Heterogeneous nucleation drives particle size segregation in sequential ozone and nitrate radical oxidation of catechol

Secondary organic aerosol formation via condensation of organic vapors onto existing aerosol transforms the chemical composition and size distribution of ambient aerosol, with implications for air quality and Earth's radiative balance. Gas-to-particle conversion is generally thought to occur on a continuum between equilibrium-driven partitioning of semivolatile molecules to the pre-existing mass size distribution and kinetic-driven condensation of low volatility molecules to the pre-existing surface area size distribution. However, we offer experimental evidence in contrast to this framework. When catechol is sequentially oxidized by O-3 and NO3 in the presence of (NH4)(2)SO4 seed particles with a single size mode, we observe a bimodal organic aerosol mass size distribution with two size modes of distinct chemical composition with nitrocatechol from NO3 oxidation preferentially condensing onto the large end of the pre-existing size distribution (similar to 750 nm). A size-resolved chemistry and microphysics model reproduces the evolution of the two distinct organic aerosol size modes-heterogeneous nucleation to an independent, nitrocatechol-rich aerosol phase.