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A particle-phase relative rates technique is used to investigate theheterogeneous reaction between OH radicals and tris-2-butoxyethyl phosphate(TBEP) at 298 K by combining aerosol time-of-flight mass spectrometry(C-ToF-MS) data and positive matrix factor (PMF) analysis. The derivedsecond-order rate constants (k2) for the heterogeneous loss of TBEP is(4.44 ± 0.45) × 10−12 cm3 molecule−1 s−1,from which an approximate particle-phase lifetime was estimated to be2.6 (2.3–2.9) days. However, large differences in the rate constants for TBEP relative to a reference compound were observed when comparing internally andexternally mixed TBEP/organic particles, and upon changes in the RH. Theheterogeneous degradation of TBEP was found to be depressed or enhanceddepending upon the particle mixing state and phase, highlighting thecomplexity of heterogeneous oxidation in the atmosphere. The effect ofgas-particle partitioning on the estimated overall lifetime (gas + particle) for several organophosphate esters (OPEs) was also examinedthrough the explicit modeling of this process. The overall atmosphericlifetimes of TBEP, tris-2-ethylhexyl phosphate (TEHP) andtris-1,3-dichloro-2-propyl phosphate (TDCPP) were estimated to be 1.9, 1.9and 2.4 days respectively, and are highly dependent upon particle size.These results demonstrate that modeling the atmospheric fate of particle-phase toxic compounds for the purpose of risk assessment must include thegas-particle partitioning process, and in the future include the effect of otherparticulate components on the evaporation kinetics and/or the heterogeneousloss rates

OH-initiated heterogeneous oxidation of tris-2-butoxyethyl phosphate: implications for its fate in the atmosphere