Chemical composition of secondary organic aerosol formed from the photooxidation of isoprene

Recent work in our laboratory has shown that the photooxidation of isoprene (2-methyl-1,3-butadiene, C5H8) leads to the formation of secondary organic aerosol (SOA). In the current study, the chemical composition of SOA from the photooxidation of isoprene over the full range of NOx conditions is investigated through a series of controlled laboratory chamber experiments. SOA composition is studied using a wide range of experimental techniques: electrospray ionization-mass spectrometry, matrix-assisted laser desorption ionization-mass spectrometry, high-resolution mass spectrometry, online aerosol mass spectrometry, gas chromatography/mass spectrometry, and an iodometric-spectroscopic method. Oligomerization was observed to be an important SOA formation pathway in all cases; however, the nature of the oligomers depends strongly on the NOx level, with acidic products formed under high-NOx conditions only. We present, to our knowledge, the first evidence of particle-phase esterification reactions in SOA, where the further oxidation of the isoprene oxidation product methacrolein under high-NOx conditions produces polyesters involving 2-methylglyceric acid as a key monomeric unit. These oligomers comprise similar to 22-34% of the high-NOx SOA mass. Under low-NOx conditions, organic peroxides contribute significantly to the low-NOx SOA mass (similar to 61% when SOA forms by nucleation and similar to 25-30% in the presence of seed particles). The contribution of organic peroxides in the SOA decreases with time, indicating photochemical aging. Hemiacetal dimers are found to form from C-5 alkene triols and 2-methyltetrols under low-NOx conditions; these compounds are also found in aerosol collected from the Amazonian rainforest, demonstrating the atmospheric relevance of these low-NOx chamber experiments.