It is challenging to reduce ground-level ozone (O3) pollution at a given locale, due in part to the contributions of both local and distant sources. We present direct evidence that the increasing regional effects have negated local control efforts for O3 pollution in Hong Kong over the past decade, by analyzing the daily maximum 8 h average O3 and Ox (=O3+NO2) concentrations observed during the high O3 season (September-November) at Air Quality Monitoring Stations. The locally produced Ox showed a statistically significant decreasing trend over 2002-2013 in Hong Kong. Analysis by an observation-based model confirms this decline in in situ Ox production, which is attributable to a reduction in aromatic hydrocarbons. However, the regional background Ox transported into Hong Kong has increased more significantly during the same period, reflecting contributions from southern/eastern China. The combined result is a rise in O3 and a nondecrease in Ox. This study highlights the urgent need for close cross-boundary cooperation to mitigate the O3 problem in Hong Kong. China's air pollution control policy applies primarily to its large cities, with little attention to developing areas elsewhere. The experience of Hong Kong suggests that this control policy does not effectively address secondary pollution, and that a coordinated multiregional program is required.

Many taxis and public buses are powered by liquefied petroleum gas (LPG) in Hong Kong. With more vehicles using LPG, they have become the major contributor to ambient volatile organic compounds (VOCs) in Hong Kong. An intervention program which aimed to reduce the emissions of VOCs and nitrogen oxides (NOx) from LPGfueled vehicles was implemented by the Hong Kong government in September 2013. Long-term real-time measurements indicated that the program was remarkably effective in reducing LPG-related VOCs, NOx and nitric oxide (NO) in the atmosphere. Receptor modeling results further revealed that propane, propene, i-butane, n-butane and NO in LPGfueled vehicle exhaust emissions decreased by 40.8±0.1, 45.7±0.2, 35.7±0.1, 47.8±0.1 and 88.6±0.7 %, respectively, during the implementation of the program. In contrast, despite the reduction of VOCs and NOx, O3 following the program increased by 0.40±0.03 ppbv (∼5.6 %). The LPGfueled vehicle exhaust was generally destructive to OH and HO2. However, the destruction effect weakened for OH and it even turned to positive contribution to HO2 during the program. These changes led to the increases of OH, HO2 and HO2 =OH ratio, which might explain the positive O3 increment. Analysis of O3-VOCs-NOx sensitivity in ambient air indicated VOC-limited regimes in the O3 formation before and during the program. Moreover, a maximum reduction percentage of NOx (i.e., 69 %) and the lowest reduction ratio of VOCs =NOx (i.e., 1.1) in LPG-fueled vehicle exhaust were determined to give a zero O3 increment. The findings are of great help to future formulation and implementation of control strategies on vehicle emissions in Hong Kong, and could be extended to other regions in China and around the world.

We analyze a photochemical smog episode to understand the oxidative capacity and radical chemistry of the polluted atmosphere in Hong Kong and the Pearl River Delta (PRD) region. A photochemical box model based on the Master Chemical Mechanism (MCM v3.2) is constrained by an intensive set of field observations to elucidate the budgets of ROx (ROx DOHCHO2CRO2) and NO3 radicals. Highly abundant radical precursors (i.e. O3, HONO and carbonyls), nitrogen oxides (NOx) and volatile organic compounds (VOCs) facilitate strong production and efficient recycling of ROx radicals. The OH reactivity is dominated by oxygenated VOCs (OVOCs), followed by aromatics, alkenes and alkanes. Photolysis of OVOCs (except for formaldehyde) is the dominant primary source of ROx with average daytime contributions of 34-47 %. HONO photolysis is the largest contributor to OH and the second-most significant source (19-22 %) of ROx. Other considerable ROx sources include O3 photolysis (11-20 %), formaldehyde photolysis (10-16 %), and ozonolysis reactions of unsaturated VOCs (3.9-6.2 %). In one case when solar irradiation was attenuated, possibly by the high aerosol loadings, NO3 became an important oxidant and the NO3-initiated VOC oxidation presented another significant ROx source (6.2 %) even during daytime. This study suggests the possible impacts of daytime NO3 chemistry in the polluted atmospheres under conditions with the co-existence of abundant O3, NO2, VOCs and aerosols, and also provides new insights into the radical chemistry that essentially drives the formation of photochemical smog in the high-NOx environment of Hong Kong and the PRD region.

Nitryl chloride (ClNO2) plays potentially important roles in atmospheric chemistry, but its abundance and effect are not fully understood due to the small number of ambient observations of ClNO2 to date. In late autumn 2013, ClNO2 was measured with a chemical ionization mass spectrometer (CIMS) at a mountain top (957 m above sea level) in Hong Kong. During 12 nights with continuous CIMS data, elevated mixing ratios of ClNO2 (>400 parts per trillion by volume) or its precursor N2O5 (>1000 pptv) were observed on six nights, with the highest ever reported ClNO2 (4.7 ppbv, 1 min average) and N2O5 (7.7 ppbv, 1 min average) in one case. Backward particle dispersion calculations driven by winds simulated with a mesoscale meteorological model show that the ClNO2/N2O5 -laden air at the high-elevation site was due to transport of urban/industrial pollution north of the site. The highest ClNO2/N2O5 case was observed in a later period of the night and was characterized with extensively processed air and with the presence of nonoceanic chloride. A chemical box model with detailed chlorine chemistry was used to assess the possible impact of the ClNO2 in the well-processed regional plume on next day ozone, as the air mass continued to downwind locations. The results show that the ClNO2 could enhance ozone by 5–16% at the ozone peak or 11–41% daytime ozone production in the following day. This study highlights varying importance of the ClNO2 chemistry in polluted environments and the need to consider this process in photochemical models for prediction of ground-level ozone and haze.