A DFT Investigation on TCPP

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 ·OH in the presence of O2/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 × 10–10 cm3molecule–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 ·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.