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30 CHAPTER 2. ATMOSPHERE AND REMOTE SENSING 2.1.12 Long Term Observations of Urban Atmospheric Radical Chemistry (TURBAN) Participating scientists Jutta Zingler, Christoph Kern, Daniel Pedersen, Valeri Matveev, Mordechai Peleg, Ulrich Platt, Menachem Luria Abstract Using Long Path DOAS and MiniDOAS, seasonal and spatial patterns in the chemistry of NO3 in an arid urban location are investigated. Its contribution to the transformation and removal of atmospheric compounds is evaluated. Long term measurements are validated and complemented by a short term intensive measurement period. Figure 2.12: Vertical NO3 profiles: Measurement geometry for the MiniDOAS part of this study. Background The nitrate radical (NO3) is a key component of nighttime chemistry in the troposphere and is responsible for the nonphotochemical production of peroxy radicals and the transformation of important species such as nitrogen oxides, VOCs, and ozone. It can be comparable to the OH radical as a sink for nitrogen oxides and VOCs. Up to this project, the only two studies to provide long term nighttime measurements of NO3 in the boundary layer were conducted in Germany at a rural coastal site [Heintz et al. , 1996] and at a rural suburban site [Geyer et al. , 2001]. One short-term study reported daytime measurements of NO3 [Geyer et al. , 2003]. Funding German Israeli Foundation for Scientific Research and Development (G.I.F.) Methods and results A long term monitoring station has been established by the Hebrew University of Jerusalem in the urban center of Jerusalem, including a Long Path DOAS system and several monitors for a variety of atmospheric trace gases and parameters. During an intensive one month joint field work campaign, IUP Heidelberg has set up a high end Long Path DOAS system aiming for quality control, high time resolution and enhancement of species investigated. A red LED as alternative light source and new technology was applied successfully during some days. Vertical profiles of NO3 have been measured using an advanced MiniDOAS system equipped with a VIS mini-spectrograph (MiniTURBAN). Stray light spectra acquired during sunrise give an idea on the concentration profiles in higher atmospheric layers. Information on photolytic rates is retrieved from solar radiation measurements with a spectral radiometer. Our long path measurements yielded positive results for NO3 during almost every night, with mixing ratios up to 300 ppt. NO3 was found during a period of very high humidity. Good agreement could be found comparing NO2 Long Path DOAS data with in situ monitor results. Outlook/Future work Evaluation improvement, intercomparison/correlation of data, quality control for long term data, profile modelling, investigation of photolysis parameters. Main publication in preparation
2.1. TROPOSPHERIC RESEARCH GROUP 31 References Ball, S. M., Langridge, J. M., & Jones, R. L. 2004. Broadband cavity enhanced absorptions spectroscopy using light-emitting diodes. Chem. Phys. Lett., 398, 68–74. Barrie, L. A., & Platt, U. 1997. Arctic tropospheric chemistry. Overview to Tellus special issue, 49B, 450–454. Bobrowski, N. 2005. Volcanic Gas Studies by MAX-DOAS. Dissertation, Universität Heidelberg. Bobrowski, N., & Filsinger, F. 2005. Mini-MAX-DOAS Manual. Universität Heidelberg. Bobrowski, N., Hönninger, G., Lohberger, F., & Platt, U. 2005. IDOAS: A new monitoring technique to study the 2D distribution of volcanic gas emissions. J. Volcanol. Geotherm. Res., Accepted for publishing. Burkholder, J. B., Curtius, J., Ravishankara, A. R., & Lovejoy, E. R. 2004. Laboratory studies of the homogeneous nucleation of iodine oxides. Atmos. Chem. Phys., 4, 19–34. Cauer, H. 2004. Schwankungen der Jodmenge der Luft in Mitteleuropa, deren Ursachen und deren Bedeutung für den Jodgehalt unserer Nahrung (Auszug). Angewandte Chemie 52, 11, 625–628. Cox, R. A., Bloss, W. J., Jones, R. L., & Rowley, D. M. 1999. OIO and the Atmospheric Cycle of Iodine. Geophys. Res. Lett., 26 (13), 1857–1860. Geyer, A., Ackermann, R., Dubois, R., Lohrmann, B., Müller, T., & Platt, U. 2001. Long-term observation of nitrate radicals in the continental boundary layer near Berlin. Atmos. Env., 35, 3619–3631. Geyer, A., Alicke, B., Ackermann, R., Martinez, M., Harder, H., Brune, W., Carlo, Piero di, Williams, E., Jobson, T., Hall, S., Shetter, R., & Stutz, J. 2003. Direct observations of daytime NO3: Implications for urban boundary layer chemistry. J. Geosphys. Res., 108 (D17), 4368. Hak, C., Pundt, I., Trick, S., Kern, C., Platt, U., Dommen, J., Ordnez, C., Prvt, A. S. H., Junkermann, W., Astorga-Llorns, C., Larsen, B. R., Mellqvist, J., Strandberg, A., Yu, Y., Galle, B., Kleffmann, J., Lörzer, J. C., Braathen, G. O., & Volkamer, R. 2005. Intercomparison of four different in-situ techniques for ambient formaldehyde measurements in urban air. Atmos. Chem. Phys. Discuss., 5, 2897–2945. Heintz, F., Platt, U., Flentje, H., & Dubois, R. 1996. Long-term observation of nitrate radicals at the Tor Station, Kap Arkona (Rügen). J. Geophys. Res., 101 (D17), 22891–22910. Hoffmann, T., O’Dowd, C. D., & Seinfeld, J. H. 2001. IO homogeneous nucleation. An explanation for coastal new particle formation. Geophys. Res. Lett., 28 (10), 1949–1952. Kern, C. 2004. Applicability of light-emitting diodes as light sources for long path DOAS measurements: A feasibility study. Diplomarbeit, Universität Heidelberg. Kern, C., Trick, S., Rippel, B., & Platt, U. 2005. Applicability of light-emitting diodes as light sources for active DOAS measurements. Appl. Opt., Accepted for publishing. Leck, C., & Bigg, E. K. 1999. Aerosol production over remote marine areas - A new route. Geophys. Res. Lett., 26, 3577–3580. Lee, J. S., Kim, Y. J., Kuk, B., Geyer, A., & Platt, U. 2005. Simultaneous Measurements of Atmospheric Pollutants and Visibility with a Long-Path DOAS System in Urban Areas. Environ. Monit. Assess., 104, 281–293. Lindberg, S., Brooks, S., Lin, C. J., Scott, K. J., Landis, M. S., Stevens, R. K., Goodsite, M., & Richter, A. 2002. Dynamic Oxidation of Gaseous Mercury in the Arctic Troposphere at Polar Sunrise. Environ. Sci. Technol., 36, 1245–1256. Louban, I. 2005. Zweidimensionale Aufnahmen von Spurenstoff-Verteilungen. Diplomarbeit, Universität Heidelberg. O’Dowd, C., Jimenez, J. L., Bahreini, R., Flagan, R. C., Seinfeld, J. H., Hämeri, K., Pirjola, L., ans S. G. Jennings, M. Kulmala, & Hoffmann, T. 2002. Marine aerosol formation from biogenic iodine emissions. Nature, 417, 632–636.
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2.7. CARBON CYCLE GROUP 111 2.7.4 I
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