Summertime photochemistry during CAREBeijing-2007: RO x budgets and O3 formation

Abstract

We analyze summertime photochemistry near the surface in Beijing, China, using a 1-D photochemical model (Regional chEmical and trAnsport Model, REAM-1D) constrained by in situ observations, focusing on the budgets of RO x (OH + HO 2 + RO 2) radicals and O3 formation. While the modeling analysis focuses on near-surface photochemical budgets, the implications for the budget of O 3 in the planetary boundary layer are also discussed. In terms of daytime average, the total RO x primary production rate near the surface in Beijing is 6.6 ppbv per hour (ppbv h -1, among the highest found in urban atmospheres. The largest primary RO x source in Beijing is photolysis of oxygenated volatile organic compounds (OVOCs), which produces HO 2 and RO 2 at 2.5 ppbv h -1 and 1.7 ppbv h -1, respectively. Photolysis of excess HONO from an unknown heterogeneous source is the predominant primary OH source at 2.2 ppbv h -1, much larger than that of O1D+H2O (0.4 ppbv h -1). The largest RO x sink is via OH + NO 2 reaction (1.6 ppbv h -1), followed by formation of RO 2NO 2 (1.0 ppbv h -1) and RONO 2 (0.7 ppbv h -1). Due to the large aerosol surface area, aerosol uptake of HO 2 appears to be another important radical sink, although the estimate of its magnitude is highly variable depending on the uptake coefficient value used. The daytime average O 3 production and loss rates near the surface are 32 ppbv h -1 and 6.2 ppbv h -1, respectively. Assuming NO 2 to be the source of excess HONO, the NO 2 to HONO transformation leads to considerable O 3 loss and reduction of its lifetime. Our observation-constrained modeling analysis suggests that oxidation of VOCs (especially aromatics) and heterogeneous reactions (e.g. HONO formation and aerosol uptake HO 2) play potentially critical roles in the primary radical budget and O 3 formation in Beijing. One important ramification is that O 3 production is neither NOx nor VOC limited, but in a transition regime where reduction of either NOx or VOCs could result in reduction of O 3 production. The transition regime implies more flexibility in the O 3 control strategies than a binary system of either NO x or VOC limited regime. The co-benefit of concurrent reduction of both NO x and VOCs in reducing column O 3 production integrated in the planetary boundary layer is significant. Further research on the spatial extent of the transition regime over the polluted eastern China is critically important for controlling regional O 3 pollution. © 2012 Author(s).