Ionic Strength Enhances the Multiphase Oxidation Rate of Sulfur Dioxide by Ozone in Aqueous Aerosols: Implications for Sulfate Production in the Marine Atmosphere.

Multiphase oxidation of sulfur dioxide (SO2) by ozone (O3) in alkaline sea salt aerosols is an important source of sulfate aerosols in the marine atmosphere. However, a recently reported low pH of fresh supermicron sea spray aerosols (mainly sea salt) would argue against the importance of this mechanism. Here, we investigated the impact of ionic strength on the kinetics of multiphase oxidation of SO2 by O3 in proxies of aqueous acidified sea salt aerosols with buffered pH of ∼4.0 via well-controlled flow tube experiments. We find that the sulfate formation rate for the O3 oxidation pathway proceeds 7.9 to 233 times faster under high ionic strength conditions of 2-14 mol kg-1 compared to the dilute bulk solutions. The ionic strength effect is likely to sustain the importance of multiphase oxidation of SO2 by O3 in sea salt aerosols in the marine atmosphere. Our results indicate that atmospheric models should consider the ionic strength effects on the multiphase oxidation of SO2 by O3 in sea salt aerosols to improve the predictions of the sulfate formation rate and the sulfate aerosol budget in the marine atmosphere.

Investigation on the budget of peroxyacetyl nitrate (PAN) in the Yangtze River Delta: Unravelling local photochemistry and regional impact.

Peroxyacetyl nitrate (PAN) is a significant indicator of atmospheric photochemical pollution, which can influence the regional distribution of ozone (O3) and hydroxyl radical (OH) through long-range transport. However, investigations of PAN incorporating comprehensive measurement and explicit modeling analysis are limited, hindering complete understandings of its temporal behavior, sources, and impacts on photochemistry. Here we conducted a 1-year continuous observation of PAN and relative atmospheric species in Nanjing located in Yangtze River Delta (YRD). The annual mean concentration of PAN was 0.62 ± 0.49 ppbv and showed a bimodal monthly variation, peaking in April-June and November-January, respectively. This pattern is different from the typical pattern of photochemistry, suggesting important contributions of other non-photochemical processes. We further analyzed the PAN budget using an observation-based model, by which, PAN from local photochemical production and regional source could be decoupled. Our results revealed that local photochemical production of PAN is the sole contributor to PAN in summer, whereas about half of the total PAN concentration is attributed to regional source in winter. Although the formation of PAN can suppress the atmospheric oxidation capacity by consuming the peroxyacetyl radical and nitrogen dioxide (NO2), our analyses suggested this effect is minor at our station (-3.2 ± 1.1 % in summer and - 7.2 ± 2.8 % in winter for O3 formation). However, it has the potential to enhance O3 and OH formation by 14.16 % and 5.93 %, if transported to cleaner environments with air pollutants halved. Overall, our study highlights the importance of both local photochemistry and regional process in PAN budget and provides a useful evaluation on the impact of PAN on atmospheric oxidation capacity.

Response of organic aerosol characteristics to emission reduction in Yangtze River Delta region.

Organic aerosol (OA) is a major component of atmospheric particulate matter (PM) with complex composition and formation processes influenced by various factors. Emission reduction can alter both precursors and oxidants which further affects secondary OA formation. Here we provide an observational analysis of secondary OA (SOA) variation properties in Yangtze River Delta (YRD) of eastern China in response to large scale of emission reduction during Chinese New Year (CNY) holidays from 2015 to 2020, and the COVID-19 pandemic period from January to March, 2020. We found a 17% increase of SOA proportion during the COVID lockdown. The relative enrichment of SOA is also found during multi-year CNY holidays with dramatic reduction of anthropogenic emissions. Two types of oxygenated OA (OOA) influenced by mixed emissions and SOA formation were found to be the dominant components during the lockdown in YRD region. Our results highlight that these emission-reduction-induced changes in organic aerosol need to be considered in the future to optimize air pollution control measures. Electronic Supplementary Material: Supplementary material is available in the online version of this article at 10.1007/s11783-023-1714-0 and is accessible for authorized users.

Air-pollutant mass concentration changes during COVID-19 pandemic in Shanghai, China.

To curb the spread of the coronavirus, China implemented lockdown policies on January 23, 2020. The resulting extreme changes in human behavior may have influenced the air pollutants concentration. However, despite these changes, hazy weather persisted in Shanghai and became a public issue. This study aims to investigate air pollutant mass concentration changes during the lockdown in Shanghai. Air pollutant mass concentration data and meteorological data during the pre-lockdown period and the level I response lockdown period were analyzed by statistical analysis and a Lagrangian particle diffusion model. The data was classified in three periods: P1 (pre-lockdown: 10 days before the Spring Festival), P2 (the first 10 days after lockdown: during the Spring Festival celebration), and P3 (the second 10 days after lockdown: after the Spring Festival). Data for the same period in 2019 were used as a reference. The results indicate that the Spring Festival holiday in 2019 resulted in a reduction in energy consumption, which led to a decrease in PM2.5 (26.4%) and NO2 (43.41%) mass concentration, but an increase in ozone mass concentration (31.39%) in P2 compared with P1. The integrated effect of the Spring Festival holiday and lockdown in 2020 resulted in a decrease in PM2.5 (36.5%) and NO2 (51.9%) mass concentrations, but an increase in ozone mass concentration (43.8%) in P2 compared with P1. After the Spring Festival, the mass concentrations of PM2.5, SO2, and NO2 increased by 74.41%, 5.52%, and 53.28%, respectively in P3 compared with P2 in 2019. However, PM2.5 and SO2 concentrations in 2020 continued to decrease, by 14.74% and 4.61%, respectively, while NO2 mass concentration increased by 7.82% in P3 compared with P2. We also found that PM2.5 mass concentration is susceptible to regional transmission from the surrounding cities. PM2.5 and other gaseous pollutants show different correlations in different periods, while NO2 and O3 always show a strong negative correlation. The principal components before the Spring Festival in 2019 were O3 and NO2, and after the Spring Festival, they were PM2.5 and CO, while the principal components before the lockdown in 2020 were PM2.5 and CO, and during lockdown they were O3 and NO2.