New formation and fate of Isoprene SOA markers revealed by field data-constrained modeling

Particulate 2-methyltetrols (2-MT) and 2-methylglyceric acid (2-MG) are typically used to indicate the abundance of isoprene-derived secondary organic aerosols (SOA). However, their formation and fate are not fully understood. In this study, we showed that particulate 2-MT and 2-MG collected at multiple monitoring sites under a wide range of atmospheric and emission conditions, with concentrations spanning six orders of magnitudes, are well reproduced with an expanded isoprene-SOA scheme implemented into the Community Multiscale Air Quality (CMAQ) model. The scheme considers their three-phase (gas-aqueous-organic phase) partitioning, formation from acid-driven multiphase reactions, and degradation by OH radicals in the gas and aqueous phases. The model results reveal that a non-aqueous formation pathway or direct biogenic emission is needed to supplement the commonly assumed acid-driven multiphase reaction process to explain the observed 2-MT concentrations. This missing pathway contributes to 20–40% of 2-MT in areas with aerosol pH<2 and more than 70% under less acidic conditions (pH~2–5), such as those encountered in the western US and China. The typical summertime gas-phase photochemical lifetimes of 2-MT and 2-MG are estimated to be 4–6 and 20–30 h, respectively, and their aqueous lifetimes are approximately 20–40 h. Our simulations show that predicted 2-MT is mainly influenced by its aqueous phase loss to OH, but 2-MG is more sensitive to gas phase OH loss due to the preferential partitioning of the two tracers in the aqueous and gas phases, respectively.