Peroxyacetyl Nitrate (PAN) Measurements During the POPCORN Campaign

During the POPCORN campaign between 3 and 24 August 1994 we measured peroxyacetyl nitrate (PAN) in a rural area of Mecklenburg-Vorpommern (North-Eastern Germany) above a corn field. A total of about 5000 PAN measurements were carried out within the three weeks of the campaign. Measured PAN mixing ratios ranged from below the detection limit of 10 ppt up to an afternoon maximum of 1 ppb. The mean value of all data was 140 ppt. The daily mean PAN mixing ratios were typically in the range of 50 to 250 ppt, but during a clean air episode PAN mixing ratios of well below 40 ppt were observed. The characteristic relative diurnal variation of the PAN mixing ratios with a late night/early morning minimum and an afternoon maximum persisted during these episodes. The daily averages of the PAN mixing ratios showed clear episodic variations which coincided with the duration of typical synoptic episodes of two to six days duration. Based on the measurements of the various parameters determining the PAN formation and destruction rates, the local budget for PAN was calculated. During daytime the calculated net photochemical formation rate of PAN was nearly always significantly higher than the observed change of the PAN concentration. This demonstrates that substantial amounts of PAN (often in the range of several hundred ppt/h) were exported from the corn field. The resulting removal of NOx to some extent effects the budget of nitrogen oxides (NOx), but the export of odd oxygen radicals in the form of PAN during daytime often amounted up to 30–50% of the OH-radical formation by ozone photolysis. Thus the importance of PAN as reservoir and transport medium for odd oxygen radicals can be very substantial and may have a significant impact on the budget and distribution of odd oxygen radicals.     

Gas chromatographic determination of peroxyacetyl nitrate: Two convenient calibration techniques

Two procedures for the calibration of an electron capture detector (ECD) for peroxyacetyl nitrate (PAN) are discussed. One is based on the first-order decay rate of the the PAN mixing ratio in conditioned glass storage vessels. The other method makes use of the photochemical generation of PAN in mixtures of acetone and NO₂ in air. For this purpose a Penray Hg lamp was inserted into a glass vessel filled with 1 atmosphere of air containing 10 ppm NO₂ and 1% acetone. After 3 min of irradiation, the average PAN mixing ratio formed was 8.87±0.25 ppmv as determined in six separate runs.     

金华地区夏秋大气中过氧乙酰硝酸酯的污染特征

过氧乙酰硝酸酯（PAN）是由VOCs和NO_x的光化学反应生成的一种典型二次污染物,比O₃更适合作为光化学污染的指示剂.2019年6—10月对浙江中部盆地金华市大气中PAN进行了在线监测,并对影响其体积分数变化的因素进行了分析,同时还分析了一次典型的光化学污染过程.结果表明,观测期间PAN的平均体积分数为0.656×10^-9,最高体积分数为4.348×10^-9,日均体积分数水平在0.130×10^-9~2.203×10^-9之间.PAN日变化特征显著,9月为明显的双峰变化,其他月份均为单峰.受气象条件的影响,夏季的污染程度显著低于秋季.9月27—30日典型污染时段内,PAN的小时均值是整个观测期均值的2.8倍,污染以本地积累为主.前体物浓度水平差异与去除机制的不同是影响PAN和O₃相关性的重要因素,此外NO/NO₂的比值是影响PAN生成速率的重要因素,PAN的峰值基本出现在NO/NO₂比值较低的时段.在生成PAN的VOCs物种中,丙烷、乙烷和间/对二甲苯所占比例较大.     

Spring time sources and sinks of Peroxyacetyl Nitrate in the UK and its contribution to acidification and nitrification of cloud water

During spring the atmospheric concentration of Peroxyacetyl Nitrate, PAN, in the UK varies over three orders of magnitude due to long range transport and local photochemical production. An experiment at Great Dun Fell was used to determine which of these sources of PAN controlled spring time concentrations and to quantify the contribution of PAN to oxidised nitrogen in cloud water. The gas phase mixing ratio of a wide range of trace gas pollutants, including PAN, along with cloud water chemical composition and aerosol/cloud droplet distributions were measured. A chemical model was developed to determine the contribution of PAN hydrolysis to cloud water nitrification and to quantify the sink strengths of PAN. Chemical reaction following thermal decomposition was found to be the dominant sink mechanism in the model but transport was the most important factor controlling PAN concentration. During cloud episodes PAN concentrations varied from 100 ppt to over 1 ppb but the calculated inorganic oxidised nitrogen loading in the cloud due to PAN dissolution and hydrolysis was an insignificant fraction of the observed total oxidised nitrogen loading of the cloud. Extrapolation of the model to persistent cloud in marine conditions showed that PAN has a negligible effect on cloud nitrification. It was concluded that PAN concentrations were heavily influenced by regional concentrations and that the hydrolysis of PAN in cloud water was an insignificant source of oxidised nitrogen in cloud water.     

Synoptic and mesoscale weather conditions during air pollution episodes in Athens,Greece

Based on regular climatological and air quality data from the Greater Athens Area (GAA), the air pollution episodes observed in Athens during the period 1983–1990 were analysed and classified. The main characteristics of atmospheric conditions during days with high air pollution concentrations are summarized too. Model simulations show that the worst air pollution episodes in Athens occur during days with a critical balance between synoptic and mesoscale circulations and/or during days with warm advection in the lower troposphere.     

Measurement of PAN in the Polluted Boundary Layer and Free Troposphere Using a Luminol-NO2 Detector Combined with a Thermal Converter

Peroxyacetyl nitrate (PAN,CH³C(O)O₂NO₂) has been measured inthe polluted boundary layer and free troposphere by thermal conversion tonitrogen dioxide (NO₂) followed by detection of thedecomposition product with a Scintrex LMA-3 NO₂-luminolinstrument. Following laboratory tests of the efficiency of PAN conversionand investigations of possible interferences, the technique was evaluated atthe West Beckham TOR (Tropospheric Ozone Research) Station near the northNorfolk coast in Eastern England between September 1989 and August 1990. PANmeasured by the new technique was reasonably well correlated with PANrecorded using electron capture gas chromatography (EC/GC). PAN was alsowell correlated with ozone (O³) in the summer months. Springand autumn episodes of simultaneously high concentrations of PAN andO³ were examined in conjunction with air parcelback-trajectories and synoptic- and local-scale meteorology in a study ofthe sources of photooxidants on the east coast of England. Spring-timemeasurements of PAN made in the free troposphere in a light aircraft ataltitudes up to 3.1 km showed the presence of 0.54 and 0.26 ppbv PAN inpolar maritime and mid-latitude oceanic air masses, respectively. Thetechnique is particularly suited to airborne applications because potentialinterferences are minimised and the frequency of measurements is higher thangenerally achieved with EC/GC methods.     

Studies of Oxidant Production at the Weybourne Atmospheric Observatory in Summer and Winter Conditions

Detailed studies have been made of the behaviour of gases and radicals involved in the production of oxidants at the Weybourne Atmospheric Observatory in both summertime and wintertime conditions. In June 1995 the range of meteorological conditions experienced varied such that ozone destruction was observed in clean northerly air flows reaching Weybourne down the North Sea from the Arctic, and ozone production was observed in varying degrees in air with different loadings of nitrogen oxides and other precursors. The transition point for ozone destruction to ozone production occurred at a nitric oxide concentration of the order of 50 pptv. Plumes of polluted air from various urban areas in the U.K. were experienced in the June campaign at Weybourne. Quantitative studies of ozone production in a plume from the Birmingham conurbation on 18 June 1995 showed that the measurement of ozone production agreed well with calculated production rates from the product of the nitric oxide and peroxy radical concentrations (r2=0.9). In wintertime conditions (October–November 1994) evidence was also found for oxidant production, defined as the sum of O3+NO2. At this time of year the peroxy radical concentrations (RO2) were much lower than observed in the summertime and the nitric oxide (NO) was much higher. There was still sufficient RO2 during the day, however, for a slow accumulation of oxidant. Confirmatory evidence for this comes from the diurnal co-variance of (O3+NO2) with PAN, an excellent tracer of tropospheric photochemistry. The same type of covariance occurs in summer between PAN and ozone. The results obtained in these series of measurements are pertinent to understanding the measures necessary to control production of regional photochemical air pollution, and to the production of ozone throughout the northern hemisphere in winter.     

Synoptic and local scale atmospheric circulation associated with air pollution episodes in an urban Mediterranean area

Air pollution episodes in urban coastal areas follow certain pre-determined patterns, being associated with certain local meteorological conditions and emission of primary pollutants. In this study, the synoptic and local scale atmospheric circulation that prevails during air pollution episodes in a coastal major city in Greece, Thessaloniki, is examined for a period of 15 years (1989–2004). The study signifies the importance of studying air pollution meteorological patterns between coastal areas with different terrain characteristics. For Thessaloniki, it was found that the episodes occur mainly during the cold period of the year, while four types of synoptic scale circulation were recognized (I, II, III, IV) and five patterns of the local scale circulation (A1, A2, B1, B2 and B3). The highest percentage of episodes is associated with the presence of an anticyclone over the northern Greece (types I and IV), being characterized by weak or very weak surface pressure gradient intensity, according to the position and extension of the anticyclone. Moreover, a temperature increase of at least 1°C during the previous 3 days is required in the lower troposphere. Consistent with the synoptic conditions, the development of the sea breeze plays a crucial role in the occurrence of the episodes, even in the cold period of the year, when the sea breeze can still develop with smaller frequency and intensity. Finally, it was found that a small number of episodes is related with the advection of polluted air masses from the industrial area in the northwest of the city and from the Eordaia area in the west, which is the largest lignite producing area of Balkans.     

对流层氮氧化物光化学转化特征研究

应用大气光化学模式研究了日间影响NOx光化学转化率的主要物理化学因子.探讨了在不同NMHC/NOx比值时,NOx光化学特征及其转化产物的变化规律.结果表明,影响NOx转化率的主要因子是阳光辐射强度和NMHC/NOx比值.但在NMHC/NOx比值很低时,光强的增加并不能显著提高NOx转化率.温度和初始臭氧浓度对NOx转化率的影响次之.相对湿度对NOx转化率的影响较小.在不同NMHC/NOx比值下,NOx转化特征和产物有很大区别.NMHC/NOx比值高时,产物中PAN＞HNO3.NMHC/NOx比值中(低)时,产物主要是HNO3,PAN等有机氮不到10%(1%).最后初步比较了模拟和观测的NOy组成.     

Concentration profiles of hydrocarbons during episodes in relation to emission pattern,model calculations and oxidants

Since 1989 precursors and reaction products involved in tropospheric oxidant formation have been monitored continuously at the Swedish west coast (Rörvik) as part of the EUROTRAC-TOR project. During the spring 1990 two periods with enhanced concentrations of air pollutants in the boundary layer were observed, one in the middle of March (17th–19th) and the other in late April (23rd–27th). In this paper the episodes are described and discussed in relation to the formation of oxidants during long range transport. For the March episode the concentrations of oxidants and precursors were calculated by a photochemical trajectory model for air parcels transported from continental Europe to Rörvik. The predictions from the model are discussed in relation to the concentrations measured.     

Modelling of the long-range transport of peroxyacetylnitrate to Scandinavia

Model calculations and field measurements have shown that when air masses accumulate emissions of hydrocarbons and nitrogen oxides from sources in continental Europe and then move towards Scandinavia without any synoptic scale break-up of the atmospheric boundary layer (e.g. frontal passages), elevated PAN concentrations in southern Norway or Sweden in the range 1–5 ppb may be caused by long-range transport. The model calculations showed that over sea, the persistence of PAN was comparable to that of ozone in an ageing air mass when the temperatures were fairly low (5–10°C). At higher temperatures the thermal decomposition of PAN made the compound less persistent than ozone. Over land, the situation may be different since the ground removal is typically three times more efficient for ozone than for PAN.According to the model, the concentration of PAN did not change very much when an ageing air mass was exposed to moderate emissions of hydrocarbons, nitrogen oxides, or both. The concentration of PAN decreased less than the concentration of ozone when an ageing air mass was exposed to high emissions of nitrogen oxides.     

A meteorological analysis of ozone episodes using HYSPLIT model and surface data

Ozone episodes (> 100 ppbv) were observed frequently in Jinan, an urban site located between the highly polluted Yangtze Delta and Beijing–Tianjin region in East China. In this study, the ozone episodes observed in 2004 were analysed using the Hybrid Single-particle Lagrangian Integrated Trajectory (HYSPLIT) model and surface meteorological data, as well as Air Pollution Index (API). The meteorological conditions of episode days and non-episode days were compared and examined, and categorization of 6 groups of backward trajectories was performed. The results show that, most episodes were caused by local photochemical production (e.g., induced by sufficient sunshine duration and high temperature) and pollutant accumulation (e.g., induced by little rainfall and low wind speed), and transport of pollutants from the highly polluted regions could significantly influence the air quality at the site, especially from Yangtze Delta region. In addition, three typical ozone episodes were analysed using HYSPLIT model to infer any long-distance transport and surface meteorological data to infer the local ozone production potential. At last, the functions and inadequacies about the usage of HYSPLIT model combined with surface meteorological data for the analysis of photochemical pollution were discussed.     

A REGIONAL MODEL STUDY OF THE VARIATIONS AND DISTRIBUTIONS OF OZONE AND ITS PRECURSORS ON EASTERN ASIA AND WEST PACIFIC OCEAN REGIONS*

A simulated study of mechanism for variations and distributions of ozone and its precursors was made by using the three-dimensional regional Eulerian model.The results showed that the ozone production was controlled by NO_x,but there is a complicated nonlinear relation between them.The photochemical reactions controlled by solar radiation are the determinative factors affecting the variations of the surface ozone and its precursors.The relations of ozone and CO,PAN were studied.We compared the simulated and observed results during the PEM-WEST A in order to better understand the photochemical processes of ozone and its precursors.     

A REGIONAL MODEL STUDY OF THE VARIATIONS AND DISTRIBUTIONS OF OZONE AND ITS PRECURSORS ON EASTERN ASIA AND WEST PACIFIC OCEAN REGIONS

A simulated study of mechanism for variations and distributions of ozone and its precursors was made by using thethree-dimensional regional Eulerian model.The results showed that the ozone production was controlled by NO,butthere is a complicated nonlinear relation between them.The photochemical reactions controlled by solar radiation arethe determinative factors affecting the variations of the surface ozone and its precursors.The relations of ozone and CO,PAN were studied.We compared the simulated and observed results during the PEM-WEST A in order to better under-stand the photochemical processes of ozone and its precursors.     

An analytical investigation of a sequence of unusual springtime ozone episodes over metropolitan Taichung in 2007

This study investigated the potential factors contributing to a series of ozone (O₃) episodes in the Taichung metropolis, which occurred during the first half of May 2007. Surface data of the meteorological parameters and air pollutant concentrations, supported by Taiwan Environmental Protection Administration, and vertical data monitored via tethersonde sampling were analysed. The analyses showed that local anthropogenic activities and physical factors such as the sea–air interaction were not the main factors contributing to the O₃ events. Excluding these potential causes, the results suggest that, during the aforementioned period, the stronger Mainland High and Pacific Low may have been responsible for the long-range transport of large quantities of O₃ from Mainland China to Taiwan. Furthermore, O₃ photochemical activity also played an important role in the O₃ episodes. The faster consumption of NO lead to a more rapid increase in the O₃ concentration.     

Measurements of peroxyacetylnitrate in the marine boundary layer over the Atlantic

The atmospheric concentration of peroxyacetylnitrate (PAN) was measured during a cruise of the R.S. Polarstern from Bremerhaven (Germany) to Rio Grande do Sul (Brazil) in September/ October 1988. The measurements were made in-situ by a combination of electron capture gaschromatography with a cryogenic preconcentration step. The theoretical lower limit of detection (3) was 0.4 ppt. The mixing ratios of PAN varied by more than three orders of magnitude from 2000 ppt in the English Channel to less than 0.4 ppt south of the Azores (38° N). South of 35° N, PAN levels were below the detection limit, except at 30–31° S off the eastern coast of South America. Here, PAN mixing ratios of 10 to 100 ppt were detected in continentally influenced air masses. Detectable levels of PAN were mostly observed in air masses of continental or high northern origin. Changes in the wind directions were usually associated with substantial changes in the PAN mixing ratios.     

区域对流层光化学过程研究

将 MM5和 RADM耦合 ,建立了一个区域大气光化学模式。用此模式来研究区域大气光化学过程。分析了大气光化学过程中前体物、自由基以及主要产物的时空分布及其随时间的变化情况。得到了大气光化学过程各主要成分的分布及其演变特征。在此基础上 ,分析了水平平流、垂直扩散及沉降以及化学转化等物理、化学过程在大气光化学过程中的相对重要性 ,结果表明 ,水平平流和垂直扩散及沉降等物理过程对大气光化学过程中各种成分的浓度分布及其随时间的变化有重要的作用。     

An insight into the formation of severe ozone episodes: modeling the 21/03/01 event in the ESCOMPTE region

High ozone concentrations are observed more and more frequently in the lower troposphere. The development of such polluted episodes is linked to a complex set of chemical, physical and dynamical parameters that interact with each other. To improve air quality, it is necessary to understand and quantify the role of all these processes on the intensity of ozone formation. The ESCOMPTE program, especially dedicated to the numerical simulation of photochemical episodes, offers an ideal frame to investigate details of the roles of many of these processes through 3D modeling. This paper presents the analysis, with a 3D eulerian model, of a severe and local episode of ozone pollution that occurred on the 21st of March 2001 in the ESCOMPTE region. This episode is particularly interesting due to the intensity of the observed ozone peaks (450 μg/m³ during 15 mn) but also because it did not occur in summer but at the beginning of spring. As part of the premodeling work of the ESCOMPTE program, this study focuses on the sensitivity of the simulated ozone peaks to various chemical and physical phenomena (long-range transport, industrial emissions, local dynamic phenomena…) to determine their influence on the rise of high local photooxidant concentrations and to better picture the photochemistry of the ESCOMPTE region. Through sensitivity tests to dynamical calculation resolution and emissions, this paper shows how the combination of sea and pond breezes with emissions of reactive VOCs can generate local intense ozone peaks.     

Photochemical characteristics of high and low ozone episodes observed in the Taehwa Forest observatory (TFO) in June 2011 near Seoul South Korea

We present a comprehensive discussion on what cause high ozone episodes at a suburban photochemical observation site of the Seoul Metropolitan Area (population ～23 million). The observational site, Taehwa Research Forest (TRF), is situated ～30 km from the center of Seoul. In June 2011, we observed two very distinctive ozone periods-high ozone (peak up to 120 ppbv) and low ozone (peak up to 60 ppbv) in the mid and early month, respectively. The trace gas measurement dataset, especially CO and NO _X clearly indicate that less anthropogenic influences during the high ozone period. Volatile organic compound (VOC) measurement results show that at the observational site, biogenic VOCs (mostly isoprene) contribute most of chemical reactivity towards OH, although toluene from anthropogenic activities was observed in higher concentrations. Back-trajectory analysis indicates that air-masses from the forest part of Korea Peninsula were dominant influences during the high ozone episode event. On the other hand, Aged air masses from China were the dominant influence during the low ozone episode event. Model calculations conducted using the University of Washington Chemical Mechanism (UWCM) box model, also consistently show that BVOC, especially isoprene photochemistry, can be the significantly contribution to local ozone formation in the given photochemical environments of TRF. These research results strongly suggest that ozone control strategy in the Eastern Asian megacities, mostly situated in surrounding forest areas should be based on the comprehensive scientific understanding in BVOC photochemistry and interplays between anthropogenic and biogenic interactions.     

European VOC Emission Estimates Evaluated by Measurements and Model Calculations

Observations and model calculations of the concentration of hydrocarbonsat five Scandinavian rural sites during March–June 1993are reported.Decreasing concentrations from March to June are observedat all sites. The highest concentrations of hydrocarbons were found in air massescoming in from the southwest to southeast, indicating that long rangetransport fromcontinental Europe and the U.K. is important in pollution episodes. An episode of elevated concentrations of hydrocarbons observed at three of the sites in the middle of Marchis described and discussed in relation to the synoptic situation and thepresenceof other chemical compounds (NO₂, PAN, total nitrate andozone).A Lagrangian numerical model is used to calculate the concentrations of theindividual hydrocarbons at the fivesites and comparison with observations is made.The calculated concentrations for nonmethane hydrocarbons with quite longchemicallifetimes agree well with the observations.For the sum of observed and calculated hydrocarbons the correlationcoefficientsare in the range of 0.65–0.88 for the five sitesand the ratio between calculated and measured concentrations was0.72–0.97, indicating thatthe European VOC emission inventory is quite well estimated.