Effective mass accommodation for partitioning of organic compounds into surface films with different viscosities

Abstract

Indoor surfaces can act as reservoirs and reaction media influencing the concentrations and type of species that people are exposed to indoors. Mass accommodation and partitioning are impacted by the phase state and viscosity of indoor surface films. We developed the kinetic multi-layer model KM-FILM to simulate organic film formation and growth, but it is computationally expensive to couple such comprehensive models with indoor air box models. Recently, a novel effective mass accommodation coefficient (α_eff) was introduced for efficient and effective treatments of gas–particle partitioning. In this study, we extended this approach to a film geometry with α_eff as a function of penetration depth into the film, partitioning coefficient, bulk diffusivity, and condensed-phase reaction rate constant. Comparisons between KM-FILM and the α_eff method show excellent agreement under most conditions, but with deviations before the establishment of quasi-equilibrium within the penetration depth. We found that the deposition velocity of species and overall film growth are impacted by bulk diffusivity in highly viscous films (D_b ∼<10⁻¹⁵ cm² s⁻¹). Reactions that lead to non-volatile products can increase film thicknesses significantly, with the extent of film growth being dependent on the gas-phase concentration, rate coefficient, partitioning coefficient and diffusivity. Amorphous semisolid films with D_b > ∼10⁻¹⁷–10⁻¹⁹ cm² s⁻¹ can be efficient SVOC reservoirs for compounds with higher partitioning coefficients as they can be released back to the gas phase over extended periods of time, while glassy solid films would not be able to act as reservoirs as gas-film partitioning is impeded.