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    Exploring the atmospheric chemistry of nitrous acid (HONO) at a rural site in Southern China
    (München : European Geopyhsical Union, 2012) Li, X.; Brauers, T.; Häseler, R.; Bohn, B.; Fuchs, H.; Hofzumahaus, A.; Holland, F.; Lou, S.; Lu, K.D.; Rohrer, F.; Hu, M.; Zeng, L.M.; Zhang, Y.H.; Garland, R.M.; Su, H.; Nowak, A.; Wiedensohler, A.; Takegawa, N.; Shao, M.; Wahner, A.
    We performed measurements of nitrous acid (HONO) during the PRIDE-PRD2006 campaign in the Pearl River Delta region 60 km north of Guangzhou, China, for 4 weeks in June 2006. HONO was measured by a LOPAP in-situ instrument which was setup in one of the campaign supersites along with a variety of instruments measuring hydroxyl radicals, trace gases, aerosols, and meteorological parameters. Maximum diurnal HONO mixing ratios of 1–5 ppb were observed during the nights. We found that the nighttime build-up of HONO can be attributed to the heterogeneous NO2 to HONO conversion on ground surfaces and the OH + NO reaction. In addition to elevated nighttime mixing ratios, measured noontime values of ≈200 ppt indicate the existence of a daytime source higher than the OH + NO→HONO reaction. Using the simultaneously recorded OH, NO, and HONO photolysis frequency, a daytime additional source strength of HONO (PM) was calculated to be 0.77 ppb h−1 on average. This value compares well to previous measurements in other environments. Our analysis of PM provides evidence that the photolysis of HNO3 adsorbed on ground surfaces contributes to the HONO formation.
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    Technical Note: Intercomparison of formaldehyde measurements at the atmosphere simulation chamber SAPHIR
    (München : European Geopyhsical Union, 2008) Wisthaler, A.; Apel, E.C.; Bossmeyer, J.; Hansel, A.; Junkermann, W.; Koppmann, R.; Meier, R.; Müller, K.; Solomon, S.J.; Steinbrecher, R.; Tillmann, R.; Brauers, T.
    The atmosphere simulation chamber SAPHIR at the Research Centre Jülich was used to test the suitability of state-of-the-art analytical instruments for the measurement of gas-phase formaldehyde (HCHO) in air. Five analyzers based on four different sensing principles were deployed: a differential optical absorption spectrometer (DOAS), cartridges for 2,4-dinitro\-phenyl\-hydrazine (DNPH) derivatization followed by off-line high pressure liquid chromatography (HPLC) analysis, two different types of commercially available wet chemical sensors based on Hantzsch fluorimetry, and a proton-transfer-reaction mass spectrometer (PTR-MS). A new optimized mode of operation was used for the PTR-MS instrument which significantly enhanced its performance for online HCHO detection at low absolute humidities. The instruments were challenged with typical ambient levels of HCHO ranging from zero to several ppb. Synthetic air of high purity and particulate-filtered ambient air were used as sample matrices in the atmosphere simulation chamber onto which HCHO was spiked under varying levels of humidity and ozone. Measurements were compared to mixing ratios calculated from the chamber volume and the known amount of HCHO injected into the chamber; measurements were also compared between the different instruments. The formal and blind intercomparison exercise was conducted under the control of an independent referee. A number of analytical problems associated with the experimental set-up and with individual instruments were identified, the overall agreement between the methods was fair.