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 twophase 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. Secondary organic aerosol (SOA) constitutes a large fraction of atmospheric aerosol. To assess its impacts on climate and air pollution, knowledge of the number of phases in internal mixtures of different SOA types is required. Atmospheric models often assume that different SOA types form a single phase when mixed. Here, we present visual observations of the number of phases formed after mixing different anthropogenic and biogenic SOA types. Mixing SOA types generated in environmental chambers with oxygen-to-carbon (O/C) ratios between 0.34 and 1.05, we found 6 out of 15 mixtures of two SOA types to result in two phase particles. We demonstrate that the number of phases depends on the difference in the average O/C ratio between the two SOA types (Δ(O/C)). Using a threshold Δ(O/C) of 0.47, we can predict the phase behavior of over 90 % of our mixtures, with one- and two-phase particles predicted for Δ(O/C)<0.47 and Δ(O/C)≥0.47, respectively. This threshold ΔO/C value provides a simple parameter to predict whether mixtures of fresh and aged SOA form one- or two-phase particles in the atmosphere. In addition, we show that phase-separated SOA particles form when mixtures of volatile organic compounds emitted from real trees are oxidized.

Biomass burning events emit large amounts of phenolic compounds, which are oxidized in the atmosphere and form secondary organic aerosol (SOA). Using the poke-flow technique, we measured relative humidity (RH)-dependent viscosities of SOA generated by the oxidation of three biomass burning phenolic compounds: catechol, guaiacol, and syringol. All systems had viscosity < 3 × 103 Pa s at RH ≳ 40% and > 2 × 108 Pa s at RH ≲ 3% at room temperature. At RH values of 0–10%, the viscosities of these SOA were at least 2 orders of magnitude higher than the viscosity of primary organic aerosol from biomass burning. We also developed a parameterization for predicting the viscosity of phenolic biomass burning SOA as a function of RH and temperature. Based on this parameterization, the viscosity of phenolic biomass burning SOA is strongly dependent on both RH and temperature. Under dry conditions, phenolic biomass burning SOA is highly viscous at room temperature (∼109 Pa s) and becomes a glass (viscosity > 1012 Pa s) when the temperature is < 280 K. For tropospheric temperature and RH values, phenolic biomass burning SOA is often in a liquid state (η < 102 Pa s) below ∼2 km altitude, a semi-solid state (102 < η < 1012 Pa s) between ∼2 and ∼9 km, and a glassy state (η > 1012 Pa s) above ∼9 km. Furthermore, the mixing time of organic molecules in a 200 nm phenolic biomass burning SOA particle exceeds 1 h above 3 km in the troposphere.

Biomass burning events emit large amounts of phenolic compounds, which are oxidized in the atmosphere and form secondary organic aerosol (SOA). Using the poke-flow technique, we measured room-temperature and relative humidity (RH)-dependent viscosities of SOA generated by the oxidation of three biomass burning phenolic compounds: catechol, guaiacol, and syringol. All systems had viscosity < 3 × 10³ Pa s at RH ⪆ 40% and > 2 × 10⁸ Pa s at RH ⪅ 3%. At RH values of 0-10%, the viscosities of these SOA were at least 2 orders of magnitude higher than the viscosity of primary organic aerosol (POA) from biomass burning. These results suggest that mixing biomass burning SOA and POA may extend the lifetime of the brown carbon in the atmosphere. Based on an extrapolation of our results to tropospheric temperature and RH values, phenolic SOA is in a glassy state (𝜂 > 10¹² Pa s) above ∼6 km in the troposphere, potentially acting as heterogeneous ice nuclei in clouds, thereby influencing climate. Furthermore, the mixing time of organic molecules in a 200 nm phenolic SOA particle exceeds 1 h above 3 km in the troposphere, which has implications for the long-range transport of pollutants.