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Secondary organic aerosol (SOA) makes a sizable contribution to fine-particulate-matter (PM2.5) pollution, especially during high-PM episodes. Past studies of SOA evolution at the episode scale mainly rely on measurements of bulk SOA mass, with few studies probing individual SOA molecular tracers. In this study, we continuously monitored (at a bi-hourly resolution) SOA tracers specific to a few common volatile organic compound (VOC) precursors at a suburban site in Hong Kong for a 4-month period from the end of August to December 2020. The SOA molecules include tracers for SOA derived from biomass burning (BB) emissions, monoaromatics, naphthalene/methylnaphthalenes, and three biogenic VOCs (isoprene, monoterpene, and sesquiterpene). Generally, the SOA tracers showed regional characteristics for both anthropogenic and biogenic SOA as well as for the BB-derived SOA. This work focused on the seasonal variation and evolution characteristics of SOA tracers during 11 city-wide PM2.5 episodes, which are defined as periods with PM2.5 concentrations exceeding 35 µg m−3 at 3 or more of the 15 general air quality monitoring stations cross the city. Mass increment ratios (MIR), calculated as the ratio of the mass concentration prior to an episode to that during an episode, were examined for individual species during each episode. During most episodes, the SOA tracer concentrations were enhanced (i.e. MIR >1), and the maximum MIR values were in the range of 5.5–11.0 for SOA tracers of different precursors. Episodes on summer and fall days showed notably larger MIR values than those falling on winter days, indicating the higher importance of SOA to the formation of summer/fall PM2.5 episodes. Simultaneous monitoring of six tracers for isoprene SOA revealed the dominance of the low-NOx pathway in forming isoprene SOA in our study region. The multiple monoterpene SOA products suggested fresher SOA in winter, evidenced by the increased presence of the early-generation products. Thus, the current study has shown by example the precursor-specific SOA chemical evolution characteristics during PM2.5 episodes in different seasons. This study also suggests the necessity to apply high-time-resolution organic marker measurement at multiple sites in order to fully capture the spatial heterogeneity of haze pollution at the city scale.

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 6.6 ppbv 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 2.5 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 ROx sink is via OH + NO2 reaction (1.6 ppbv h−1), followed by formation of RO2NO2 (1.0 ppbv h−1) and RONO2 (0.7 ppbv h−1). 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 32 ppbv h−1 and 6.2 ppbv h−1, respectively. Assuming NO2 to be the source of excess HONO, the NO2 to HONO transformation 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.

Using a GC/FID/MS system, we analyzed the mixing ratio of 16 halocarbon species in more than 100 air samples collected in 2004 from the Pearl River Delta (PRD) region of southern China. The results revealed that there are elevated mixing ratios for most of halocarbons, especially for HClC = CCl2 (trichloroethylene, TCE), CH2Cl2 (dichloromethane, DCM), CH3 Br (bromomethane), HCFC-22, CHCl3 (trichloromethane), CCl4 (tetrachloromethane), Cl2C = CCl2 (perchloroethylene, PCE), CH3CCl3 (methyl chloroform, MCF), and CFC-12. Comparisons were done with the data from TRACE-P and ALE/GAGE/AGAGE experiments, we found that the large variability in mixing ratios (relative standard deviation ranged from 9.31 % to 96.55 %) of the halocarbons suggested substantial local emissions from the PRD region in 2004. Correlations between the mixing ratio of each species and carbon monoxide (CO) was examined, and then the emission of each halocarbon was quantified based on scaling the optimized CO emission inventory with the slope of the regression line fitted to each species relative to CO. The calculated results revealed that mass of CH2Cl2 (7.0 Gg), CH3CCl3 (6.7 Gg), and Cl2C = CCl2 (2.3 Gg) accounted for about 62.9 % of total halocarbon emissions, it suggested a significant contribution from solvent use in the PRD region. Emissions of HCFC-22 (3.5 Gg), an alternative refrigerant to chlorofluorocarbons (CFCs), were about 2.3 times greater than those of CFC-12 (1.6 Gg). CFC-12 and HCFC-22 accounted for 21.5 % of total emissions of halocarbons, so that the refrigerant would be the second largest source of halocarbons. However, the ratio approach found only minor emissions of CFCs, such as CFC-11, and the emission of CFC-114 and CFC-113 were close to zero. Emissions of other anthropogenic halocarbons, such as CCl4, CHCl3, CH3Br, and CH3Cl, were also estimated. Where possible, the emissions estimated from the measured ratios were compared with results from source inventory techniques, we found that both approaches gave emissions at similar magnitude for most of the halocarbons, except CFC-11. The comparison suggested that the ratio method may be a useful tool for assessing regional halocarbon emissions, and emission uncertainty could be further reduced by incorporating both longer-term and higher-frequency observations, as well as improving the accuracy of the CO inventory.