Development and evaluation of a new compact mechanism for aromatic oxidation in atmospheric models

Abstract:

Aromatic hydrocarbons (mainly benzene, toluene, and xylenes) play an important role in atmospheric chemistry but the associated chemical mechanisms are complex and uncertain. Spare representation of this chemistry in models is needed for computational tractability. Here we develop a new compact mechanism for aromatic chemistry (GC13) that captures current knowledge from laboratory and computational studies with only 17 unique species and 44 reactions. We compare GC13 to six other currently used mechanisms of varying complexity in box model simulations of environmental chamber data and diurnal boundary layer chemistry, and show that GC13 provides results consistent with or better than more complex mechanisms for oxygenated products (alcohols, carbonyls, dicarbonyls), ozone, and hydrogen oxide (HO_x  OH + HO₂) radicals. GC13 features in particular increased radical recycling and increased ozone destruction from phenoxy-phenylperoxy radical cycling relative to other mechanisms. We implement GC13 into the GEOS-Chem global chemical transport model and find higher glyoxal yields and net ozone loss from aromatic chemistry compared to other mechanisms. Aromatic oxidation in the model contributes 23 %, 5 %, and 8 % of global glyoxal, methylglyoxal, and formic acid production respectively, and has mixed effects on formaldehyde. It drives small decreases in global tropospheric OH (−2.2 %), NO_x ( NO + NO₂; −3.7 %) and ozone (−0.8 %), but a large increase in NO₃ (+22 %) from phenoxy-phenylperoxy radical cycling. Regional effects in polluted environments can be substantially larger, especially from photolysis of carbonyls produced by aromatic oxidation, which drives large wintertime increases in OH and ozone concentrations.