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Large‐eddy simulation of biogenic VOC chemistry during the DISCOVER‐AQ 2011 campaign

Biogenic volatile organic compounds (BVOCs) are oxidized quickly in the atmosphere to form oxygenated VOC (OVOC) and play crucial roles in the formation of ozone and secondary organic aerosols. We use the National Center for Atmospheric Research's large‐eddy simulation model and Deriving Information on Surface Conditions from Column and Vertically Resolved Observations Relevant to Air Quality 2011 flight data to understand the role of boundary layer turbulence on the atmospheric chemistry of key BVOC species and their oxidation products. We simulate three distinct convective environments during the campaign, representing fair weather conditions (case 1: 1 July), a convective event dominated by southwesterly flow (case 2: 11 July), and a polluted event with high temperature and convection (case 3: 29 July). Isoprene segregation is greatest in the lower boundary layer under warm and convective conditions, reaching up to a 10% reduction in the isoprene‐OH reaction rate. Under warm and convective conditions, the BVOC lifetimes lengthen due to increased isoprene emission, elevated initial chemical concentrations, and OH competition. Although turbulence‐driven segregation has less influence on the OVOC species, convection mixes more OVOC into the upper atmospheric boundary layer (ABL) and increases the total OH reactivity. Production and loss rates of ozone above 2 km in all the three cases indicate in situ ozone formation in addition to vertical convective transport of ozone from the surface and aloft, consistent with the increased contribution of OH reactivity from OVOC. Together, these results show that total OH reactivity in the ABL increases under warmer and stronger convective conditions due to enhanced isoprene emission and the OVOC contribution to ozone formation.