Atmospheric stability of six particulate biogenic secondary organic aerosol markers towards photolysis, hydroxyl radicals and ozone

This study aimed to investigate the kinetics of the heterogeneous reactions of six biogenic secondary organic aerosol (BSOA) markers of atmospheric interest, i.e. the terebic, terpenylic, cis-pinonic, pinic, 3-methyl-1,2,3-butanetricarboxylic (MBTCA) and β-caryophyllinic acids. For this purpose, these compounds were individually adsorbed onto silica model particles and exposed either to solar irradiation, hydroxyl radicals, or ozone. Marker concentrations extracted from particles were subsequently analyzed by liquid chromatography coupled to quadrupole time-of-flight mass spectrometry (LC-QTOF/MS). Pseudo-first-order rate constants were derived from simulations (using either exponential functions or the tangent slope at t₀) of particulate marker concentration decays as a function of exposure time to different oxidants or light. Second-order rate constants were calculated considering the oxidant concentrations under different experimental conditions. The overall atmospheric lifetime of each marker was calculated, revealing that β-caryophyllinic acid is the most reactive compound studied, with a lifetime of <14.3 min, followed by cis-pinonic acid (8.6 h), MBTCA (19 h), pinic acid (>2.8 days), terpenylic acid (>4.8 days), and terebic acid (>5.8 years).This work confirms that the atmospheric stability of some BSOA markers is insufficient, to justify their relevance as tracers of particle formation or aging processes.