Regional differences in gas–particle partitioning and deposition of semivolatile organic compounds on a global scale

Abstract

Variability in gas–particle partitioning of semivolatile organic compounds (SOCs) and related atmospheric processes (particle-associated deposition, rain washout and degradation) are investigated on a global scale. Two different sorption approaches (one using the octanol-air partition coefficient, K OA, and one based on poly-parameter linear free energy relationships, ppLFER) and two different atmospheric box models (unit-world and highly spatially and temporally resolved) are applied. In the unit-world model, the overall deposition and atmospheric fate of SOCs calculated with the K OA-based sorption approach are similar to the ones calculated with the ppLFER approach. Rain washout dominates the atmospheric removal of polar chemicals in the unit-world model while non-polar chemicals are removed mainly through degradation or particle-associated deposition. In contrast, big differences and a high sensitivity to the selected sorption approach are found in the spatially and temporally resolved model. The highly resolved geographic variability cannot be represented using the K OA-based approach if aerosol components other than OM are of importance for sorption. In particular, aerosols in dry regions (desert) and regions with low OM aerosols (arctic, some oceanic regions) are more appropriately described by the ppLFER approach. With the ppLFER approach, good agreement between modeled deposition fluxes and measurement data are found for higher chlorinated PCBs and TCDD/Fs. In general, we recommend the ppLFER approach for highly resolved environmental fate models.