Global simulations of monoterpene-derived peroxy radical fates and the distributions of highly oxygenated organic molecules (HOMs) and accretion products

Abstract

We evaluate monoterpene-derived peroxy radical (MT-RO2) unimolecular autoxidation and self- and cross-reactions with other RO2 species in the GEOS-Chem global chemical transport model. The formation of associated highly oxygenated organic molecules (HOMs) and accretion products are tracked in competition with other bimolecular reactions. Autoxidation is the dominant fate up to 6–8 km for first-generation MT-RO2, which can undergo unimolecular H shifts. Reaction with NO can be a more common fate for H-shift rate constants < 0.1 s−1 or at altitudes higher than 8 km due to the imposed Arrhenius temperature dependence of unimolecular H shifts. For MT-derived HOM-RO2, generated by multistep autoxidation of first-generation MT-RO2, reaction with other RO2 species is predicted to be the major fate throughout most of the boreal and tropical forest regions, whereas reaction with NO dominates in the temperate and subtropical forests of the Northern Hemisphere. The newly added reactions result in an approximate 4 % global average decrease in HO2 and RO2, mainly due to faster self-/cross-reactions of MT-RO2, but the impact upon HO2, OH, and NOx abundances is only important in the planetary boundary layer (PBL) over portions of tropical forests. Predicted HOM concentrations in MT-rich regions and seasons can exceed total organic aerosol predicted by the standard version of the GEOS-Chem model depending on the parameters used. Comparisons to observations reveal that large uncertainties remain for key reaction parameters and processes, especially with respect to the photochemical lifetime and volatility of HOMs as well as the rates and branching of associated RO2 accretion products. Further observations and laboratory studies related to MT-RO2-derived HOMs and gas-phase RO2 accretion product formation kinetics – especially their atmospheric fate, such as gas–particle partitioning, multiphase chemistry, and net secondary organic aerosol formation – are needed.