Vapor wall deposition in Teflon chambers

Teflon chambers are ubiquitous in studies of atmospheric chemistry. Secondary organic aerosol (SOA) formation can be underestimated, owing to deposition of SOA-forming vapors to the chamber wall. We present here an experimental protocol and a model framework to constrain the vapor-wall interactions in Teflon chambers. We measured the wall deposition rates of 25 oxidized organic compounds generated from the photooxidation of isoprene, toluene, alpha-pinene, and dodecane in two chambers that had been extensively used and in two new unused chambers. We found that the extent of prior use of the chamber did not significantly affect the sorption behavior of the Teflon films. Among the 25 compounds studied, the maximum wall deposition rate is exhibited by the most highly oxygenated and least volatile compounds. By optimizing the model output to the observed vapor decay profiles, we identified that the dominant parameter governing the extent of wall deposition of a compound is its wall accommodation coefficient (alpha(w,i)), which can be correlated through its volatility with the number of carbons and oxygens in the molecule. By doing so, the wall-induced deposition rate of intermediate/semi-volatile organic vapors can be reasonably predicted based on their molecular constituency. The extent to which vapor wall deposition impacts measured SOA yields depends on the competition between uptake of organic vapors by suspended particles and the chamber wall. The timescale associated with vapor wall deposition can vary from minutes to hours depending on the value of alpha(w,i). For volatile and intermediate volatility organic compounds (small alpha(w,i)), gas-particle partitioning will dominate wall deposition for typical particle number concentrations in chamber experiments. For compounds characterized by relatively large alpha(w,i), vapor transport to particles is suppressed by competition with the chamber wall even with perfect particle accommodation.