Peroxyacetyl Nitrate Mixing Ratios Research Articles

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.

Decoupling peroxyacetyl nitrate from ozone in Chinese outflows observed at Gosan Climate Observatory

Abstract. We measured peroxyacetyl nitrate (PAN) and other reactive species such as O3, NO2, CO, and SO2 with aerosols including mass, organic carbon (OC), and elemental carbon (EC) in PM2. 5 and K+ in PM1. 0 at Gosan Climate Observatory in Korea (33.17° N, 126.10° E) during 19 October–6 November 2010. PAN was determined through fast gas chromatography with luminol chemiluminescence detection at 425 nm every 2 min. The PAN mixing ratios ranged from 0.1 (detection limit) to 2.4 ppbv with a mean of 0.6 ppbv. For all measurements, PAN was unusually better correlated with PM2. 5 (Pearson correlation coefficient, γ = 0.79) than with O3 (γ = 0.67). In particular, the O3 level was highly elevated with SO2 at midnight, along with a typical midday peak when air was transported rapidly from the Beijing areas. The PAN enhancement was most noticeable during the occurrence of haze under stagnant conditions. In Chinese outflows slowly transported over the Yellow Sea, PAN gradually increased up to 2.4 ppbv at night, in excellent correlation with a concentration increase in PM2. 5 OC and EC, PM2. 5 mass, and PM1. 0 K+. The high K+ concentration and OC ∕ EC ratio indicated that the air mass was impacted by biomass combustion. This study highlights PAN decoupling with O3 in Chinese outflows and suggests PAN as a useful indicator for diagnosing continental outflows and assessing their perturbation of regional air quality in northeast Asia.

Peroxyacetyl nitrate measurements by thermal dissociation–chemical ionization mass spectrometry in an urban environment: performance and characterizations

Peroxyacetyl nitrate (PAN) is an important indicator of photochemical smog and has adverse effects on human health and vegetation growth. A rapid and highly selective technique of thermal dissociation–chemical ionization mass spectrometry (TD-CIMS) was recently developed to measure the abundance of PAN in real time; however, it may be subject to artifact in the presence of nitric oxide (NO). In this study, we tested the interference of the PAN signal induced by NO, evaluated the performance of TD-CIMS in an urban environment, and investigated the concentration and formation of PAN in urban Hong Kong. NO caused a significant underestimation of the PAN signal in TD-CIMS, with the underestimation increasing sharply with NO concentration and decreasing slightly with PAN abundance. A formula was derived to link the loss of PAN signal with the concentrations of NO and PAN, which can be used for data correction in PAN measurements. The corrected PAN data from TDCIMS were consistent with those from the commonly used gas chromatography with electron capture detection, which confirms the utility of TD-CIMS in an urban environment in which NO is abundant. In autumn of 2010, the hourly average PAN mixing ratio varied from 0.06 ppbv to 5.17 ppbv, indicating the occurrence of photochemical pollution in urban Hong Kong. The formation efficiency of PAN during pollution episodes was as high as 3.9 to 5.9 ppbv per 100 ppbv ozone. The efficiency showed a near-linear increase with NOx concentration, suggesting a control policy of NOx reduction for PAN pollution. Open image in new window

Global Budget and Distribution of Peroxyacetyl Nitrate (PAN) for Present and Preindustrial Scenarios

A global 3-D chemistry and transport model, STOCHEM integrated with a detailed VOC oxidation scheme (CRI v2-R5) has been employed to study the important NOx reservoir compound, peroxyacetyl nitrate (PAN). Globally, PAN is produced entirely by the reaction of acetyl peroxy radicals (CH3CO3) with NO2 and up to 2.0 ppb of PAN is found over the polluted regions of North America during June- July-August for the present scenario. The imbalances between model and measurement data are noted, with STOCHEM-CRI overestimating PAN mixing ratios relative to the measurement data by +17 and +80 pptv for the lower and upper troposphere, respectively. The inclusion of additional HOx recycling mechanisms (e.g. related to isoprene oxidation) in STOCHEM-CRI causes a decrease in PAN in a present scenario by as much as 40% over sink regions and reduces the model-measurement disagreement by 90% for the lower troposphere and 40% for the upper troposphere. The lower NOx emissions and CH3CO3 formation upon including HOx recycling in a preindustrial scenario led to a decrease in PAN formation by as much as 40%. The decrease in PAN formation results in less nitrogen being transported to remote regions which in turn leads to the greatest percentage change in O3 concentration (9% decrease) in the equatorial regions.

Twin-cuvette measurement technique for investigation of dry deposition of O<sub>3</sub> and PAN to plant leaves under controlled humidity conditions

Abstract. We present a dynamic twin-cuvette system for quantifying the trace-gas exchange fluxes between plants and the atmosphere under controlled temperature, light, and humidity conditions. Compared with a single-cuvette system, the twin-cuvette system is insensitive to disturbing background effects such as wall deposition. In combination with a climate chamber, we can perform flux measurements under constant and controllable environmental conditions. With an Automatic Temperature Regulated Air Humidification System (ATRAHS), we are able to regulate the relative humidity inside both cuvettes between 40 and 90 % with a high precision of 0.3 %. Thus, we could demonstrate that for a cuvette system operated with a high flow rate (> 20 L min−1), a temperature-regulated humidification system such as ATRAHS is an accurate method for air humidification of the flushing air. Furthermore, the fully automatic progressive fill-up of ATRAHS based on a floating valve improved the performance of the entire measurement system and prevented data gaps. Two reactive gas species, ozone (O3) and peroxyacetyl nitrate (PAN), were used to demonstrate the quality and performance of the twin-cuvette system. O3 and PAN exchange with Quercus ilex was investigated over a 14 day measurement period under controlled climate chamber conditions. By using O3 mixing ratios between 32 and 105 ppb and PAN mixing ratios between 100 and 350 ppt, a linear dependency of the O3 flux as well as the PAN flux in relation to its ambient mixing ratio could be observed. At relative humidity (RH) of 40 %, the deposition velocity ratio of O3 and PAN was determined to be 0.45. At that humidity, the deposition of O3 to the plant leaves was found to be only controlled by the leaf stomata. For PAN, an additional resistance inhibited the uptake of PAN by the leaves. Furthermore, the formation of water films on the leaf surface of plants inside the chamber could be continuously tracked with our custom built leaf wetness sensors. Using this modified leaf wetness sensor measuring the electrical surface conductance on the leaves, an exponential relationship between the ambient humidity and the electrical surface conductance could be determined.

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.

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.

Trends in peroxyacetyl nitrate (PAN) in the upper troposphere and lower stratosphere over southern Asia during the summer monsoon season: regional impacts

Abstract. We analyze temporal trends of peroxyacetyl nitrate (PAN) retrievals from the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS) during 2002–2011 in the altitude range 8–23 km over the Asian summer monsoon (ASM) region. The greatest enhancements of PAN mixing ratios in the upper troposphere and lower stratosphere (UTLS) are seen during the summer monsoon season from June to September. During the monsoon season, the mole fractions of PAN show statistically significant (at 2σ) positive trends from 0.2 ± 0.05 to 4.6 ± 3.1 ppt yr−1 (except between 12 and 14 km) which is higher than the annual mean trends of 0.1 ± 0.05 to 2.7 ± 0.8 ppt yr−1. These rising concentrations point to increasing NOx (= NO + NO2) and volatile organic compound (VOC) emissions from developing nations in Asia, notably India and China. We analyze the influence of monsoon convection on the distribution of PAN in UTLS with simulations using the global chemistry–climate model ECHAM5-HAMMOZ. During the monsoon, transport into the UTLS over the Asian region primarily occurs from two convective zones, one the South China Sea and the other over the southern flank of the Himalayas. India and China host NOx-limited regimes for ozone photochemical production, and thus we use the model to evaluate the contributions from enhanced NOx emissions to the changes in PAN, HNO3 and O3 concentrations in the UTLS. From a set of sensitivity experiments with emission changes in particular regions, it can be concluded that Chinese emissions have a greater impact on the concentrations of these species than Indian emissions. According to SCanning Imaging Absorption SpectroMeter for Atmospheric CHartographY (SCIAMACHY) NO2 retrievals NOx emissions increases over India have been about half of those over China between 2002 and 2011.

Application of a GC-ECD for measurements of biosphere–atmosphere exchange fluxes of peroxyacetyl nitrate using the relaxed eddy accumulation and gradient method

Abstract. Peroxyacetyl nitrate (PAN) may constitute a significant fraction of reactive nitrogen in the atmosphere. Current knowledge about the biosphere–atmosphere exchange of PAN is limited, and only few studies have investigated the deposition of PAN to terrestrial ecosystems. We developed a flux measurement system for the determination of biosphere–atmosphere exchange fluxes of PAN using both the hyperbolic relaxed eddy accumulation (HREA) method and the modified Bowen ratio (MBR) method. The system consists of a modified, commercially available gas chromatograph with electron capture detection (GC-ECD, Meteorologie Consult GmbH, Germany). Sampling was performed by trapping PAN onto two pre-concentration columns; during HREA operation one was used for updraft and one for downdraft events, and during MBR operation the two columns allowed simultaneous sampling at two measurement heights. The performance of the PAN flux measurement system was tested at a natural grassland site, using fast-response ozone (O3) measurements as a proxy for both methods. The measured PAN fluxes were comparatively small (daytime PAN deposition was on average −0.07 nmol m−2 s−1) and, thus, prone to significant uncertainties. A major challenge in the design of the system was the resolution of the small PAN mixing ratio differences. Consequently, the study focuses on the performance of the analytical unit and a detailed analysis of errors contributing to the overall uncertainty. The error of the PAN mixing ratio differences ranged from 4 to 15 ppt during the MBR and between 18 and 26 ppt during the HREA operation, while during daytime measured PAN mixing ratios were of similar magnitude. Choosing optimal settings for both the MBR and HREA method, the study shows that the HREA method did not have a significant advantage towards the MBR method under well-mixed conditions as was expected.

Application of a Gas Chromatography/Luminol Detection System for Peroxyacetyl Nitrate Airborne Measurement

We constructed and tested an airborne peroxyacetyl nitrate (PAN) monitoring system based on luminol chemiluminescence detection with fast gas chromatography. This system allowed for simultaneous measurement of PAN and nitrogen dioxide (<TEX>$NO_2$</TEX>) with a time resolution of <2 min. Actual sample masses within the fixed volume sample loop at various altitudes and temperatures were adjusted to standard atmosphere, using measured pressures and temperatures. The airborne PAN measurement system was evaluated during two field studies above the southern Korean Peninsula in August and October 2009. The detection limit based on the ISO approach was 0.035 ppbv PAN, well below the observed concentrations of 0.185-1.49 ppbv during these studies. Under these conditions, the PAN mixing ratios were positively correlated with <TEX>$O_x$</TEX> (<TEX>$O_x=O_3+NO_2$</TEX>), with slopes varying between 0.014 and 0.033 and intercepts between 22.6 and 55.1 ppbv <TEX>$O_x$</TEX>. The intercepts corresponded roughly to background <TEX>$O_x$</TEX> mixing ratios in central Europe; however, the slopes were above the range of slopes reported in other studies. We also enhanced the durability, safety, and ease of maintenance of the PAN monitoring system by redesigning the structure of the conventional luminol cell.

Transport of PAN and NOy from different source regions to the Swiss high alpine site Jungfraujoch

The effect of intercontinental transport on measurements of nitrogen oxides (NOx), peroxyacetyl nitrate (PAN) and reactive nitrogen species (NOy) at the high altitude site Jungfraujoch (3580 m asl), Switzerland, was evaluated using a combination of backward trajectories and chemical filters (NOy to carbon monoxide (CO) ratio). Mixing ratios associated with air masses transported from the planetary boundary layers (PBL) of the three continental source regions Europe, North America, and Asia, and of free tropospheric origin were characterized. The analysis was applied to PAN, NOx and NOy measurements of the period 1997–1998, and to a period more than 10 years later covering several months in 2008 and 2009–2010. The results show that the mixing ratios of PAN, NOx and NOy are largest in air advected from the European PBL. In contrast to previous studies, our results indicate that the springtime maximum in PAN and NOy mixing ratios is largely attributable to air originating from the European PBL whereas air of free tropospheric origin and intercontinental transport contribute less significantly. PAN and NOy mixing ratios in air masses classified as free tropospheric are also highest in spring but substantially lower than those influenced by European PBL air. Air masses last influenced by the North American source region show considerably lower mixing ratios of nitrogen species than European air masses suggesting that a large fraction of NOy is removed during intercontinental transport probably due to washout of soluble species such as HNO3. The seasonal contributions from different source regions to PAN mixing ratios at Jungfraujoch were evaluated. The average European contribution is highest during the warm seasons with 47–57% in 1997–1998 and 61–69% in 2009–2010. The maximum contribution of North American air masses is also observed in the warm season and was about 5–7% in 1997–1998 and 6–10% in 2009–2010. Air from Asian source regions did not make a significant contribution due to the limited number of cases of direct transport from Asia, but when they occurred the air masses contained significant pollutant levels.

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.

Emission Ratios for Ammonia and Formic Acid and Observations of Peroxy Acetyl Nitrate (PAN) and Ethylene in Biomass Burning Smoke as Seen by the Tropospheric Emission Spectrometer (TES).

We use the Tropospheric Emission Spectrometer (TES) aboard the NASA Aura satellite to determine the concentrations of the trace gases ammonia (NH3) and formic acid (HCOOH) within boreal biomass burning plumes, and present the first detection of peroxy acetyl nitrate (PAN) and ethylene (C2H4) by TES. We focus on two fresh Canadian plumes observed by TES in the summer of 2008 as part of the Arctic Research of the Composition of the Troposphere from Aircraft and Satellites (ARCTAS-B) campaign. We use TES retrievals of NH3 and HCOOH within the smoke plumes to calculate their emission ratios (1.0% ± 0.5% and 0.31% ± 0.21%, respectively) relative to CO for these Canadian fires. The TES derived emission ratios for these gases agree well with previous aircraft and satellite estimates, and can complement ground-based studies that have greater surface sensitivity. We find that TES observes PAN mixing ratios of ~2 ppb within these mid-tropospheric boreal biomass burning plumes when the average cloud optical depth is low (<0.1) and that TES can detect C2H4 mixing ratios of ~2 ppb in fresh biomass burning smoke plumes.

Free tropospheric peroxyacetyl nitrate (PAN) and ozone at Mount Bachelor: potential causes of variability and timescale for trend detection

Abstract. We report on the first multi-year springtime measurements of PAN in the free troposphere over the US Pacific Northwest. The measurements were made at the summit of Mount Bachelor (43.979° N, 121.687° W; 2.7 km a.s.l.) by gas chromatography with electron capture detector during spring 2008, 2009 and 2010. This dataset provides an observational estimate of the month-to-month and springtime interannual variability of PAN mixing ratios in this region. Springtime seasonal mean (1 April–20 May) PAN mixing ratios at Mount Bachelor varied from 100 pptv to 152 pptv. The standard deviation of the three seasonal means was 28 pptv, 21 % of the springtime mean. We summarize the interannual variability in three factors expected to drive PAN variability: biomass burning, transport efficiency over the central and eastern Pacific, and transport temperature. Zhang et al. (2008) used the GEOS-Chem global chemical transport model to show that rising Asian NOx emissions from 2000 to 2006 resulted in a relatively larger positive trend in PAN than O3 over western North America. However the model results only considered monotonic changes in Asian emissions, whereas other factors, such as biomass burning, isoprene emissions or climate change can induce greater variability in the atmospheric concentrations and thus extend the time needed for trend detection. We combined the observed variability in PAN and O3 at Mount Bachelor with a range of possible future trends in these species to determine the observational requirements to detect such trends. Though the relative increase in PAN is expected to be larger than that of O3, PAN is more variable. If PAN mixing ratios are currently increasing at a rate of 4 % per year due to rising Asian emissions, we would detect a trend with 13 years of measurements at a site like Mount Bachelor. If the corresponding trend in O3 is 1 % per year, the trends in O3 and PAN would be detected on approximately the same timescale.

An aircraft-borne chemical ionization – ion trap mass spectrometer (CI-ITMS) for fast PAN and PPN measurements

Abstract. An airborne chemical ionization ion trap mass spectrometer instrument (CI-ITMS) has been developed for tropospheric and stratospheric fast in-situ measurements of PAN (peroxyacetyl nitrate) and PPN (peroxypropionyl nitrate). The first scientific deployment of the FASTPEX instrument (FASTPEX = Fast Measurement of Peroxyacyl nitrates) took place in the Arctic during 18 missions aboard the DLR research aircraft Falcon, within the framework of the POLARCAT-GRACE campaign in the summer of 2008. The FASTPEX instrument is described and characteristic properties of the employed ion trap mass spectrometer are discussed. Atmospheric data obtained at altitudes of up to ~12 km are presented, from the boundary layer to the lowermost stratosphere. Data were sampled with a time resolution of 2 s and a 2σ detection limit of 25 pmol mol−1. An isotopically labelled standard was used for a permanent on-line calibration. For this reason the accuracy of the PAN measurements is better than ±10% for mixing ratios greater than 200 pmol mol−1. PAN mixing ratios in the summer Arctic troposphere were in the order of a few hundred pmol mol−1 and generally correlated well with CO. In the Arctic boundary layer and lowermost stratosphere smaller PAN mixing ratios were observed due to a combination of missing local sources of PAN precursor gases and efficient removal processes (thermolysis/photolysis). PPN, the second most abundant PAN homologue, was measured simultaneously. Observed PPN/PAN ratios range between ~0.03 and 0.3.

Meteorological controls on observed peroxyacetyl nitrate at Mount Bachelor during the spring of 2008

A suite of gas phase and aerosol measurements were made during spring 2008 at the summit of Mount Bachelor (2763 m asl), located in central Oregon. Here we focus on observations of peroxyacetyl nitrate (PAN) for the period of 3 April to 18 June 2008. During this period, PAN mixing ratios ranged from below detection limit to 527 pptv, with a campaign mean of 119 pptv. Our analysis indicates that the variability in PAN was predominantly a function of synoptic scale processes. Three plumes containing elevated PAN were analyzed in detail. Two of these plumes were of Asian origin, and one was associated with North American sources. The Asian plumes were observed on 17–18 April and 12–13 May. Both were associated with elevated PAN, CO, O3, and aerosol scattering (σsp). The relationship between PAN and O3 varied with air mass temperature within the 17–18 April plume, and we exploited this to derive an O3 production efficiency per unit of PAN decomposed of 51–73 mol mol−1. The second Asian plume (12–13 May) was more dilute, characterized by lower CO and σsp. This event had a larger PAN/CO slope, consistent with relatively colder subsidence as calculated by trajectories. We traced the pathways of the plumes using a global chemical transport model (GEOS‐Chem) alongside trajectories to show that the plumes crossed the Pacific at different rates and following different routes. The plume observed on April 17–18 traveled over the great circle, while the later plume took a slower more southern path across the Pacific.

Continuous measurement of peroxyacetyl nitrate (PAN) in suburban and remote areas of western China

Knowledge on atmospheric abundance of peroxyacetyl nitrate (PAN) is important in assessing the severity of photochemical pollution, and for understanding chemical transformation of reactive odd nitrogen and its impact on the budget of tropospheric ozone (O 3). In summer 2006, continuous measurements of PAN were made using an automatic GC–ECD analyzer with an on-line calibrator at a suburban site of Lanzhou (LZ) and a remote site of Mt. Waliguan (WLG) in western China, with concurrent measurements of O 3, total reactive nitrogen (NO y ) and carbon monoxide (CO). At LZ, several photochemical episodes were observed during the study, and the average mixing ratio of PAN (plus or minus standard deviation) was 0.76 (±0.89) ppbv with the maximum value of 9.13 ppbv, compared to an average value of 0.44 (±0.16) ppbv at remote WLG. The PAN mixing ratios in LZ exhibited strong diurnal variations with a maximum at noon, while enhanced concentrations of PAN were observed in the evening and a minimum in the afternoon at WLG. The daily O 3 and PAN concentration maxima showed a strong correlation ( r 2 = 0.91) in LZ, with a regression slope (PAN/O 3) of 0.091 ppbv ppbv −1. At WLG, six well-identified pollution plumes (lasting 2–8 h) were observed with elevated concentrations of PAN (and other trace gases), and analysis of backward particle release simulation shows that the high-PAN events at WLG were mostly associated with the transport of air masses that had passed over LZ.

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 &lt;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.

Gaseous fluxes of peroxyacetyl nitrate (PAN) into plant leaves

ABSTRACTPeroxyactyl nitrate (PAN) is the most abundant of the gaseous organic nitrates produced from the photochemistry of hydrocarbons and NOx (i.e. ozone and smog production). PAN is known to be toxic to plants and also as a reservoir for the transport nitrogen dioxide in the troposphere. Here, the effect of vegetation on PAN deposition was investigated in four plant species by measuring leaf fluxes of PAN in a dynamic leaf chamber using atmospheric PAN fumigations between 0.7 and 18 nmol mol−1. A linear relationship was observed between PAN flux and ambient PAN mixing ratio for all species. Depending on the species, measured PAN flux varied between 11 and 24 pmol m−2 s−1. Measured fluxes of PAN accounted for 12–48% of the PAN flux predicted solely from modelled stomatal conductance to PAN, suggesting the presence of a mesophyllic resistance to PAN uptake. The brief (approximately 5–10 min) exposure to PAN during uptake measurements did not affect photosynthesis, transpiration or conductance to water vapour. Increasing stomatal resistance by varying the vapour pressure gradient between the leaf chamber and leaf internal air space led to a corresponding drop in PAN uptake. Varying leaf nitrogen and total leaf–ascorbate concentrations did not appear to influence PAN uptake as had been reported for other reactive odd‐nitrogen gases. Measured and model‐predicted PAN fluxes were offset, but correlated suggesting that PAN flux could be estimated using established stomatal conductance algorithms.