Quantification of Gas-Wall Partitioning in Teflon Environmental Chambers Using Rapid Bursts of Low-Volatility Oxidized Species Generated in Situ

Abstract

Partitioning of gas-phase organic compounds to the walls of Teflon environmental chambers is a recently reported phenomenon than can affect the yields of reaction products and secondary organic aerosol (SOA) measured in laboratory experiments. Reported time scales for reaching gas-wall partitioning (GWP) equilibrium (τGWE) differ by up to 3 orders of magnitude, however, leading to predicted effects that vary from substantial to negligible. A new technique is demonstrated here in which semi- and low-volatility oxidized organic compounds (saturation concentration c* < 100 μg m(-3)) were photochemically generated in rapid bursts in situ in an 8 m(3) environmental chamber, and then their decay in the absence of aerosol was measured using a high-resolution chemical ionization mass spectrometer (CIMS) equipped with an "inlet-less" NO3(-) ion source. Measured τGWE were 7-13 min (rel. std. dev. 33%) for all compounds. The fraction of each compound that partitioned to the walls at equilibrium follows absorptive partitioning theory with an equivalent wall mass concentration in the range 0.3-10 mg m(-3). Measurements using a CIMS equipped with a standard ion-molecule reaction region showed large biases due to the contact of compounds with walls. On the basis of these results, a set of parameters is proposed for modeling GWP in chamber experiments.