Photochemical Formation of C₁–C₅ Alkyl Nitrates in Suburban Hong Kong and over the South China Sea

Alkyl nitrates (RONO₂) are important reservoirs of atmospheric nitrogen, regulating nitrogen cycling and ozone (O₃) formation. In this study, we found that propane and <i>n</i>-butane were significantly lower at the offshore site (WSI) in Hong Kong (<i>p</i> < 0.05), whereas C₃–C₄ RONO₂ were comparable to the suburban site (TC) (<i>p</i> > 0.05). Stronger oxidative capacity at WSI led to more efficient RONO₂ formation. Relative incremental reactivity (RIR) was for the first time used to evaluate RONO₂–precursor relationships. In contrast to a consistently volatile organic compounds (VOC)-limited regime at TC, RONO₂ formation at WSI switched from VOC-limited regime during O₃ episodes to VOC and nitrogen oxides (NO_<i>x</i>) colimited regime during nonepisodes. Furthermore, unlike the predominant contributions of parent hydrocarbons to C₄–C₅ RONO₂, the production of C₁–C₃ RONO₂ was more sensitive to other VOCs like aromatics and carbonyls, which accounted for ∼40–90% of the productions of C₁–C₃ alkylperoxy (RO₂) and alkoxy radicals (RO) at both sites. This resulted from the decomposition of larger RO₂/RO and the change of OH abundance under the photochemistry of other VOCs. This study advanced our understanding of the photochemical formation of RONO₂, particularly the relationships between RONO₂ and their precursors, which were not confined to the parent hydrocarbons

Secondary Formation and Impacts of Gaseous Nitro-Phenolic Compounds in the Continental Outflow Observed at a Background Site in South China

Nitro-phenolic compounds (NPs) have attracted increasing attention because of their health risks and impacts on visibility, climate, and atmospheric chemistry. Despite many measurements of particulate NPs, the knowledge of their gaseous abundances, sources, atmospheric fates, and impacts remains incomplete. Here, 18 gaseous NPs were continuously measured with a time-of-flight chemical ionization mass spectrometer at a background site in South China in autumn and winter. Abundant NPs were observed in the continental outflows from East Asia, with a total concentration up to 122.1 pptv. Secondary formation from the transported aromatics dominated the observed NPs, with mono-NPs exhibiting photochemical daytime peaks and nighttime enrichments of di-NPs and Cl-substituted NPs. The budget analysis indicates that besides the •OH oxidation of aromatics, the NO3• oxidation also contributed significantly to the daytime mono-NPs, while the further oxidation of mono-NPs by NO3• dominated the nocturnal formation of di-NPs. Photolysis was the main daytime sink of NPs and produced substantial HONO, which would influence atmospheric oxidation capacity in downwind and background regions. This study provides quantitative insights on the formation and impacts of gaseous NPs in the continental outflow and highlights the role of NO3• chemistry in the secondary nitro-aromatics production that may facilitate regional pollution

Molecular Composition of Oxygenated Organic Molecules and Their Contributions to Organic Aerosol in Beijing

The understanding at a molecular level of ambient secondary organic aerosol (SOA) formation is hampered by poorly constrained formation mechanisms and insufficient analytical methods. Especially in developing countries, SOA related haze is a great concern due to its significant effects on climate and human health. We present simultaneous measurements of gas-phase volatile organic compounds (VOCs), oxygenated organic molecules (OOMs), and particle-phase SOA in Beijing. We show that condensation of the measured OOMs explains 26–39% of the organic aerosol mass growth, with the contribution of OOMs to SOA enhanced during severe haze episodes. Our novel results provide a quantitative molecular connection from anthropogenic emissions to condensable organic oxidation product vapors, their concentration in particle-phase SOA, and ultimately to haze formation