Seasonal characteristics of atmospheric peroxyacetyl nitrate (PAN) in a coastal city of Southeast China: Explanatory factors and photochemical effects

Peroxyacetyl nitrate (PAN) acting as a typical indicator of photochemical pollution can redistribute NOx and modulate O3 production. Coupled with the observation-based model (OBM) and a generalized additive model (GAM), the intensive observation campaigns were conducted to reveal the pollution characteristics of PAN and its impact on O3, the contributions of influencing factors to PAN formation were also quantified in this paper. The F-values of GAM results reflecting the importance of the influencing factors showed that ultraviolet radiation (UV, F-value = 60.64), Ox (Ox = NO2+O3, 57.65), and air temperature (T, 17.55) were the main contributors in the PAN pollution in spring, while the significant effects of Ox (58.45), total VOCs (TVOCs, 21.63) and T (20.46) were found in autumn. The PAN formation rate in autumn was 1.58 times higher than that in spring, relating to the intense photochemical reaction and meteorological conditions. Without considering the transformation of peroxyacetyl radical (PA) and PAN, acetaldehyde contributed to the dominant production of PA (46 ± 4 %), followed by methylglyoxal (28 ± 3 %) and radical cycling (19 ± 3 %). The PAN formation was highly VOC-sensitive, and sufficient NOx (compared with VOCs abundance) would not be the limited factor for atmospheric photochemistry. PAN could promote or inhibit O3 formation under high or low ROx levels, respectively. The PAN promoting O3 formation mainly occurred during the periods of 11:00–16:00 (local time) when the favorable meteorological conditions (high UV and T) stimulated the photochemical reactions to offer ROx radicals, which accounted for 17 % of the whole monitoring periods in spring and 31 % in autumn. In this study, the formation mechanism of PAN and its effect on ozone were identified, which might be helpful to improve the scientific understanding of photochemical pollution in coastal areas.

Measurement report: Fast photochemical production of peroxyacetyl nitrate (PAN) over the rural North China Plain during haze events in autumn

Photochemical pollution over the North China Plain (NCP) is attracting much concern. We usually view peroxyacetyl nitrate (PAN) as the second most important photochemical pollutant featuring high mixing ratios during warm seasons. Our observations at a background site in the NCP identified high PAN concentrations, even during haze events in autumn. The substantial increasing ratios of PAN, by 244 % and 178 %, over the morning hours (08:00–12:00 local time) on 20 and 25 October 2020 were 10.6 and 7.7 times larger than those on clean days. Polluted days are characterized by higher temperature, higher humidity, and anomalous southerly winds compared with clean days. Enhanced local photochemistry has been identified as being the dominant factor that controls the PAN increase in the morning at the rural site, as the time when prevailing wind turns to a southerly wind is too late to promote direct transport of PAN from the polluted urban region. By removing the effect of direct transport of PAN, we provide a quantitative assessment of net PAN chemical production rate of 0.45 ppb h−1 for the mornings of polluted days, also demonstrating the strong local photochemistry. Using observations and calculated photolysis rates, we find that acetaldehyde oxidation by hydroxyl radical (OH) is the primary pathway of peroxyacetyl radical formation at the rural site. Acetaldehyde concentrations and production rates of HOx (HOx= OH + HO2) on polluted days are 2.8 and 2 times as large as those on clean days, leading to a remarkable increase in PAN in the morning. Formaldehyde (HCHO) photolysis dominates the daytime HOx production, thus contributing to fast photochemistry of PAN. Our observational results suggest the cause of a rapid increase in PAN during haze events in autumn at a rural site of the NCP and provide evidence of important role of HCHO photolysis in secondary pollutants at lower nitrogen oxide emissions. This highlights the urgency of carrying out strict volatile organic compound controls over the NCP during the cold season and not just in summer.

Measurement report: Fast photochemical production of peroxyacetyl nitrate (PAN) over the rural North China Plain during cold-season haze events

Photochemical pollution over the North China Plain (NCP) are attracting considerable concern. Peroxyacetyl nitrate (PAN) is usually viewed as the second most important photochemical pollutant featuring high mixing ratios during warm seasons. Our observations at a background site in the NCP identified high PAN concentrations even during cold-season haze events. The abrupt increasing rates of PAN by 244 % and 178 % over the morning hours (8:00–12:00) on 10/20 and 10/25, 2020 were 10.6 and 7.7 times those on clean days. The pollution days were characterized by higher temperature and humidity, accompanied by anomalous southerlies. Enhanced local photochemistry has been identified as the dominant factor that controls PAN increase in the morning at the rural site, as the time when prevailing wind turned to southerlies was too late to facilitate direct transport of PAN from the polluted urban region. By removing the effect of direct transport of PAN, we provide a quantitative assessment of net PAN chemical production rate of 0.45 ppb h−1 on the polluted morning, also demonstrating the strong local photochemistry. Using observations and calculated photolysis rates, we find that oxidation of acetaldehyde by hydroxyl radical (OH) is the primary pathway of peroxyacetyl radical formation at the rural site. Acetaldehyde concentrations and production rates of HOx (HOx = OH + HO2) radical on pollution days were 2.8 and 2 times that on clean days, respectively, leading to the abrupt increase of PAN in the morning. Formaldehyde (HCHO) photolysis dominates the daytime HOx production thus contributing to fast photochemistry of PAN. Our observational results fully explain the cause of rapid increase of PAN during cold days at a rural site of the NCP, as well as provide the evidence of important role of HCHO photolysis in secondary pollutants at lower nitrogen oxide emissions. This highlights the imperative to implement strict volatile organic compounds controls out of summer seasons over the NCP.

Verrucomicrobial methanotrophs grow on diverse C3 compounds and use a homolog of particulate methane monooxygenase to oxidize acetone

Short-chain alkanes (SCA; C2-C4) emitted from geological sources contribute to photochemical pollution and ozone production in the atmosphere. Microorganisms that oxidize SCA and thereby mitigate their release from geothermal environments have rarely been studied. In this study, propane-oxidizing cultures could not be grown from acidic geothermal samples by enrichment on propane alone, but instead required methane addition, indicating that propane was co-oxidized by methanotrophs. “Methylacidiphilum” isolates from these enrichments did not grow on propane as a sole energy source but unexpectedly did grow on C3 compounds such as 2-propanol, acetone, and acetol. A gene cluster encoding the pathway of 2-propanol oxidation to pyruvate via acetol was upregulated during growth on 2-propanol. Surprisingly, this cluster included one of three genomic operons (pmoCAB3) encoding particulate methane monooxygenase (PMO), and several physiological tests indicated that the encoded PMO3 enzyme mediates the oxidation of acetone to acetol. Acetone-grown resting cells oxidized acetone and butanone but not methane or propane, implicating a strict substrate specificity of PMO3 to ketones instead of alkanes. Another PMO-encoding operon, pmoCAB2, was induced only in methane-grown cells, and the encoded PMO2 could be responsible for co-metabolic oxidation of propane to 2-propanol. In nature, propane probably serves primarily as a supplemental growth substrate for these bacteria when growing on methane.

Observation-Based Summer O3 Control Effect Evaluation: A Case Study in Chengdu, a Megacity in Sichuan Basin, China

Ground-level ozone (O3), which is mainly from the photochemical reactions of NOx and volatile organic compounds (VOCs), has become a crucial pollutant obstructing air quality improvement in China. Understanding the composition, temporal variability and source apportionment of VOCs is necessary for determining effective control measures to minimize VOCs and their related photochemical pollution. To provide a comprehensive analysis of VOC sources and their contributions to ozone formation in the city of Chengdu—a megacity with the highest rates of industrial and economic development in southwest China—we conducted a one-month monitoring project at three urban sites (Shuangliu, Xindu, Junpingjie; SL, XD and JPJ, respectively) along the main north–south meteorological transport channel before and during the implemented control measures. Alkanes were the dominant group at each site, contributing to around 50% of the observed total VOCs, followed by oxygen-containing VOCs (OVOCs), aromatics, halohydrocarbons and alkenes. During the control period, the mixing ratios of most measured VOC species decreased, and O3 concentrations were down by at least 20%. VOC species experiencing the most effect from control were aromatics and OVOCs, which had higher O3 formation reactivity. This indicated that the control policies had significant influence on reductions of reactive VOC species. We also identified VOC sources at SL and XD using positive matrix factorization (PMF) and assessed their contributions to photochemical O3 formation by calculating the O3 formation potential (OFP) based on mass concentrations and maximum incremental reactivity of related VOCs. Five dominant VOC sources were identified, with the highest contributions from vehicular exhaust and fuel evaporation before control, followed by solvent utilization, biogenic background and secondary formation, and industrial emissions. Contribution from vehicular exhaust was reduced the most at SL, while at XD, secondary formation VOCs decreased significantly. VOCs from vehicular and industrial emissions and solvent utilization were found to be the dominant precursors for OFPs, particularly the species of xylenes, toluene and propene. Our results therefore suggest that priority should be given to the alleviation of photochemical pollutants for effective control of O3 formation in Chengdu. The findings from this work have important implications for formulating effective emission control policies in Chengdu.

Exploring the inconsistent variations in atmospheric primary and secondary pollutants during the 2016 G20 summit in Hangzhou, China: implications from observations and models

Complex aerosol and photochemical pollution (ozone and peroxyacetyl nitrate, PAN) frequently occur in eastern China, and mitigation strategies to effectively alleviate both kinds of pollution are urgently needed. Although the effectiveness of powerful control measures implemented by the Chinese State Council has been comprehensively evaluated in terms of reducing atmospheric primary pollutants, the effectiveness in mitigating photochemical pollution is less assessed and therefore the underlying mechanisms are still poorly understood. The stringent emission controls implemented from 24 August to 6 September 2016 during the summit for the Group of Twenty (G20) provide us a unique opportunity to address this issue. Surface concentrations of atmospheric O3, PAN, and their precursors including volatile organic compounds (VOCs) and nitrogen dioxides (NOx), in addition to the other trace gases and particulate matter, were measured at the National Reference Climatological Station (NRCS) (30.22∘ N, 120.17∘ E, 41.7 m a.s.l) in urban Hangzhou. We found significant decreases in atmospheric PAN, NOx, total VOCs, PM2.5, and sulfur dioxide (SO2) under the unfavorable meteorological conditions during G20 (DG20) relative to the adjacent period before and after G20 (BG20 and AG20), indicating that the powerful control measures were effective in reducing the pollutant emissions in Hangzhou. Unlike with the other pollutants, daily maximum 8 h average (DMA8) O3 exhibited a slight increase and then decrease from BG20 to AG20, which was mainly attributed to the variation in the solar irradiation intensity and regional transport in addition to the contribution from the implementation of stringent control measures. Results from an observation-based chemical model (OBM) indicated that acetaldehyde and methylglyoxal (MGLY) were the most important second-generation precursors of PAN, accounting for 37.3 %–51.6 % and 22.8 %–29.5 % of the total production rates including the reactions of OVOCs, propagation of other radicals, and other minor sources. Moreover, we confirmed the production of PAN and O3 was sensitive to VOCs throughout the whole period, specifically dominated by aromatics in BG20 and DG20 but by alkenes in AG20. These findings suggested that reducing emissions of aromatics, alkenes, and alkanes would mitigate photochemical pollution including PAN and O3. Source appointment results attributed the reductions of VOC source and ozone formation potentials (OFPs) during G20 to the effective emission controls on traffic (vehicle exhaust) and industrial processes (solvent utilization and industrial manufacturing). However, fuel combustion and biogenic emissions both weakened such an effect with a sizable contribution to the VOC mixing ratios (18.8 % and 20.9 %) and OFPs (25.6 % and 17.8 %), especially during the latter part of G20 (G20 II) when anthropogenic VOCs were substantially reduced. This study highlights the effectiveness of stringent emission controls in relation to traffic and industrial sources, but a coordinated program related to controlling fuel combustion and biogenic emissions is also required to address secondary pollution.