Phase Behavior of Internal Mixtures of Hydrocarbon-like Primary Organic Aerosol and Secondary Aerosol Based on Their Differences in Oxygen-to-Carbon Ratios

Abstract

The phase behavior, the number and type of phases, in atmospheric particles containing mixtures of hydrocarbon-like organic aerosol (HOA) and secondary organic aerosol (SOA) is important for predicting their impacts on air pollution, human health, and climate. Using a solvatochromic dye and fluorescence microscopy, we determined the phase behavior of 11 HOA proxies (O/C = 0–0.29) each mixed with 7 different SOA materials generated in environmental chambers (O/C 0.4–1.08), where O/C represents the average oxygen-to-carbon atomic ratio. Out of the 77 different HOA + SOA mixtures studied, we observed two phases in 88% of the cases. The phase behavior was independent of relative humidity over the range between 90% and <5%. A clear trend was observed between the number of phases and the difference between the average O/C ratios of the HOA and SOA components (ΔO/C). Using a threshold ΔO/C of 0.265, we were able to predict the phase behavior of 92% of the HOA + SOA mixtures studied here, with one-phase particles predicted for ΔO/C < 0.265 and two-phase particles predicted for ΔO/C ≥ 0.265. The threshold ΔO/C value provides a relatively simple and computationally inexpensive framework for predicting the number of phases in internal SOA and HOA mixtures in atmospheric models.

Abstract

Studying the internal mixtures of primary organic aerosol (POA) and secondary organic aerosol (SOA) materials, we show that most POA + SOA mixtures exhibit phase-separated particles and that this miscibility gap can be predicted using the difference in the average elemental oxygen-to-carbon ratio of the organic components.