Formation of organic tracers for isoprene SOA under acidic conditions

The chemical compositions of a series of secondary organic aerosol (SOA) samples, formed by irradiating mixtures of isoprene and NO in a smog chamber in the absence or presence of acidic aerosols, were analyzed using derivatization-based GC–MS methods. In addition to the known isoprene photooxidation products 2-methylglyceric acid, 2-methylthreitol, and 2-methylerythritol, three other peaks of note were detected: one of these was consistent with a silylated-derivative of sulfuric acid, while the remaining two were other oxidized organic compounds detected only when acidic aerosol was present. These two oxidation products were also detected in field samples, and their presence was found to be dependent on both the apparent degree of aerosol acidity as well as the availability of isoprene aerosol. The average concentrations of the sum of these two compounds in the ambient PM2.5 samples ranged from below the GC–MS detection limit during periods when the isoprene emission rate or apparent acidity were low to approximately 200 ng m−3 (calibrations being based on a surrogate compound) during periods of high isoprene emissions. These compounds presently unidentified have the potential to serve as organic tracers of isoprene SOA formed exclusively in the presence of acidic aerosol and may also be useful in assessments in determining the importance and impact of aerosol acidity on ambient SOA formation.