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

Evidence for Reducing Volatile Organic Compounds to Improve Air Quality from Concurrent Observations and In Situ Simulations at 10 Stations in Eastern China

Ground-level ozone (O3) has been an emerging air pollution in China and interacts with fine particulate matters (PM2.5). We synthesized observations of O3 and its precursors in two summer months of 2020 at 10 sites in the Zhejiang province, East China and simulated the in situ photochemistry. O3 pollution in the northeastern Zhejiang province was more serious than that in the southwest. The site-average daytime O3 increment correlated well (R2 = 0.73) with the total reactivity of volatile organic compounds (VOCs) and carbon monoxide toward the hydroxyl radical (OH) in urban areas. Model simulation revealed that the main function of nitrogen oxides (NOx) at the rural sites where isoprene accounted for >85% of OH reactivity of VOCs was to facilitate the radical cycling. With NOx reduction from 0 to 90%, the self-reactions between peroxy radicals (Self-Rxns), a proven pathway for secondary organic aerosol formation, were intensified by up to 23-fold in a NOx-rich environment. In contrast, reducing VOCs could weaken the Self-Rxns while reducing O3 production rate and atmospheric oxidation capacity. This study observes and simulates O3 chemistry based on extensive measurements in typical Chinese cities, highlighting the necessity of reducing VOCs for co-benefit of O3 and PM2.5

Does Ozone Pollution Share the Same Formation Mechanisms in the Bay Areas of China?

As important regions of transition between land and sea, the three bay areas of Bohai Bay (BHB), Hangzhou Bay (HZB), and Pearl River Estuary (PRE) in China often suffer from severe photochemical pollution despite scarce anthropogenic emissions. To understand the causes of high ozone (O3) concentrations, the high O3 episode days associated with special synoptic systems in the three bays were identified via observations and simulated by the weather research and forecasting coupled with community multiscale air quality (WRF-CMAQ) model. It was revealed that the interaction between synoptic winds and mesoscale breezes resulted in slow wind speeds over the HZB and PRE, where air pollutants transported from upwind cities gained a long residence time and subsequently participated in intensive photochemical reactions. The net O3 production rates within the bay areas were even comparable to those in surrounding cities. This finding was also applicable to BHB but with lower net O3 production rates, while high levels of background O3 and the regional transport from farther upwind BHB partially elevated the O3 concentrations. Hence, these three bay areas served as O3 “pools” which caused the accumulation of air pollutants via atmospheric dynamics and subsequent intense photochemical reactions under certain meteorological conditions. The results may be applicable to other similar ecotones around the world

Secondary Organic Aerosol Formation from Urban Roadside Air in Hong Kong

Motor vehicle emissions are an important but poorly constrained source of secondary organic aerosol (SOA). Here, we investigated in situ SOA formation from urban roadside air in Hong Kong during winter time using an oxidation flow reactor (OFR), with equivalent atmospheric oxidation ranging from several hours to several days. The campaign-average mass enhancement of OA, nitrate, sulfate, and ammonium upon OFR aging was 7.0, 7.2, 0.8, and 2.6 μg m–3, respectively. To investigate the sources of SOA formation potential, we performed multilinear regression analysis between measured peak SOA concentrations from OFR and the concentrations of toluene that represent motor vehicle emissions and cooking OA from positive matrix factorization (PMF) analysis of ambient OA. Traffic-related SOA precursors contributed 92.3%, 92.4%, and 83.1% to the total SOA formation potential during morning rush hours, noon and early afternoon, and evening meal time, respectively. The SOA production factor (PF) was approximately 5.2 times of primary OA (POA) emission factor (EF) and the secondary particulate matter (PM) PF was approximately 2.6 times of primary particles EF. This study highlights the potential benefit of reducing secondary PM production from motor vehicle emissions in mitigating PM pollutions