Gas-Wall Partitioning of Organic Compounds in a Teflon Film Chamber and Potential Effects on Reaction Product and Aerosol Yield Measurements

Gas-wall partitioning of organic compounds (OC) that included C-8-C-16 n-alkanes and 1-alkenes and C-8-C-13 2-alcohols and 2-ketones was investigated in two Teflon FEP chambers whose walls were either untreated, oxidized in sunlight, or previously exposed to secondary organic aerosol (SOA). Partitioning was nearly independent of chamber treatment, reversible, and obeyed Henry's law. The fraction of an OC that partitioned to the walls at equilibrium ranged from 0 to similar to 65%. Values increased with increasing carbon number within an OC class and for OC with similar vapor pressures increased in the order n-alkanes <1-alkenes <2-alcohols <2-ketones. Estimated time constants for achieving partitioning equilibrium ranged from similar to 60 min for n-alkanes to <= 8 min for 2-ketones. The observations are consistent with a sorption mechanism in which OC dissolve into the film but are restricted to the near-surface region by a sharp permeability gradient that develops in response to OC-induced stresses in polymer chains. When the results were analyzed using a model analogous to one commonly employed for gas-particle partitioning, it was estimated that the sorption properties of the chamber walls were equivalent to organic aerosol mass concentrations of 2, 4, 10, and 24 mg m(-3) with respect to the partitioning of n-alkanes, 1-alkenes, 2-alcohols, and 2-ketones. These values are up to similar to 4 orders of magnitude larger than concentrations used in most laboratory studies of SOA, which are typically 1-10(3) mu g m(-3), meaning that if full partitioning equilibrium is established in the chamber then semi-volatile OC will reside overwhelmingly in the chamber walls. Model simulations of gas-particle-wall partitioning were also carried out using the experimental data, and demonstrate quantitatively the large potential effects of Teflon walls on measured yields of gas-phase OC products and SOA.