Peroxyacetyl Nitrate (PAN) Measurements During the POPCORN Campaign

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Abstract

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

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