Production Of 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.

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.

Characterization of peroxyacetyl nitrate (PAN) under different PM2.5 concentration in wintertime at a North China rural site

As a secondary pollutant of photochemical pollution, peroxyacetyl nitrate (PAN) has attracted a close attention. A four-month campaign was conducted at a rural site in North China Plain (NCP) including the measurement of PAN, O3, NOx, PM2.5, oxygenated volatile organic compounds (OVOCs), photolysis rate constants of NO2 and O3 and meteorological parameters to investigate the wintertime characterization of photochemistry from November 2018 to February 2019. The results showed that the maximum and mean values of PAN were 4.38 and 0.93 ± 0.67 ppbv during the campaign, respectively. The PAN under different PM2.5 concentrations from below 75 μg/m3 up to 250 μg/m3, showed different diurnal variation and formation rate. In the PM2.5 concentration range of above 250 μg/m3, PAN had the largest daily mean value of 0.64 ppbv and the fastest production rate of 0.33 ppbv/hr. From the perspective of PAN's production mechanism, the light intensity and precursors concentrations under different PM2.5 pollution levels indicated that there were sufficient light intensity and high volatile organic compounds (VOCs) and NOx precursors concentration even under severe pollution level to generate a large amount of PAN. Moreover, the bimodal staggering phenomenon of PAN and PM2.5 provided a basis that PAN might aggravate haze through secondary organic aerosols (SOA) formation.

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.

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.

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.

PAN–Precursor Relationship and Process Analysis of PAN Variations in the Pearl River Delta Region

Peroxy acetyl nitrate (PAN) is an important photochemical product formed from the reactions between volatile organic compounds (VOCs) and nitrogen oxides (NOx) under sunlight. In this study, a field measurement was conducted at a rural site (the backgarden site, or BGS) of the Pearl River Delta (PRD) region in 2006, with the 10 min maximum PAN mixing ratios of 3.9 ppbv observed. The factors influencing the abundance of PAN at the BGS site was evaluated by the process analysis through the Weather Research and Forecasting-Community Multiscale Air Quality (WRF-CMAQ) model. The results suggested that the increase of PAN abundance at the BGS site was mainly controlled by the gas-phase chemistry, followed by vertical transport, while its loss was modulated mainly by dry deposition and horizontal transport. As the dominant important role of gas-phase chemistry, to provide detailed information on the photochemical formation of PAN, a photochemical box model with near-explicit chemical mechanism (i.e., the master chemical mechanism, MCM) was used to explore the relationship of photochemical PAN formation with its precursors based on the measured data at the BGS site. It was found that PAN formation was VOC-limited at the BGS site, with the oxidation of acetaldehyde the most important pathway for photochemical PAN production, followed by the oxidation and photolysis of methylglyoxal (MGLY). Among all the primary VOC precursors, isoprene and xylenes were the main contributors to PAN formation. Overall, our study provides new insights into the PAN photochemical formation and its controlling factors, and highlighted the importance of gas chemistry on the PAN abundance in the PRD region.

Observations of Acyl Peroxy Nitrates During the Front Range Air Pollution and Photochemistry Éxperiment (FRAPPÉ)

AbstractWe report on measurements of acyl peroxy nitrates (APNs) obtained from two ground sites and the NSF/National Center for Atmospheric Research C‐130 aircraft during the 2014 Front Range Air Pollution and Photochemistry Éxperiment (FRAPPÉ). The relative abundance of the APNs observed at the Boulder Atmospheric Observatory (BAO) indicates that anthropogenic emissions of volatile organic compounds (VOCs) are the dominant drivers of photochemistry during days with the most elevated peroxyacetyl nitrate (PAN). Reduced major axis regression between propionyl peroxynitrate (PPN) and PAN observed at BAO and from the C‐130 produced a slope of 0.21 (R2 = 0.92). Periods of lower PPN/PAN ratios (~0.10) were associated with cleaner background air characterized by lower ammonia and formic acid abundances. The abundance of methacryloyl peroxynitrate relative to PAN only exceeded 0.05 at BAO when PAN mixing ratios were <300 parts per trillion by volume, implying low influence of isoprene oxidation during periods with substantial local PAN production. We show an example of a day (19 July) where high O3 was not accompanied by enhanced local PAN production. The contribution of biogenic VOCs to local O3 production on the other days in July with elevated O3 (22, 23, 28, and 29 July 2014) was small; evidence is provided in the high abundance of PPN to PAN (slopes between 0.18 and 0.26). The PAN chemistry observed from surface and aircraft platforms during FRAPPÉ implies that anthropogenic VOCs played a dominant role in PAN production during periods with the most O3 and that the relative importance of biogenic hydrocarbon chemistry decreased with increasing O3 production during FRAPPÉ.

Regional and hemispheric influences on measured spring peroxyacetyl nitrate (PAN) mixing ratios at the Auchencorth UK EMEP supersite

This work presents 15-min averaged measurements of peroxyacetyl nitrate (PAN) obtained during spring 2014 (24/04/2014 – 06/05/2014) at the Auchencorth UK EMEP supersite (southeast Scotland). The aim of this analysis was to investigate the conditions producing the distribution of PAN mixing ratios at the supersite in spring 2014. Air mass back trajectories showed the majority of air masses to have spent substantial time over the UK, continental Europe or Scandinavia prior to arrival at Auchencorth. The median and 95th percentile PAN mixing ratios observed were 0.46ppb and 1.03ppb, respectively. The median mixing ratio was elevated compared with previous PAN measurements during springtime (April–May) in southeast Scotland (corresponding median mixing ratios April–May 1994–1998: 0.1–0.3ppb), which is hypothesised to be due to conditions conducive to regional (European) photochemical PAN production. Additionally, PAN mixing ratios during regionally influenced conditions (0.4–1.5ppb) were substantially more elevated from hemispheric background mixing ratios (0.4–0.6ppb) than for ozone (O3, regional: 10–45ppb, hemispheric: 30–40ppb). PAN and O3 both impact upon vegetation and human health and it is necessary to understand the extent to which hemispheric and regional processes contribute to their abundances in different locations. Regional processes can both increase and decrease PAN and O3 mixing ratios compared to imported hemispheric background mixing ratios. This study concludes that during the measurement period in spring 2014 at the Auchencorth supersite, regional PAN and O3 modifying processes enhanced PAN mixing ratios more than for O3.

Measurements of Peroxyacetyl Nitrate at a Background Site in the Pearl River Delta Region: Production Efficiency and Regional Transport

Peroxyacetyl nitrate (PAN) is a trace constituent of the atmosphere but plays important roles in air pollution and atmospheric chemistry. To understand the chemical and transport processes of PAN in the Pearl River Delta (PRD) region, measurements of PAN, its precursors and related parameters were made at a regional background site in late summer and late autumn of 2011. Despite the fairly low ambient levels of PAN in general, several photochemical episodes with peak concentrations of PAN and ozone (O3) as high as 4.86 and 189 ppbv were observed when the region was under influence of a tropical cyclone. PAN showed a seasonal variation with higher levels in autumn than in summer. PAN production efficiency, defined as the amount of PAN formed per unit amount of nitrogen oxides (NOx) oxidized, was examined for the polluted PRD plumes, which indicated that PAN production accounted for on average approximately one third of the NOz formation. The photochemical production efficiency of PAN was much lower with respect to that of O3, suggesting that ~2.9 ppbv of PAN could be produced per formation of 100 ppbv of O3 in the PRD plumes. Varying air masses including maritime air, regional air masses from the PRD, and continental outflow from eastern China were identified, which showed different chemical signatures in terms of both pollution levels and NOz budget. The highest abundances of PAN were measured in the PRD air masses, compared to the lowest concentrations in the marine air. Overall, the present study provides some new insights into the photochemical production and regional transport of PAN in the PRD region, where such investigations were very scarce before.

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.

On the use of an explicit chemical mechanism to dissect peroxy acetyl nitrate formation

Peroxy acetyl nitrate (PAN) is a key component of photochemical smog and plays an important role in atmospheric chemistry. Though it has been known that PAN is produced via reactions of nitrogen oxides (NOx) with some volatile organic compounds (VOCs), it is difficult to quantify the contributions of individual precursor species. Here we use an explicit photochemical model – Master Chemical Mechanism (MCM) model – to dissect PAN formation and identify principal precursors, by analyzing measurements made in Beijing in summer 2008. PAN production was sensitive to both NOx and VOCs. Isoprene was the predominant VOC precursor at suburb with biogenic impact, whilst anthropogenic hydrocarbons dominated at downtown. PAN production was attributable to a relatively small class of compounds including NOx, xylenes, trimethylbenzenes, trans/cis-2-butenes, toluene, and propene. MCM can advance understanding of PAN photochemistry to a species level, and provide more relevant recommendations for mitigating photochemical pollution in large cities.

Variations of regional background peroxyacetyl nitrate in marine boundary layer over Baengyeong Island, South Korea

Concurrent two-week measurements of peroxyacetyl nitrate (PAN), other photochemically reactive species (including O3, CO, NO2, and volatile organic compounds), and aerosols (water-soluble ionic species, organic and elemental carbon, and trace metals) were made at an atmospheric monitoring station on Baengyeong Island in the summer and autumn of 2010 and winter and spring of 2011. PAN mixing ratios ranged from the below the detection limit of 0.01–2.47 ppbv, with a median of 0.04, 0.58, 0.32, 0.17 ppbv during the summer, autumn, winter; and spring, respectively. Although the photochemical ages determined from the PAN/NOx ratios indicated that the measurement site was situated under a relatively clean marine boundary layer, significant and abrupt increases in PAN were frequently observed due to transport from nearby land masses, mainly China and South Korea. The vertical trend of PAN with a mid-altitude maximum observed in this study is consistent with previous aircraft campaigns near the site. However, the PAN concentration recorded in this study was about two times higher than those of previous studies at remote marine surface sites in the southern Yellow Sea. In most cases, the marine boundary layer acted as an overall sink for PAN. However, we found that in-situ photochemical production of insoluble PAN also contributes to maintaining high-PAN mixing ratios in the boundary layer over the Yellow Sea and plays a role in the regional transport of reactive nitrogen species.

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.

Eddy covariance fluxes of acyl peroxy nitrates (PAN, PPN and MPAN) above a Ponderosa pine forest

Abstract. During the Biosphere Effects on AeRosols and Photochemistry EXperiment 2007 (BEARPEX-2007), we observed eddy covariance (EC) fluxes of speciated acyl peroxy nitrates (APNs), including peroxyacetyl nitrate (PAN), peroxypropionyl nitrate (PPN) and peroxymethacryloyl nitrate (MPAN), above a Ponderosa pine forest in the western Sierra Nevada. All APN fluxes are net downward during the day, with a median midday PAN exchange velocity of −0.3 cm s−1; nighttime storage-corrected APN EC fluxes are smaller than daytime fluxes but still downward. Analysis with a standard resistance model shows that loss of PAN to the canopy is not controlled by turbulent or molecular diffusion. Stomatal uptake can account for 25 to 50% of the observed downward PAN flux. Vertical gradients in the PAN thermal decomposition (TD) rate explain a similar fraction of the flux, suggesting that a significant portion of the PAN flux into the forest results from chemical processes in the canopy. The remaining "unidentified" portion of the net PAN flux (~15%) is ascribed to deposition or reactive uptake on non-stomatal surfaces (e.g. leaf cuticles or soil). Shifts in temperature, moisture and ecosystem activity during the summer – fall transition alter the relative contribution of stomatal uptake, non-stomatal uptake and thermochemical gradients to the net PAN flux. Daytime PAN and MPAN exchange velocities are a factor of 3 smaller than those of PPN during the first two weeks of the measurement period, consistent with strong intra-canopy chemical production of PAN and MPAN during this period. Depositional loss of APNs can be 3–21% of the gross gas-phase TD loss depending on temperature. As a source of nitrogen to the biosphere, PAN deposition represents approximately 4–19% of that due to dry deposition of nitric acid at this site.

Characteristic behavior of peroxyacetyl nitrate (PAN) in Seoul megacity, Korea

We measured the concentrations of peroxyacetyl nitrate (PAN) and other photochemically reactive species, including O 3, NO 2, and non-methane hydrocarbons (NMHCs), in the Seoul Metropolitan area (SMA) during May through June in 2004 and 2005. PAN was determined using a fast chromatograph with luminol-based chemiluminescence detection. Mixing ratios of PAN ranged from below the detection limit (0.1 ppbv) to 10.4 ppbv with an average of 0.8 ppbv. O 3 concentrations ranged from 0 to 141 ppbv. The average PAN/O 3 ratio of 0.07 was higher than that observed in cities of Europe and North America (0.02) where control strategies have been enforced to reduce hydrocarbon emissions through extensively reformulated gasoline programs. Strong positive correlations between daily PAN and O 3 maxima during the day demonstrate that similar photochemical factors controlled the production of these two chemicals. However, relationships between PAN and its precursors, NO 2 and NMHCs, suggest that PAN production was more sensitive to NO 2 than NMHCs levels whereas O 3 production was limited by the overall availability of NMHCs. It is likely that the compositions of NMHCs in SMA were favorable for PAN production because of the low fractions of oxygenated compounds in automobile fuels. PAN maxima were observed around noon, which was 2–3 h earlier than the much broader O 3 maxima that occurred in the midafternoon. After reaching the maximum, PAN concentrations rapidly dropped within a few hours, which could be largely due to thermal destruction and to limited production under the typically low NO 2 levels that occurred in the early afternoon. The heterogeneous destruction of particulate matter could be an additional sink for PAN in SMA.

Seasonal variation of peroxyacetylnitrate (PAN) in coastal Antarctica measured with a new instrument for the detection of sub-part per trillion mixing ratios of PAN

Abstract. An automated gas chromatograph with sample pre-concentration for the measurement of peroxyacetylnitrate (PAN) was constructed with a minimum detection limit below 1 pptv. This instrument was deployed at the British Antarctic Survey's Halley Research Station, Antarctica (75.6° S, 26.6° W) as part of the CHABLIS (Chemistry of the Antarctic Boundary Layer and the Interface with Snow) campaign. Hourly measurements were carried out between July 2004 and February 2005 with observed maximum and minimum mixing ratios of 52.3 and <0.6 pptv, respectively with a mean PAN mixing ratio for the measurement period of 9.2 pptv (standard deviation: 6.2 pptv). The changes in PAN mixing ratios typically occurred over periods of several days to a week and showed a strong similarity to the variation in alkenes. The mixing ratio of PAN at Halley has a possible seasonal cycle with a winter maximum and summer minimum, though the cycle is incomplete and the data are very variable. Calculations indicate that gross local PAN production is approximately 1 pptv d−1 in spring and 0.6 pptv d−1 in summer. Net loss of PAN transported to Halley in the summer is a small gas-phase source of NOx and net production of PAN in the spring is a very small NOx sink.

Effects of additional nonmethane volatile organic compounds, organic nitrates, and direct emissions of oxygenated organic species on global tropospheric chemistry

This work evaluates the sensitivity of tropospheric ozone and its precursors to the representation of nonmethane volatile organic compounds (NMVOCs) and organic nitrates. A global 3‐D tropospheric chemistry/transport model (IMPACT) has been exercised initially using the GEOS‐Chem chemical reaction mechanism. The model was then extended by adding emissions and photochemical reactions for aromatic and terpenoid hydrocarbons, and by adding explicit representation of hydroxy alkyl nitrates produced from isoprene. Emissions of methanol, phenol, acetic acid and formic acid associated with biomass burning were also added. Results show that O3 increases by 20% in most of the troposphere, peroxyacetyl nitrate (PAN) increases by 30% over much of the troposphere and OH increases by 10%. NOx (NO + NO2) decreases near source regions and increases in remote locations, reflecting increased transport of NOx away from source regions by organic nitrates. The increase in O3 was driven largely by the increased role of PAN as a transporter of NOx and by the rerelease of NOx from isoprene nitrates. The increased PAN production was associated with increases in methyl glyoxal and hydroxyacetone. Comparison with measured values show reasonable agreement for O3 and PAN, but model measurement agreement does not either improve or degrade in the extended model. The extended model shows improved agreement with measurements for methanol, acetic acid and peroxypropional nitrate (PPN). Results from the extended model were consistent with measured alkyl nitrates and glycolaldehyde, but hydroxyacetone and methyl glyoxal were overestimated. The latter suggests that the effect of the isoprene nitrates is somewhat smaller than estimated here. Although the model measurement comparison does not show specific improvements with the extended model, it provides a more complete description of tropospheric chemistry that we believe is important to include.

Synoptic‐scale transport of reactive nitrogen over the western Pacific in spring

Pathways of synoptic‐scale uplifted transport of pollutants from East Asia and their effects on chemical distributions of NOy species are investigated based on a subset of the aircraft data obtained during the NASA Transport and Chemical Evolution over the Pacific (TRACE‐P) experiment, conducted in February–April 2001. Meteorological and chemical analyses indicate that 73% of the uplifted transport was associated with warm conveyor belts (WCBs) and convective outflow (COF), which transported air masses strongly impacted by biomass burning over Southeast Asia. The rest (27%) of the uplifted air masses originated over coastal regions of northeast China, where fossil fuel combustion was a dominant source of pollutants. Both WCB associated with a midlatitude cyclone and COF associated with a stationary front over southeast China are examined in detail for the April 4 case. During the TRACE‐P period, low NOx(= NO + NO2)/NOy ratios in the WCB and COF indicate that a significant part of the NOx was oxidized to nitric acid (HNO3) and peroxyacetyl nitrate (PAN) during transport. Low HNO3/NOy ratios in the WCB and COF airstreams indicate that a large amount of HNO3 was removed during transport on timescales within 1–3 days. PAN was found to be the dominant form of NOy in air masses transported by the WCB and COF, likely due to the production of PAN in regions of biomass burning and industrial emissions, as well as due to the rapid removal of HNO3 during transport. For emissions that were transported to the free troposphere by WCBs and COF, about 10–20% of the NOy remained after transport to the free troposphere, and 30% of the NOy surviving in the boundary layer in limited cases. The results indicate that the WCB and COF provide both an efficient sink for HNO3 and an efficient mechanism for the transport of PAN from the boundary layer to the free troposphere over the western Pacific.