Carbonyls are an important group of volatile organic compounds (VOCs) that play critical roles in tropospheric chemistry. To better understand the formation mechanisms of carbonyl compounds, extensive measurements of carbonyls and related parameters were conducted in Beijing in summer 2008. Formaldehyde (11.17 ± 5.32 ppbv), acetone (6.98 ± 3.01 ppbv), and acetaldehyde (5.27 ± 2.24 ppbv) were the most abundant carbonyl species. Two dicarbonyls, glyoxal (0.68 ± 0.26 ppbv) and methylglyoxal (MGLY; 1.10 ± 0.44 ppbv), were also present in relatively high concentrations. An observation-based chemical box model was used to simulate the in situ production of formaldehyde, acetaldehyde, glyoxal, and MGLY and quantify their contributions to ozone formation and ROx budget. All four carbonyls showed similar formation mechanisms but exhibited different precursor distributions. Alkenes (mainly isoprene and ethene) were the dominant precursors of formaldehyde, while both alkenes (e.g., propene, i-butene, and cis-2-pentene) and alkanes (mainly i-pentane) were major precursors of acetaldehyde. For dicarbonyls, both isoprene and aromatic VOCs were the dominant parent hydrocarbons of glyoxal and MGLY. Photolysis of oxygenated VOCs was the dominant source of ROx radicals (approximately >80% for HO2 and approximately >70% for RO2) in Beijing. Ozone production occurred under a mixed-control regime with carbonyls being the key VOC species. Overall, this study provides some new insights into the formation mechanisms of carbonyls, especially their parent hydrocarbon species, and underlines the important role of carbonyls in radical chemistry and ozone pollution in Beijing. Reducing the emissions of alkenes and aromatics would be an effective way to mitigate photochemical pollution in Beijing.

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.

Peroxy acetyl nitrate (PAN) is a key component of photochemical smog and plays an important role in atmospheric chemistry. Though it has been known that PAN is produced via reactions of nitrogen oxides (NOx) with some volatile organic compounds (VOCs), it is difficult to quantify the contributions of individual precursor species. Here we use an explicit photochemical model--Master Chemical Mechanism (MCM) model--to dissect PAN formation and identify principal precursors, by analyzing measurements made in Beijing in summer 2008. PAN production was sensitive to both NOx and VOCs. Isoprene was the predominant VOC precursor at suburb with biogenic impact, whilst anthropogenic hydrocarbons dominated at downtown. PAN production was attributable to a relatively small class of compounds including NOx, xylenes, trimethylbenzenes, trans/cis-2-butenes, toluene, and propene. MCM can advance understanding of PAN photochemistry to a species level, and provide more relevant recommendations for mitigating photochemical pollution in large cities.