Atmospheric Peroxyacetyl Nitrate 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.

Seasonal discrepancies and inter-relationship of peroxyacetyl nitrate (PAN), ozone, and other environmental factors in Hangzhou, East China

Peroxyacetyl nitrate (PAN, CH3C(O)OONO2) and ozone (O3) are both important photochemical products, both of which are detrimental to air quality, human health and ecosystem. In this study, we measured atmospheric PAN, O3 and other pollutants in Hangzhou during the whole 2021 year. Observed results revealed that the average concentrations of PAN and O3 during the whole observation period were 1.59 and 27.09 ppbv, respectively. PAN concentrations declined from the weekday to weekend, while O3 presented the reverse pattern. The abundance of PAN and O3 showed different variations in all seasons. Serious photochemical pollution in spring and autumn were featured by higher PAN levels (mean of 1.74 and 1.66 ppbv); whereas those in summer and spring were characterized by higher O3 levels (mean of 32.34 and 30.98 ppbv). With the extremely higher PAN/O3 ratio of 0.10, the results suggested the high-level photochemical pollution in Hangzhou. In all seasons, the diurnal peak of PAN appeared earliest in summer could be associated with rapid decomposition rate of PAN at noon with higher temperatures. The correlation between PAN and other factors varies across all seasons due to the environmental conditions are unique in each season. Through analysis of conditional probability function (CPF) and toluene/benzene ratio, traffic sources were identified as the main factor contributing to high PAN and O3 accumulation at a regional scale. Furthermore, backward trajectory analysis revealed that marine air masses affected the air of the monitoring site in both summer and autumn; whereas continental air masses impacted it in both spring and winter. This study provides novel insights into photochemical pollution process in a coastal city, eastern China.

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.

Seasonal variation characteristics of atmospheric peroxyacetyl nitrate (PAN) and its source apportionment in a megacity in southern China

Owing to its biotoxicity and inductive effect on photochemical pollution, atmospheric peroxyacetyl nitrate (PAN), which is a typical product of atmospheric photochemical reactions, has attracted much research attention. However, to the best of our knowledge, few comprehensive studies have been conducted on the seasonal variation and key influencing factors of PAN concentrations in southern China. In this study, PAN, ozone (O3), precursor volatile organic compound (VOC), and other pollutant concentrations were measured online for 1 year (from October 2021 to September 2022) in Shenzhen, a megacity in the Greater Bay Area of China. The average concentrations of PAN and peroxypropionyl nitrate (PPN) were 0.54 and 0.08 parts per billion (ppb), and the maximum hourly concentrations reached 10.32 and 1.01 ppb, respectively. The results of the generalized additive model (GAM) showed that the atmospheric oxidation capacity and precursor concentration were the most important factors affecting the PAN concentration. According to the steady-state model, the average cumulative contribution to the peroxyacetyl (PA) radical formation rate by six major carbonyl compounds was calculated at 4.2 × 106 molecules cm−3 s−1, and acetaldehyde (63.0 %) and acetone (13.9 %) contributed the most. Furthermore, the photochemical-age-based parameterization method was used to analyze the source contributions of carbonyl compounds and PA radicals. The results showed that although the primary anthropogenic (40.2 %), biogenic (27.8 %), and secondary anthropogenic (16.4 %) sources were the most important contributors of PA radicals, the biogenic and secondary anthropogenic source contributions both increased considerably in summer, and the cumulative proportion of both sources reached ~70 % in July. In addition, a comparison of PAN pollution processes in different seasons revealed that in summer and winter, the PAN concentration was predominantly limited by precursors and meteorological parameters, such as light intensity, respectively.

Heterogeneous Reaction of Peroxyacetyl Nitrate on Real-World PM2.5 Aerosols: Kinetics, Influencing Factors, and Atmospheric Implications.

The formation and decomposition of peroxyacetyl nitrate (PAN), an important atmospheric nitrogen oxide reservoir, can impact the level and cycling of free radicals and nitrogen compounds in the atmosphere. PAN sinks are poorly understood, highlighting the importance of elucidating the heterogeneous reaction of PAN on aerosol surfaces. Here, we report for the first time the uptake behavior, kinetics, and potential mechanism of PAN uptake on real-world aerosol PM2.5 using a flow tube system. The uptake coefficients (γ) of PAN increased non-linearly from (1.5 ± 0.7) × 10-5 at 0% relative humidity (RH) to (9.3 ± 2.0) × 10-5 at 80% RH. The γ decrease with increasing initial PAN concentration is consistent with the Langmuir-Hinshelwood mechanism. Organic components of aerosols may promote heterogeneous loss of PAN through redox reactions. Higher γ occurs with higher water content, lower pH, and lower ionic strength in the aqueous phase of aerosols. The present study suggests that heterogeneous reaction of PAN on ambient aerosols plays a non-negligible role in the atmospheric PAN budget and provides new insights into the role of PAN in promoting atmospheric oxidation capacity during hazy periods with cold and wet weather conditions.

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.

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.

Peroxyacetyl nitrate (PAN) in the border of Beijing, Tianjin and Hebei of China: Concentration, source apportionment and photochemical pollution assessment

A one-year observation of atmospheric peroxyacetyl nitrate (PAN) in the border of Beijing-Tianjin-Hebei (BTH) was conducted during 2018–2019 to assess the photochemical pollution in this region. PAN daily average was 2.23, 3.72, 5.34 and 2.44 ppb(v) in October, January, April and July. The higher PAN here compared to previous studies on urban Beijing implies the deterioration of photochemical pollution in BTH region. High positive correlation between PAN and CO in October and January points to the important role of tropospheric accumulation in PAN level in fall and winter; while ΔO3/ΔPAN analysis implies that the photochemical pollution was more aged in this border than in urban Beijing, and more aged in October than in April. Based on the calculations of PAN photochemical formation and thermal decomposition, PAN yield rate was determined, 0.20, 0.07, 0.47 and 0.08 ppt·s−1 for daily average, 0.87, 0.32, 0.95 and 0.93 ppt·s−1 for daily maximum, respectively in October, January, April, and July. Local photochemical pollutions still existed in the border of BTH in non-winter seasons. Potential source contribution function analysis (PSCF) found that the grids that most potentially contribute to high PAN appeared around the border site in July, 50–100 km away in direction of southwest in January, both around this site and along the southern trajectory clusters in October and April. Transport of PAN from South Hebei and Tianjin to Beijing could be seen in non-summer seasons. Regression analyses further quantified the contribution of regional transport to PAN in the border, roughly 65% (April and October), 93% (January) and 48% (July) at noon time. Finally, the comparison in PAN during 12:00–16:00 under various winds explores the more severe photochemical pollutions in South Hebei and Tianjin compared to Beijing in non-summer seasons, but the same level of photochemical pollutions in various cities of BTH in summer.

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.

Atmospheric fate of peroxyacetyl nitrate in suburban Hong Kong and its impact on local ozone pollution

Peroxyacetyl nitrate (PAN) is an important reservoir of atmospheric nitrogen, modulating reactive nitrogen cycle and ozone (O3) formation. To understand the origins of PAN, a field measurement was conducted at Tung Chung site (TC) in suburban Hong Kong from October to November 2016. The average level of PAN was 0.63 ± 0.05 ppbv, with a maximum of 7.30 ppbv. Higher PAN/O3 ratio (0.043–0.058) was captured on episodes, i.e. when hourly maximum O3 exceeded 80 ppbv, than on non-episodes (0.01), since O3 production was less efficient than PAN when there was an elevation of precursors (i.e. volatile organic compounds (VOCs) and nitrogen oxide (NOx)). Model simulations revealed that oxidations of acetaldehyde (65.3 ± 2.3%), methylglyoxal (MGLY, 12.7 ± 1.2%) and other oxygenated VOCs (OVOCs) (8.0 ± 0.6%), and radical cycling (12.2 ± 0.8%) were the major production pathways of peroxyacetyl (PA) radical, while local PAN formation was controlled by both VOCs and nitrogen dioxide (NO2). Among all VOC species, carbonyls made the highest contribution (59%) to PAN formation, followed by aromatics (26%) and biogenic VOCs (BVOCs) (10%) through direct oxidation/decomposition. Besides, active VOCs (i.e. carbonyls, aromatics, BVOCs and alkenes/alkynes) could stimulate hydroxyl (OH) production, thus indirectly facilitating the PAN formation. Apart from primary emissions, carbonyls were also generated from oxidation of first-generation precursors, i.e., hydrocarbons, of which xylenes contributed the most to PAN production. Furthermore, PAN formation suppressed local O3 formation at a rate of 2.84 ppbv/ppbv, when NO2, OH and hydroperoxy (HO2) levels decreased and nitrogen monoxide (NO) value enhanced. Namely, O3 was reduced by 2.84 ppbv per ppbv PAN formation. Net O3 production rate was weakened (∼36%) due to PAN photochemistry, so as each individual production and loss pathway. The findings advanced our knowledge of atmospheric PAN and its impact on O3 production.

GC/NICI-MS法を用いた東アジアにおける大気中PANの季節変化観測

GC/NICI-MS法を用いた東アジアにおける大気中PANの季節変化観測

Influence of local air pollution on the deposition of peroxyacetyl nitrate to a nutrient-poor natural grassland ecosystem

Abstract. Dry deposition of peroxyacetyl nitrate (PAN) is known to have a phytotoxic impact on plants under photochemical smog conditions, but it may also lead to higher productivity and threaten species richness of vulnerable ecosystems in remote regions. However, underlying mechanisms or controlling factors for PAN deposition are not well understood and studies on dry deposition of PAN are limited. In this study, we investigate the impact of PAN deposition on a nutrient-poor natural grassland ecosystem situated at the edge of an urban and industrialized region in Germany. PAN mixing ratios were measured within a 3.5 months summer to early autumn period. In addition, PAN fluxes were determined with the modified Bowen ratio technique for a selected period. The evaluation of both stomatal and non-stomatal deposition pathways was used to model PAN deposition over the entire summer–autumn period. We found that air masses at the site were influenced by two contrasting pollution regimes, which led to median diurnal PAN mixing ratios ranging between 50 and 300 ppt during unpolluted and between 200 and 600 ppt during polluted episodes. The measured PAN fluxes showed a clear diurnal cycle with maximal deposition fluxes of ~−0.1 nmol m−2 s−1 (corresponding to a deposition velocity of 0.3 cm s−1) during daytime and a significant non-stomatal contribution was found. The ratio of PAN to ozone deposition velocities was found to be ~0.1, which is much larger than assumed by current deposition models. The modelled PAN flux over the entire period revealed that PAN deposition over an entire day was 333 μg m−2 d−1 under unpolluted and 518 μg m−2 d−1 under polluted episodes. Additionally, thermochemical decomposition PAN deposition accounted for 32% under unpolluted episodes and 22% under polluted episodes of the total atmospheric PAN loss. However, the impact of PAN deposition as a nitrogen source to the nutrient-poor grassland was estimated to be only minor, under both unpolluted and polluted episodes.

Summertime distributions of peroxyacetyl nitrate (PAN) and peroxypropionyl nitrate (PPN) in Beijing: Understanding the sources and major sink of PAN

Peroxyacetyl nitrate (PAN), a major secondary pollutant in the atmosphere, has received much concern for its particular importance in atmospheric chemistry and adverse effects on human and plants. Atmospheric PAN and PPN were measured by using a gas chromatograph equipped with electron capture detector (GC-ECD) from June to September 2010, and the source and major sink for PAN were firstly studied in Beijing. The distinct diurnal variations of PAN and PPN with maximum in the afternoon were observed, and the mean and maximum values were 2.61 ± 2.57 ppbv (N = 839) and 12.5 ppbv for PAN and 0.52 ± 0.38 ppbv (N = 152) and 2.16 ppbv for PPN during the measuring period, respectively. Good correlation (R = 0.85) between PAN and PPN with a slope (ΔPPN/ΔPAN) of 0.134 indicated that anthropogenic volatile organic compounds (AVOCs) dominated the photochemical formation of PANs in Beijing. Further, we found acetaldehyde was the predominant carbonyl precursor of PAN with the contribution of 59.7% to the total peroxyacetyl (PA) radical. Methyl glyoxal, methacrolein, acetone, methyl vinyl ketone, and biacetyl contributed 7.1%, 8.8%, 19.7%, 3.4%, and 1.3% to total PA radical, respectively. Anti-correlation between PAN concentrations and the NO/NO2 ratios was found during the whole investigating period. In addition, the amount of PAN lost by thermal decomposition (TPAN) accounted for remarkable fractions of PAN observed under high temperature during both daytime and nighttime.

Analysis of elevated springtime levels of Peroxyacetyl nitrate (PAN) at the high Alpine research sites Jungfraujoch and Zugspitze

Abstract. The largest atmospheric peroxyacetyl nitrate (PAN) mole fractions at remote surface sites in the Northern Hemisphere are commonly observed during the months April and May. Different formation mechanisms for this seasonal maximum have previously been suggested: hemispheric-scale production from precursors accumulated during the winter months, increased springtime transport from up-wind continents or increased regional-scale production in the atmospheric boundary layer from recent emissions. The two high Alpine research sites Jungfraujoch (Switzerland) and Zugspitze (Germany) exhibit a distinct and consistent springtime PAN maximum. Since these sites intermittently sample air masses of free-tropospheric and boundary layer origin, they are ideally suited to identify the above-mentioned PAN formation processes and attribute local observations to these. Here we present a detailed analysis of PAN observations and meteorological conditions during May 2008 when PAN levels were especially elevated at both sites. The highest PAN concentrations were connected with anticyclonic conditions, which persisted in May 2008 for about 10 days with north-easterly advection towards the sites. A backward dispersion model analysis showed that elevated PAN concentrations were caused by the combination of favourable photochemical production conditions and large precursor concentrations in the European atmospheric boundary layer. The results suggest that the largest PAN values in spring 2008 at both sites were attributable to regional-scale photochemical production of PAN in the (relatively cold) planetary boundary layer from European precursors, whereas the contribution of inter-continental transport or free-tropospheric build-up was of smaller importance for these sites.

Seasonal and diurnal variations of atmospheric peroxyacetyl nitrate, peroxypropionyl nitrate, and carbon tetrachloride in Beijing

Atmospheric peroxyacetyl nitrate (PAN), peroxypropionyl nitrate (PPN), and carbon tetrachloride (CCl4) were measured from September 2010 to August 2011 in Beijing. PAN exhibited low values from mid-autumn to early spring (October to March) with monthly average concentrations ranging from 0.28 to 0.73 ppbV, and increased from early spring to summer (March to August), ranging from 1.37–3.79 ppbV. The monthly variation of PPN was similar to PAN, with low values (below detection limit to 0.18 ppbV) from mid-autumn to early spring, and a monthly maximum in September (1.14 ppbV). The monthly variation of CCl4 was tightly related to the variation of temperature, exhibiting a minimum in winter (69.3 pptV) and a maximum of 180.6 pptV in summer. Due to weak solar intensity and short duration, PAN and O3 showed no distinct diurnal patterns from morning to night during winter, whereas for other seasons, they both exhibited maximal values in the late afternoon (ca. 15:00 to 16:00 local time) and minimal values during early morning and midnight. Good linear correlations between PAN and PPN were found in autumn (R = 0.91), spring (R = 0.94), and summer (R = 0.81), with slopes of 0.130, 0.222, and 0.133, respectively, suggesting that anthropogenic hydrocarbons dominated the photochemical formation of PANs in Beijing. Positive correlation between PAN and O3 in summer with the low slopes (ΔO3/ΔPAN) ranging from 9.92 to 18.0 indicated serious air pollution in Beijing, and strong negative correlation in winter reflected strong O3 consumption by NO titration and less thermal decompositin of PAN.

Peroxyacetyl nitrate (PAN) in the urban atmosphere

Peroxyacetyl nitrate (PAN) in air has been well known as the indicator of photochemical smog due to its frequent occurrences in Seoul metropolitan area. This study was implemented to assess the distribution characteristics of atmospheric PAN in association with relevant parameters measured concurrently. During a full year period in 2011, PAN was continuously measured at hourly intervals at two monitoring sites, Gwang Jin (GJ) and Gang Seo (GS) in the megacity of Seoul, South Korea. The annual mean concentrations of PAN during the study period were 0.64±0.49 and 0.57±0.46ppb, respectively. The seasonal trends of PAN generally exhibited dual peaks in both early spring and fall, regardless of sites. Their diurnal trends were fairly comparable to each other. There was a slight time lag (e.g., 1h) in the peak occurrence pattern between O3 and PAN, as the latter trended to peak after the maximum UV irradiance period (16:00 (GJ) and 17:00 (GS)). The concentrations of PAN generally exhibited strong correlations with particulates. The results of this study suggest that PAN concentrations were affected sensitively by atmospheric stability, the wet deposition of NO2, wind direction, and other factors.

Direct and simultaneous determination of trace-level carbon tetrachloride, peroxyacetyl nitrate, and peroxypropionyl nitrate using gas chromatography-electron capture detection

Gas chromatography equipped with electron capture detector (GC-ECD) has been widely used for detecting atmospheric peroxyacetyl nitrate (PAN) and peroxypropionyl nitrate (PPN). However, to the best of our knowledge, only a few capillary columns have been adopted for separation to achieve the direct and simultaneous analysis of the two atmospheric pollutants. This paper demonstrates a novel method for directly and simultaneously measuring atmospheric carbon tetrachloride (CCl4), PAN, and PPN using GC-ECD with a DB-1 separation column. The responses of the GC-ECD to PAN, PPN, and CCl4 were individually calibrated by using gas mixtures prepared via volatilization of synthesized solutions of PAN and PPN or high-purity CCl4 reagent in a Teflon Bag. The concentrations of PAN and PPN in the synthesized solutions were quantified by ion chromatography (IC). Further calibration of the GC-ECD for PAN was conducted by in situ photochemical formation of gaseous PAN which was quantified by a NOx analyzer. The two calibration methods agreed well with each other, and the overall uncertainties for measuring atmospheric PAN were estimated to be ±13% and ±15% based on the calibrations of IC and NOx, respectively. The detection limits (three times the signal to noise ratio) for PAN, PPN, and CCl4 were estimated to be 22, 36, and 5pptv (parts per trillion by volume), respectively. The atmospheric concentrations of these compounds were measured for several days in August in Beijing, and the values obtained in this study were found to be in good agreement with the data reported in the literature for Beijing using other GC-ECD methods.

Natural and Anthropogenic Ethanol Sources in North America and Potential Atmospheric Impacts of Ethanol Fuel Use

We used an ensemble of aircraft measurements with the GEOS-Chem chemical transport model to constrain present-day North American ethanol sources, and gauge potential long-range impacts of increased ethanol fuel use. We find that current ethanol emissions are underestimated by 50% in Western North America, and overestimated by a factor of 2 in the east. Our best estimate for year-2005 North American ethanol emissions is 670 GgC/y, with 440 GgC/y from the continental U.S. We apply these optimized source estimates to investigate two scenarios for increased ethanol fuel use in the U.S.: one that assumes a complete transition from gasoline to E85 fuel, and one tied to the biofuel requirements of the U.S. Energy Indepence and Security Act (EISA). For both scenarios, increased ethanol emissions lead to higher atmospheric acetaldehyde concentrations (by up to 14% during winter for the All-E85 scenario and 2% for the EISA scenario) and an associated shift in reactive nitrogen partitioning reflected by an increase in the peroxyacetyl nitrate (PAN) to NO(y) ratio. The largest relative impacts occur during fall, winter, and spring because of large natural emissions of ethanol and other organic compounds during summer. Projected changes in atmospheric PAN reflect a balance between an increased supply of peroxyacetyl radicals from acetaldehyde oxidation, and the lower NO(x) emissions for E85 relative to gasoline vehicles. The net effect is a general PAN increase in fall through spring, and a weak decrease over the U.S. Southeast and the Atlantic Ocean during summer. Predicted NO(x) concentrations decrease in surface air over North America (by as much 5% in the All-E85 scenario). Downwind of North America this effect is counteracted by higher NO(x) export efficiency driven by increased PAN production and transport. From the point of view of NO(x) export from North America, the increased PAN formation associated with E85 fuel use thus acts to offset the associated lower NO(x) emissions.

Determination of Atmospheric Peroxyacetyl Nitrate by Gas Chromatography with a Deep Cryogenic Collection Method

Determination of Atmospheric Peroxyacetyl Nitrate by Gas Chromatography with a Deep Cryogenic Collection Method