Distribution of organophosphate esters between the gas phase and PM2.5 in urban Dalian, China

We investigated the concentrations and seasonal variations of organophosphate esters (OPEs) in the gas phase and PM₂.₅ (particulate matter with an aerodynamic diameter <2.5 μm) in an urban area of Dalian, China, as well as their gas-particle partitioning. The total concentrations of OPEs in the gas phase were in the range of 0.056–6.38 ng/m³ with the mean concentration of 0.83 ± 1.24 ng/m³, while the concentrations of OPEs in the PM₂.₅ were in the range of 0.32–3.46 ng/m³ with the mean concentration of 1.21 ± 0.67 ng/m³. Tris-(1-chloro-2-propyl) phosphate (TCIPP) was the dominant congener in the gaseous phase, followed by tris-(2-chloroethyl) phosphate (TCEP) and tri-n-butylphosphate (TNBP), whereas TCEP was the dominant species in the PM₂.₅, followed by TCIPP and triphenyl phosphate (TPHP). Seasonality was discovered for OPEs in both gas phase and PM₂.₅ with their concentrations higher in hot seasons, which may due to the temperature-driven emission or gas-particle partitioning. The PM₂.₅-bound fractions of OPEs varied significantly between seasons. Tricresyl phosphate (TMPP), tri(2-ethylhexyl) phosphate (TEHP), 2-ethylhexyl diphenyl phosphate (EHDPP), and TPHP were mostly adsorbed onto fine particles, while TNBP, TCEP, TCIPP, and tris(1,3-dichloro-2-propyl) phosphate (TDCIPP) distributed in both gas and fine particle phases. The predicted PM₂.₅-bound fractions by Kₒₐ-based model were closer to the measurements for TCIPP, TDCIPP, and TPHP, whereas the predictions by Junge-Pankow model were closer to the measurements for TMPP and tris (2-butoxyethyl) phosphate (TBOEP). However, the predictions of both models cannot accurately match the measured gas-particle partitioning of TNBP and TCEP.