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Many atmospheric and chemical variables influence the partitioningequilibrium between gas phase and condensed phases of compounds implicatedin the formation of secondary organic aerosol (SOA). The large number offactors and their interaction makes it often difficult to assess theirrelative importance and concerted impact. Here we introduce atwo-dimensional space which maps regions of dominant atmospheric phasedistribution within a coordinate system defined by equilibrium partitioncoefficients between the gas phase, an aqueous phase and a water-insolubleorganic matter (WIOM) phase. Placing compounds formed from the oxidation ofn-alkanes, terpenes and mono-aromatic hydrocarbons on the maps based on theirpredicted partitioning properties allows for a simple graphical assessmentof their equilibrium phase distribution behaviour. Specifically, it allowsfor the simultaneous visualisation and quantitative comparison of the impacton phase distribution of changes in atmospheric parameters (such astemperature, salinity, WIOM-phase polarity, organic aerosol load, and liquidwater content) and chemical properties (such as oxidation state, molecularsize, functionalisation, and dimerisation). The graphical analysis revealsthat the addition of hydroxyl, carbonyl and carboxyl groups increases theaffinity of aliphatic, alicyclic and aromatic hydrocarbons for the aqueousphase more rapidly than their affinity for WIOM, suggesting that the aqueousphase may often be relevant even for substances that are considerably largerthan the C2 and C3 compounds that are typically believed to be associatedwith aqueous SOA. In particular, the maps identify some compounds thatcontribute to SOA formation if partitioning to both WIOM and aqueous phaseis considered but would remain in the gas phase if either condensed phasewere neglected. For example, many semi-volatile α-pinene oxidationproducts will contribute to aqueous SOA under the conditions of high liquid water contentencountered in clouds but would remain vapours in wet aerosol.It is conceivable to develop parameterisations of "partitioning basissets" that group compounds with comparable partitioning properties, which – when combined with data on the abundance of those groups of compounds –could serve in the simulation of SOA formation

atmospheric chemistry and physics

Using the chemical equilibrium partitioning space to explore factors influencing the phase distribution of compounds involved in secondary organic aerosol formation