Influence of Particle Surface Area Concentration on the Production of Organic Particulate Matter in a Continuously Mixed Flow Reactor.

Organic particulate matter (PM) was produced at different particle surface area concentrations S in a continuously mixed flow reactor (CMFR). The apparent PM yield from the dark ozonolysis of α-pinene increased from 24.5 ± 0.7% to 57.1 ± 0.6% for an increase in S from 0.55 to 2.87 × 10 μm·surface cm·volume. The apparent yield saturated for S > 2.1 × 10 μm cm. There was hysteresis in the apparent yield for experiments of increasing compared to decreasing S. The relative timescales of gas-particle interactions, gas-wall interactions, and thereby particle-wall cross interactions could explain the results. The PM carbon oxidation state and oxygen-to-carbon atomic ratio decreased from -0.19 to -0.47 and 0.62 to 0.51, respectively, for increasing S, suggesting that greater partitioning of semivolatile organic species into the PM contributed to the increased PM yield. A thorough understanding of the role of gas-wall interactions on apparent PM yield is essential for the extension of laboratory results into predictions of atmospheric PM production, and comparative results from CMFRs and batch reactors can be informative in this regard.