Articles | Volume 14, issue 22
Atmos. Chem. Phys., 14, 12195–12207, 2014
Atmos. Chem. Phys., 14, 12195–12207, 2014

Research article 19 Nov 2014

Research article | 19 Nov 2014

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

Y. Liu1,*, L. Huang1,**, S.-M. Li1, T. Harner1, and J. Liggio1 Y. Liu et al.
  • 1Atmospheric Science and Technology Directorate, Science and Technology Branch, Environment Canada, Toronto, M3H 5T4, Canada
  • *now at: Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing, 100085, China
  • **now at: Environmental Monitoring and Reporting Branch, Ontario Ministry of the Environment and Climate Change, Toronto, M9P 3V6, Canada

Abstract. A particle-phase relative rates technique is used to investigate the heterogeneous 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 derived second-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 be 2.6 (2.3–2.9) days. However, large differences in the rate constants for TBEP relative to a reference compound were observed when comparing internally and externally mixed TBEP/organic particles, and upon changes in the RH. The heterogeneous degradation of TBEP was found to be depressed or enhanced depending upon the particle mixing state and phase, highlighting the complexity of heterogeneous oxidation in the atmosphere. The effect of gas-particle partitioning on the estimated overall lifetime (gas + particle) for several organophosphate esters (OPEs) was also examined through the explicit modeling of this process. The overall atmospheric lifetimes of TBEP, tris-2-ethylhexyl phosphate (TEHP) and tris-1,3-dichloro-2-propyl phosphate (TDCPP) were estimated to be 1.9, 1.9 and 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 the gas-particle partitioning process, and in the future include the effect of other particulate components on the evaporation kinetics and/or the heterogeneous loss rates.

Final-revised paper