OH initiated heterogeneous degradation of organophosphorus compounds

Organophosphorus compounds (OPs) have been extensively used worldwide as flame retardants, plasticizers, antifoaming agents, and additives because of their favorable physicochemical characteristics. The global consumption of OPs is likely to greatly increase due to the phasing out of bromine-containing flame retardants (BFRs) with OPs identified as possible substitutes. In most applications, OPs easily leach out of the material into the environment via volatilization, abrasion, and dissolution and have been observed widely in atmospheric particles even in polar regions. However, little is known about their atmospheric fate. The Canadian Chemicals Management Plan (CMP) has targeted OP FRs for risk assessment, including assessing stability and atmospheric transport potential of OP FRs and other priority chemicals that are associated primarily with particles. In the current study, OH initiated heterogeneous reaction kinetics of tris(1,3-dichloro-2-propyl) phosphate (TDCPP), tris-2-ethylhexyl-phosphate (TEHP), tris-2-butoxyethyl-phosphate (TBEP), and tri-phenyl phosphate (TPhP) coated on (NH4)2SO4 were investigated using a photo-chemical flow tube which was coupled to an Aerosol Mass Spectrometer (AMS) and Proton Transfer Reaction Mass Spectrometer (PTR-MS). second-order rate constants (k₂) for the heterogeneous loss of TPhP, TEHP and TDCPP were (2.07×0.19)×10^-12, (2.69×0.63)×10^-12 and (9.22×0.92)×10^{-13 c}m³ molecule^-1 s^-1, respectively, from which approximate atmospheric lifetimes were estimated to be 5.6 (5.2-6.0), 4.3 (3.5-5.6), and 12.6 (11.4-14.0) days. These results represent the first reported estimates of heterogeneous rate constants for these species, and suggest that particle bound OPEs will be highly persistent in the atmosphere, supporting the assumption that OPEs can undergo medium or long-range transport, as proposed on the basis of field measurements.