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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 ROx (OH + HO2 + RO2) radicals and O3 formation. While the modeling analysis focuses on near-surface photochemical budgets, the implications for the budget of O3 in the planetary boundary layer are also discussed. In terms of daytime average, the total ROx primary production rate near the surface in Beijing is 6.6ppbv per hour (ppbv h-1, among the highest found in urban atmospheres. The largest primary ROx source in Beijing is photolysis of oxygenated volatile organic compounds (OVOCs), which produces HO2 and RO2 at 2.5ppbv h-11 and 1.7ppbv h-1, respectively. Photolysis of excess HONO from an unknown heterogeneous source is the predominant primary OH source at 2.2ppbv h-1, much larger than that of O¹D+H2O (0.4 ppbv h-11). The largest ROx sink is via OH + NO2 reaction (1.6 ppbv h-11), followed by formation of RO2NO2 (1.0 ppbv h-1) and RONO2 (0.7 ppbv h-11). Due to the large aerosol surface area, aerosol uptake of HO2 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 O3 production and loss rates near the surface are 32ppbv h-1 and 6.2ppbv h-1, respectively. Assuming NO2 to be the source of excess HONO, the NO2 to HONO trans formation leads to considerable O3 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 HO2) play potentially critical roles in the primary radical budget and O3 formation in Beijing. One important ramification is that O3 production is neither NOx nor VOC limited, but in a transition regime where reduction of either NOx or VOCs could result in reduction of O3 production. The transition regime implies more flexibility in the O3 control strategies than a binary system of either NOx or VOC limited regime. The co-benefit of concurrent reduction of both NOx and VOCs in reducing column O3 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 O3 pollution. [ABSTRACT FROM AUTHOR]

The concentrations of air pollutants such as nitrogen oxides and ozone characterised by very fast chemical reactions can significantly vary within urban street-canyon due to the short distances between sources and receptor. With the primary objective to analyse this issue, NO, NO2, NO x , O3, BTX, and wind flow field were continuously measured for 1 week at two heights (a street-level yard and a 25-m-high rooftop) in an urban canyon in Suzhou (China). The yard ozone concentrations were found to be up to six times lower than on the roof. Different frequency distributions (FD), dynamical and chemical processes of the pollutant variations from yard to roof are discussed to explain the findings. The predominant factors for the dissimilar pollutant vertical diffusion at the two measurement locations were associated to dissimilar fluid-dynamic and heterogeneous removal effects that likely induced dissimilar ozone chemical processes relative to NO x and BTX precursors. [Copyright &y& Elsevier]

We analyze the observations of near-surface peroxy acetyl nitrate (PAN) and its precursors in Beijing, China in August of 2007. The levels of PAN are remarkably high (up to 14 ppbv), surpassing those measured over other urban regions in recent years. Analyses employing a 1-D version of a chemical transport model (Regional chEmical and trAnsport Model, REAM) indicate that aromatic non-methane hydrocarbons (NMHCs) are the dominant (55-75%) PAN source. The major oxidation product of aromatics that produces acetyl peroxy radicals is methylglyoxal (MGLY). PAN and O(3) in the observations are correlated at daytime; aromatic NMHCs appear to play an important role in O(3) photochemistry. Previous NMHC measurements indicate the presence of reactive aromatics at high levels over broad polluted regions of China. Aromatics are often ignored in global and (to a lesser degree) regional 3D photochemical transport models; their emissions over China as well as photochemistry are quite uncertain. Our findings suggest that critical assessments of aromatics emissions and chemistry (such as the yields of MGLY) are necessary to understand and assess ozone photochemistry and regional pollution export in China.

Based on an air pollution modeling system coupling with the non-hydrostatic fifth generation mesoscale meteorological model (MM5) and the regional modeling system for aerosols and deposition (REMSAD), the forecast results of NOx and SO2 in August and September 2002 in Nanjing were assimilated with the optimal interpolation method and the ensemble Kalman filter. The results show that the improvement rates of deviation mean value of NOx and SO2 after assimilated with the optimal interpolation method are 34.20% and 47.53%, and the improvement rates of root mean square errors are 31.95% and 42.04% respectively. It is also demonstrated that the improvement rates of deviation mean value of NOx and SO2 after assimilated with the ensemble Kalman filter with 30 ensemble members are 26.73% and 60.75%, and the improvement rates of root mean square errors are 25.20% and 55.16% respectively. So, the optimal interpolation method and the ensemble Kalman filter both can improve the quality of the initial state from the air pollution numerical prediction model. The comparative experiments on the assimilation performance with the optimal interpolation method and the ensemble Kalman filter with 61 ensemble members were performed, and the experiments demonstrate that the assimilation performance of the ensemble Kalman filter with 61 ensemble members were improved compared with 30 ensemble members, and with the increase of the ensemble members, the improvement to the initial state of NOx and SO2 with the ensemble Kalman filter will be better than the optimal interpolation method.