Peroxyacetyl Nitrate Formation Research Articles

Sensitivity of atmospheric peroxyacetyl nitrate (PAN) formation and its impact on ozone pollution in a coastal city

Peroxyacetyl nitrate (PAN) ranks among the troposphere's most prevalent organic peroxy radicals, and the photochemical production and loss pathways of PAN are mainly related to the generation and consumption of PA radicals. PA radicals can affect the atmospheric O3 generation by competing or providing precursors and affecting the atmospheric radical cycling. Field measurements took place at two sites in Shenzhen: the suburban site of Yangmeikeng Station (YMK) from September to October 2018, and the urban site of University town of Shenzhen (DXC) from September to October 2019. The average PAN levels of YMK and DXC were 0.57 and 0.87 ppb, which were similar to PAN concentrations in other southeastern coastal regions and lower than those in inland and northern regions in China. The model simulations showed that except PAN thermal decomposition, acetaldehyde (40.7% and 24.9%), other OVOCs (40.0% and 59.2%) and radical cycling (19.3% and 16.0%) were the major production pathways peroxyacetyl (PA) radicals at YMK and DXC. During the sampling period, the production of PAN resulted in a decreasing of local O3 generation at YMK (5.32 ± 3.2 ppb) and DXC (3.53 ± 12.21 ppb). The findings could make us more comprehensively understand the mechanism of atmospheric formation of PAN in urban and suburban sites in Shenzhen and its influence on the process of atmospheric photochemical reaction in Shenzhen.

Peroxyacetyl nitrate can be used as a comprehensive indicator of air pollution complex

With the acceleration of air cleaning activities in China, air pollution has entered a new stage characterized by seasonal interplay and predominance of fine particulate matter (PM2.5) and ozone (O3) pollutants. However, the differing peak seasons of these two pollution preclude the use of a unified indicator for air pollution complex. Given that peroxyacetyl nitrate (PAN) originates from secondary formation and persists under low-temperature conditions for extended periods, it is vital to determine whether its concentration can be used as an indicator to represent air pollution, not only in summer but also in winter. Here, PAN observational data from 2018 to 2022 for Beijing were analyzed. The results showed that during photochemical pollution events in summer, secondary formation of PAN was intense and highly correlated with O3 (R = 0.8), while during PM2.5 pollution events in winter, when the lifetime of PAN is extended due to the low temperature, the PAN concentration was highly consistent with the PM2.5 concentration (R = 0.9). As a result, the PAN concentration essentially exhibited consistency with both the seasonal trends in the exceedance of air pollution (R = 0.6) and the air quality index (R = 0.8). When the daily average concentration exceeds 0.5 and 0.9 ppb, the PAN concentration can be used as a complementary indicator of the occurrence of primary and secondary standard pollution, respectively. This study demonstrated the unique role of PAN as an indicator of air pollution complex, highlighting the comprehensive ability for air quality characterization and reducing the burden of atmospheric environment management.

Pollution characteristics of peroxyacetyl nitrate in karst areas in Southwest China

In recent years, the issue of photochemical pollution in the Guangxi region of China has escalated considerably. However, there remains a notable dearth of related research in this area. Peroxyacetyl nitrate (PAN), recognized as a reliable indicator of photochemical pollution, was the focus of our study. This study marks the inaugural observation of PAN levels in Guilin, a renowned world tourist destination situated in a typical karst region, during 1–31 October 2021. Throughout this observation period, the average volume concentration of PAN ranged from 0.087 to 2.559 ppb, which was 3.61 times higher than the South China background site of the Nanling. Combined with meteorological factors and potential source analysis, the causes of a typical high-value PAN process were explored during 24–29 October. The results showed that, during this high-value PAN event, pollution primarily originated from the horizontal transport of polluted air masses and the descent of high-altitude air masses from Hunan Province in the northeast direction. Additionally, the meteorological conditions, including high temperatures, intense radiation, and low humidity, fostered local PAN formation. Notably, traffic emissions emerged as the primary source of PAN's locally generated precursor volatile organic compounds. Furthermore, we estimated the background concentration of O3 to be approximately 20.347 ppb based on PAN monitoring data, constituting 44.4% of the total O3 levels in Guilin City. This study offers valuable insights for addressing and mitigating photochemical pollution in southern Chinese cities, while providing a theoretical foundation for regional pollution control efforts.摘要桂林是世界著名的地处喀斯特地区的旅游胜地, 其光化学污染问题日益严重.过氧乙酰硝酸酯(PAN)被认为是光化学污染的可靠指标, 也是本研究的重点. 本研究于2021年10月首次观测了桂林的PAN的浓度为0.087–2.559 ppb, 同时探讨了PAN典型高值过程的成因. 此次污染主要来源于东北方向污染气团的水平和高空输送, 同时, 高温, 强辐射和低湿度等气象条件也促进了本地PAN的形成. 本研究同时估算了桂林市的O3背景浓度为20.347 ppb.这项研究为城市的光化学污染控制工作提供了理论基础.

O3 and PAN in southern Tibetan Plateau determined by distinct physical and chemical processes

Abstract. Tropospheric ozone (O3) and peroxyacetyl nitrate (PAN) are both photochemical pollutants harmful to the ecological environment and human health. In this study, measurements of O3 and PAN as well as their precursors were conducted from May to July 2019 at Nam Co station (NMC), a highly pristine high-altitude site in the southern Tibetan Plateau (TP), to investigate how distinct transport processes and photochemistry contributed to their variations. Results revealed that, despite highly similar diurnal variations with steep morning rises and flat daytime plateaus that were caused by boundary layer development and downmixing of free-tropospheric air, day-to-day variations in O3 and PAN were in fact controlled by distinct physicochemical processes. During the dry spring season, air masses rich in O3 were associated with high-altitude westerly air masses that entered the TP from the west or the south, which frequently carried high loadings of stratospheric O3 to NMC. During the summer monsoon season, a northward shift of the subtropical jet stream shifted the stratospheric downward entrainment pathway also to the north, leading to direct stratospheric O3 entrainment into the troposphere of the northern TP, which traveled southwards to NMC within low altitudes via northerly winds in front of ridges or closed high pressures over the TP. Westerly and southerly air masses, however, revealed low O3 levels due to the overall less stratospheric O3 within the troposphere of low-latitude regions. PAN, however, was only rich in westerly or southerly air masses that crossed over polluted regions such as northern India, Nepal or Bangladesh before entering the TP and arriving at NMC from the south during both spring and summer. Overall, the O3 level at NMC was mostly determined by stratosphere–troposphere exchange (STE), which explained 77 % and 88 % of the observed O3 concentration in spring and summer, respectively. However, only 0.1 % of the springtime day-to-day O3 variability could be explained by STE processes, while 22 % was explained during summertime. Positive net photochemical formation was estimated for both O3 and PAN based on observation-constrained box modeling. Near-surface photochemical formation was unable to account for the high O3 level observed at NMC, nor was it the determining factor for the day-to-day variability of O3. However, it was able to capture events with elevated PAN concentrations and explain its day-to-day variations. O3 and PAN formation were both highly sensitive to NOx levels, with PAN being also quite sensitive to volatile organic compound (VOC) concentrations. The rapid development of transportation networks and urbanization within the TP may lead to increased emissions and loadings in NOx and VOCs, resulting in strongly enhanced O3 and PAN formation in downwind pristine regions, which should be given greater attention in future studies.

A WRF-CMAQ modeling of atmospheric peroxyacetyl nitrate and source apportionment in Central China

Atmospheric peroxyacetyl nitrate (PAN), as an essential constituent in the photochemical smog, is formed from photochemical reactions between volatile organic compounds (VOCs) and NOx. However, limited regional studies on distribution, formation and sources of PAN restrict the further understanding of the atmospheric behavior and environmental significance of PAN. In this study, the variation characteristics of PAN and the influencing factors to PAN concentrations were investigated using the WRF-CMAQ model simulation in the central China during July 2019. The results showed that the monthly mean concentration of PAN in the near-surface layer was 0.4 ppbv and increased with the height rising, accompanied by strong intra-day variation. The process analysis suggested that the removal was mainly controlled by dry deposition (57 %), followed by the gas-phase chemistry (43 %) which was mainly attributed to the thermal decomposition. Based on the sensitivity simulation, PAN concentrations decreased effectively in most of the simulated regions when precursors of VOCs and NOx emissions were reduced, and PAN concentrations were more sensitive to VOCs emissions than NOx emissions. The reduction of NOx and VOCs could lead to enhanced atmospheric oxidation in east-central region, which in turn hindered the decrease of PAN concentrations. During the simulation period, we found that emissions from industry and transportation sectors had the greatest impact on PAN concentrations in the central China, with contributions of 39 %–49 % and 33 %–41 %, respectively.

Anthropogenic Pollutants Induce Changes in Peroxyacetyl Nitrate Formation Intensity and Pathways in a Mountainous Background Atmosphere in Southern China.

Mountainous background areas are typically considered to have a clean atmosphere where peroxyacetyl nitrate (PAN) can be decomposed. This study demonstrated that PAN was photochemically formed with a simulated production rate of 0.28 ± 0.06 ppbv h-1 in the Nanling mountains (1690 m a.s.l.) of South China and that net PAN formation was dependent on both volatile organic compounds (VOCs) and NOx precursors (transition regime). In contrast to dominated acetaldehyde oxidation in previous urban and rural research, PAN at Nanling was primarily formed by methylglyoxal (38%), acetaldehyde (28%), radicals (20%), and other oxygenated volatile organic compounds (OVOCs) (13%). Moreover, when polluted air masses invaded the Nanling mountains, the PAN production rate was altered, primarily because anthropogenic aromatics intensified PAN formation via the oxidized pathways of methylglyoxal, other OVOCs, and radicals. Finally, net PAN formation at Nanling reduced the hydroxyl radical level by consuming NOx, impaired local radical cycling, and thereby suppressed local O3 production. This suppressing effect was exacerbated on polluted days. The findings of this study deepen our understanding of PAN photochemistry and the impact of anthropogenic intrusions on the background atmosphere of mountainous regions.

Strong relations of peroxyacetyl nitrate (PAN) formation to alkene and nitrous acid during various episodes

Peroxyacetyl nitrate (PAN) is one of the critical secondary pollutants in photochemical smog. This study investigated the relationship between PAN and PAN precursors with the Regional Atmospheric Chemical Mechanism version 2 model in six episodes recorded in Zhengzhou. In all episodes, peroxyacetyl radical (PA) was primarily produced by acetaldehyde oxidation, with more than 70% contributions. In photochemical episodes and photochemical-haze co-occurring episodes (combined episodes), methylglyoxal secondarily contributes 8.1%–10.6% to PA while in haze pollution, the propagation of other radicals to PA is the second most important source (12.0%–19.1%). Among anthropogenic non-methane hydrocarbons, alkene restricted PAN formation as first-generation precursors, with the relative incremental reactivity of PAN (RIRPAN) more than 0.6 during three-type episodes. Nitrous acid (HONO) also played important role in PAN formation. Especially during photochemical episodes, RIRPAN(HONO) reached 0.79, which was comparable to the RIRPAN value of alkene. Through sensitivity analysis of the relative formation of PAN to O3 (the amount of PAN generated when 100 ppb O3 formed), HONO was identified as the key precursor of PAN in haze pollution by promoting the oxidation of NMHC, while alkene predominated the relative formation of PAN to O3 in photochemical and combined pollution through producing acetaldehyde. The sensitivity of PAN to HONO is obviously enhanced with higher NOx/VOC ratios during photochemical and combined pollution.

Investigatory Studies on Pattern in Enhancement in Fine Particulate Matter in the Delhi during winters

Smog is a harmful mixture of fog, smoke, dust and air pollutants such as nitrogen oxides, volatile organic compounds etc. Ground ozone can cause distressing health effect. Smog is a complex atmospheric pollutant mixture consisting of ozone, a pollutant with adverse effects on human health, vegetation, and materials; other eye-irritant and phytotoxic pollutants (such as aldehydes and peroxyacetyl nitrates); nitrogen dioxide (cause of the “whiskey-brown” color in the Los-Angeles atmosphere); and fine particles that cause adverse health effects, reduce visibility, and cause the “brown cloud” phenomenon. Photochemical smog is produced by vehicular emission mainly. Here we are discussing chemistry of formation of PAN (Peroxyacetyl nitrate), its impact environment & human health.

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

Abstract. 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. Model simulations revealed that acetaldehyde oxidation (46 %±4 %) contributed to the dominant formation pathway of PA (hence PAN), followed by methylglyoxal oxidation (28 %±3 %) and radical cycling (19 %±3 %). The PAN formation was highly VOC sensitive, as surplus NOx (compared with VOCs abundance) prevented NOx from being the limiting factor photochemical formation of secondary pollution. At our site, PAN promoted and inhibited O3 formation under high and low ROx levels, respectively. The PAN promoting O3 formation mainly occurred during the periods of 11:00–16:00 (local time) when the favourable 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. The analysis of PAN formation mechanism and its positive or negative effect on ozone provided scientific insights into photochemical pollution mechanisms under various pollution scenarios in coastal areas.

Influence of thermal decomposition and regional transport on atmospheric peroxyacetyl nitrate (PAN) observed in a megacity in southern China

Peroxyacetyl nitrate (PAN) is a typical secondary product of photochemical smog and is widely considered an indicator when evaluating the severity of photochemical pollution, but there have been few quantitative studies on the thermal decomposition of ambient PAN in southern China. In this study, online sampling of PAN and ozone (O3) was conducted from August to November 2020, which is the most severe photochemical pollution period of the year, in Shenzhen, a megacity in southern China. During the sampling period, two photochemical pollution periods occurred in August (EP1) and October (EP2). The mean O3 concentrations during EP1 and EP2 were very close, 36.3 and 36.9 ppb, respectively, while PAN concentrations were very different (0.66 and 1.06 ppb, respectively). The diurnal variation showed that the PAN formation rate in the initial stage of photochemical reactions (9:00–11:00) during EP1 was significantly faster than that during EP2, while there was significant consumption at noon and almost complete decomposition at night in EP1. Calculating the thermal decomposition of PAN (TPAN), we found that the average concentration of TPAN in EP1 was 8.47 ppb, approximately 9 times that in EP2 (0.94 ppb), which significantly reduced the concentration of PAN in EP1. This indicates that when using PAN as an indicator of photochemical reaction activity, the consumption of PAN due to thermal decomposition must be considered. In addition, we found that regional transport may significantly contribute to the formation of PAN by increasing the concentration of precursor VOCs, although the lifetime of PAN was only a few hours due to a large amount of thermal decomposition.

Seasonal discrepancies in peroxyacetyl nitrate (PAN) and its correlation with ozone and PM2.5: Effects of regional transport from circumjacent industrial cities

Peroxyacetyl nitrate (PAN) is the most important reservoir of nitrogen oxides, with effects on atmospheric oxidation capacity and regional nitrogen distribution. The first yearlong observational study of PAN was conducted from September 2018 to August 2019 at a suburban site and an urban site in Zhengzhou, Henan Province, central China. Compared with studies over the past two decades, summer PAN pollution at the suburban site and winter PAN pollution at both sites were more significant, with annual average concentrations of 1.96 ± 1.44 and 2.01 ± 1.59 ppbv, respectively. Seasonal PAN discrepancies between the urban and suburban areas were analyzed in detail. Active PAN formation, regional transport, photochemical precursors, and PAN lifetime played key roles during seasons with elevated PAN (winter and spring). According to the results of cluster analysis and potential source contribution function analysis, during the cold months, short-distance air mass transport from the east, south, and southeast of Henan Province and southern Hebei Province increased PAN pollution in urban Zhengzhou. PAN source areas were located in circumjacent industrial cities surrounding Zhengzhou except in the northeastern direction. Based on the relationships between pollutant concentrations, wind speed, and wind direction, a strong positive correlation between PAN and PM2.5 (and O3) existed in winter due to their joint transport. A slow-moving, low-height air mass passed through surrounding industrial cities before reaching the study area, carrying both pollutants and leading to strong consistency between PAN and O3 levels. The long-term PAN characteristics described in this study will help clarify the causes of regional air pollution in inland city agglomerations. Moreover, the PAN correlations and joint transport of PAN and PM2.5 (or O3) support the use of PAN as an indicator of air pollution introduced from surrounding industrial areas.

Formation of peroxyacetyl nitrate (PAN) and its impact on ozone production in the coastal atmosphere of Qingdao, North China.

Peroxyacetyl nitrate (PAN), acting as a relatively long-lived reservoir for both NOx and radicals, plays a crucial role in ozone (O3) formation in the troposphere. However, its quantitative impacts on radical concentrations and O3 production were rarely studied in the coastal atmosphere. In this study, ambient concentrations of PAN, O3, and related species were simultaneously measured from October 5 to November 10, 2018 (autumn), and July 14 to August 24, 2019 (summer) at a rural coastal site in Qingdao, North China. The formation mechanism of PAN and its impact on in-situ O3 production were explored with an observation-based chemical box model. Photochemical formation of PAN and O3 was controlled by both NOx and VOCs, and acetaldehyde and methylglyoxal were the main contributors to PAN formation. However, the sensitivities of PAN to precursors were larger than that of O3 in autumn while smaller in summer, which was mainly caused by the rapid decomposition of PAN at high temperatures. Zero-out sensitivity simulation showed that PAN could either promote or inhibit the in-situ O3 formation by affecting the radical chemistry. It tended to suppress O3 production by competing with precursors and terminating radical chain reactions under low-NOx and low-ROx circumstances but enhanced O3 production by supplying RO2 radicals under conditions with sufficient NOx. This study provides some new complementary insights into the formation mechanism of PAN and its impacts on O3 production, and has implications for the formulation of control policy to mitigate regional photochemical pollution in northern China.

Aerosol Promotes Peroxyacetyl Nitrate Formation During Winter in the North China Plain.

Peroxyacetyl nitrate (PAN) is an important indicator for photochemical pollution, formed similar to ozone in the photochemistry of certain volatile organic compounds (VOCs) in the presence of nitrogen oxides, and has displayed surprisingly high concentrations during wintertime that were better correlated to particulate rather than ozone concentrations, for which the reasons remained unknown. In this study, wintertime observations of PAN, VOCs, PM2.5, HONO, and various trace gases were investigated to find the relationship between aerosols and wintertime PAN formation. Wintertime photochemical pollution was affirmed by the high PAN concentrations (average: 1.2 ± 1.1 ppb, maximum: 7.1 ppb), despite low ozone concentrations. PAN concentrations were determined by its oxygenated VOC (OVOC) precursor concentrations and the NO/NO2 ratios and can be well parameterized based on the understanding of their chemical relationship. Data analysis and box modeling results suggest that PAN formation was mostly contributed by VOC aging processes involving OH oxidation or photolysis rather than ozonolysis pathways. Heterogeneous reactions on aerosols have supplied key photochemical oxidants such as HONO, which produced OH radicals upon photolysis, promoting OVOC formation and thereby enhancing PAN production, explaining the observed PM2.5-OVOC-PAN intercorrelation. In turn, parts of these OVOCs might participate in the formation of secondary organic aerosol, further aggravating haze pollution as a feedback. Low wintertime temperatures enable the long-range transport of PAN to downwind regions, and how that will impact their oxidation capacity and photochemical pollution requires further assessment in future studies.

Simultaneous observation of atmospheric peroxyacetyl nitrate and ozone in the megacity of Shanghai, China: Regional transport and thermal decomposition.

Atmospheric peroxyacetyl nitrate (PAN) and ozone (O3) are two typical indicators for photochemical pollution that have adverse effects on the ecosystem and human health. Observation networks for these pollutants have been expanding in developed regions of China, such as North China Plain (NCP) and Pearl River Delta (PRD), but are sparse in Yangtze River Delta (YRD), meaning their concentration and influencing factors remain poorly understood. Here, we performed a one-year measurement of atmospheric PAN, O3, particulate matter with aerodynamic diameter smaller than 2.5μm (PM2.5), nitrogen oxides (NOx), carbon monoxide (CO), and meteorological parameters from December 2016 to November 2017 in Shanghai. Overall, high hourly maximum PAN and O3 were found to be 7.0 and 185ppbv in summer, 6.2 and 146ppbv in autumn, 5.8 and 137ppbv in spring, and 6.0 and 76.7ppbv in winter, respectively. Continental air masses probably carried atmospheric pollutants to the sampling site, while frequent maritime winds brought in less polluted air masses. Furthermore, positive correlations (R: 0.72-0.85) between PAN and O3 were found in summer, indicating a predominant role of photochemistry in their formation. Unlike in summer, weak or no correlations between PAN and O3 were featured during the other seasons, especially in winter, due to their different loss pathways. Unexpectedly, positive correlations between PAN and PM2.5 were found in all seasons. During summer, moderate correlation could be attributed to the strong photochemistry acting as a common driver in the formation of secondary aerosols and PAN. During winter, high PM2.5 might promote PAN production through HONO production, hence resulting in a good positive correlation. Additionally, the loss of PAN by thermal decomposition (TPAN) only accounted for a small fraction (ca. 1%) of the total (PAN+TPAN) during a typical winter episode, while it significantly reached 14.4ppbv (71.1% of the total) in summer.

Markedly Enhanced Levels of Peroxyacetyl Nitrate (PAN) During COVID‐19 in Beijing

AbstractHigh levels of secondary air pollutants during COVID‐19 in China have aroused great concern. In Beijing, measured daily mean peroxyacetyl nitrate (PAN) concentrations reached 4 ppb over the lockdown period (24 January to 15 February), whose averages were 2–3 times that before lockdown (1–23 January). The lockdown PAN levels also reached a high historical record based on our long‐term measurements (2016–2019). Unlike ozone and PM2.5, PAN formation depends on less complex photochemistry between NOx and volatile organic compounds (VOCs), providing a novel approach to investigate the wintertime photochemistry during COVID‐19. The GEOS‐Chem simulations suggest a markedly enhanced photochemistry by a factor of 2 during the lockdown. Change of meteorology featuring with anomalous wind convergence under higher temperatures is the main reason for enhanced photochemical formation of PAN, while chemically nonlinear feedbacks also play a role. Our results suggest implementing targeted VOC emission controls in the context of increasing photochemical pollution over this complex polluted region.

Effect of potential HONO sources on peroxyacetyl nitrate (PAN) formation in eastern China in winter

As an important secondary photochemical pollutant, peroxyacetyl nitrate (PAN) has been studied over decades, yet its simulations usually underestimate the corresponding observations, especially in polluted areas. Recent observations in north China found unusually high concentrations of PAN during wintertime heavy haze events, but the current model still cannot reproduce the observations, and researchers speculated that nitrous acid (HONO) played a key role in PAN formation. For the first time we systematically assessed the impact of potential HONO sources on PAN formation mechanisms in eastern China using the Weather Research and Forecasting/Chemistry (WRF-Chem) model in February of 2017. The results showed that the potential HONO sources significantly improved the PAN simulations, remarkably accelerated the ROx (sum of hydroxyl, hydroperoxyl, and organic peroxy radicals) cycles, and resulted in 80%–150% enhancements of PAN near the ground in the coastal areas of eastern China and 10%–50% enhancements in the areas around 35–40°N within 3 km during a heavy haze period. The direct precursors of PAN were aldehyde and methylglyoxal, and the primary precursors of PAN were alkenes with C > 3, xylenes, propene and toluene. The above results suggest that the potential HONO sources should be considered in regional and global chemical transport models when conducting PAN studies.

Impacts of precursors on peroxyacetyl nitrate (PAN) and relative formation of PAN to ozone in a southwestern megacity of China

Abstract Peroxyacetyl nitrate (PAN), an important species of photochemical smog, has received much concern for its impact on atmospheric chemistry and relation with other pollutants including ozone (O3). This study conducted PAN measurements at the CS site (urban area) and the NQ site (suburban area) of Chongqing in summer in 2015. Maximum PAN concentrations were 12.17 (mean: 2.05 ± 1.94 ppbv) and 8.53 ppbv (mean: 0.84 ± 0.89 ppbv) at the CS and NQ sites, respectively. An observation-based box model coupled with RACM2 was applied to explore PAN formation mechanisms and its key precursors. Results showed that PAN formation was limited by both nitrogen dioxides (NOX) and volatile organic compounds (VOCs) at both sites, and NOX and nitrous acid were essential PAN precursors, especially on polluted days. For VOCs, key first-generation precursors were identified as alkenes and aromatics at the CS site (aromatics and isoprene at the NQ site). On polluted days, the relative production efficiency of PAN to O3 enhanced more significantly at the NQ site (0.9 times) than at the CS site (0.4 times), which was related to formation/destruction reactivities of PAN and O3. Furthermore, this study firstly explored the quantitative impacts of precursors to the relative formation of PAN to O3, and the results indicated that NOX predominated their relative formation at both sites. For VOCs, urban alkenes and suburban aromatics contributed to elevated PAN formation relative to O3, and the increase of aromatics dominated the PAN enhancement relative to O3 during the polluted period.

Characteristics of peroxyacetyl nitrate (PAN) in a coastal city of southeastern China: Photochemical mechanism and pollution process

Peroxyacetyl nitrate (PAN) can effectively indicate photochemical pollution, and also plays a vital role in regional oxidant balance. One-year continuous monitoring of PAN in a coastal city of southeastern China was investigated. The mean concentration of PAN in winter (0.64 ppb) was close to that in autumn (0.73 ppb), indicating that photochemical pollution was still non-negligible in the cold season. The peak occurrence time between O3 and PAN had a delay of 1–2 h in four seasons, due to the rapid decomposition rate of PAN in midday. Emission sources of the precursors are located to the south of the monitoring site, so high concentrations of PAN and O3 are frequently observed under southerly wind conditions. The air mass with low concentration of PAN (0.22–0.34 ppb) and O3 (18.17–23.67 ppb) originated from the ocean with less anthropogenic air pollutants. Continental air mass with high PAN concentration might be related to the contribution of heterogeneous reactions of PM2.5 to the promotion of PAN formation. In the polluted case, PAN concentration was often higher than 1.0 ppb and reached the peak of 4.2 ppb, suggesting the influence of photochemical reactions and local accumulation. High concentrations of HONO and sufficient ultraviolet radiation might be the main factors for rapid photochemical production of PAN. Besides, the lifetime of PAN in winter under the condition of high PM2.5 concentration (≥35 μg·m−3) was up to 3.246 days. This study provided insights into photochemical mechanism and pollution process in a coastal city of southeastern China.

The abundance and inter-relationship of atmospheric peroxyacetyl nitrate (PAN), peroxypropionyl nitrate (PPN), O3, and NOy during the wintertime in Beijing, China

Although atmospheric peroxyacetyl nitrate (PAN) and O3 have been extensively measured in Beijing during the summertime, the abundances of PAN, peroxypropionyl nitrate (PPN) and the total odd-reactive nitrogen budget (NOy) and their inter-relationship have been studied comparatively less in the winter. Here we measured atmospheric PAN, PPN, O3, NOx, and NOy in Beijing from Nov. 2012 to Jan. 2013. Compared with our previous results in the summertime, much lower levels were observed in the winter, with the mean and maximum values of 311.8 and 1465 pptv for PAN, 52.8 and 850.6 pptv for PPN, and 11.6 and 36.7 ppbv for O3. In contrast, high levels were found as 94.2 and 374.9 ppbv for NOy, with a major constituent of NOx (75.9%). The source to the west and northwest made the significant contribution to the relatively high O3 concentrations during nighttime. PAN concentrations were highly related with the PAN-rich air mass transported from the southeast during the nighttime, whereas predominated by local photochemical production during the daylight. The distributions of NOx and NOy were dominated by local emission and photochemical production during daylight but also influenced by air masses transported from south direction during nighttime. Significant positive correlation (R2 = 0.9, p < 0.0001) between PAN and PPN with a slope (∆PPN/∆PAN) of 0.17 indicated that anthropogenic volatile organic compounds (AVOCs) dominated the photochemical formation of PANs in Beijing, and the independent relationship between the PPN/PAN ratio and PAN (>500 pptv) implied a steady state between PAN and PPN achieving rapidly in the polluted air masses. Negative correlation and slopes between PAN and O3 likely resulted from their weak photochemical productions in the winter, coupled with the large NO sources which acted as a local sink for O3, but much less so for PAN due to its enhanced thermal stability under low temperature.

Dispersion-box modeling investigation of the influences of gasoline, diesel, M85 and E85 vehicle exhaust emission on photochemistry

Alternative transportation fuels (ATFs) can reduce air pollution. However, the influence of conventional fuels—diesel and gasoline, and particularly ATFs on photochemical air pollution is not well-characterized, limiting assessments of ATFs and air quality. This is mainly due to frequent use of lumped chemical mechanisms by related atmospheric modeling. Here we hypothesized that applying a chemical mechanism that is specifically developed according to both emission fractions and photochemical ozone creation potential of volatile organic compounds (VOCs) is key to gaining reliable insights into the impact of transportation fuels on photochemistry. We used a heterogeneous chemical mechanism with 927 reactions and relatively detailed emission inventories to specifically meet the requirements for reliable simulation of the effect of exhaust emissions from vehicles fueled by selected model fuels—diesel, gasoline, and mixtures of 15% gasoline with 85% ethanol (E85) or 85% methanol (M85)—on photochemistry. These dispersion-box model simulations revealed a strong influence of atmospheric background balance between VOCs and nitrogen oxides (NOX = [NO] + [NO2]) on the impact of exhaust emissions on photochemistry, with higher tendency toward ozone (O3) formation or destruction for more VOC-limited or NOX-limited conditions, respectively. Accordingly, higher [NOX]/[VOC] exhaust emission, such as from diesel and M85, resulted in lower O3, not only locally but also downwind of the emission. This offers a new perspective and measure for transportation fuel assessment. Rapid conversion of O3 to hydroxyl and hydroperoxyl radicals downwind of the exhaust emission indicates the importance of simulating the impact of road transportation on photochemistry at high spatial and temporal resolution. Peroxyacetyl nitrate formation was more sensitive to VOC emission under VOC-limited conditions than to NOX emission under NOX-limited conditions. Secondary formaldehyde dominated over primary emitted formaldehyde several minutes after emission. These findings should be verified using a 3D modeling study under varying meteorological conditions.