References

ACP

Atmospheric Chemistry and Physics

ACP

1680-7324

Copernicus GmbH

Göttingen, Germany

10.5194/acp-10-2795-2010

Nocturnal nitrogen oxides at a rural mountain-site in south-western Germany

Crowley

J. N.

¹ Schuster

¹ Pouvesle

¹ Parchatka

¹ Fischer

¹ Bonn

² Bingemer

² Lelieveld

Max-Planck-Institut für Chemie, Atmospheric Chemistry Dept., Mainz, Germany

Universität Frankfurt, Fachbereich Geowissenschaften, Frankfurt am Main, Germany

25 03 2010

10 6 2795 2812

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A new, two-channel instrument for simultaneous NO3 and N2O5 monitoring was used to make the first comprehensive set of nocturnal NOx measurements (NO, NO2, NO3 and N2O5) at the Taunus Observatory, a rural mountain site (Kleiner Feldberg) in South-western Germany. In May 2008, NO3 and N2O5 mixing ratios were well above the instrumental detection limit (a few ppt) on all nights of the campaign and were characterised by large variability. The concentrations of NO3, N2O5 and NO2 were consistent with the equilibrium constant, K2, defining the rates of formation and thermal dissociation of N2O5. A steady-state lifetime analysis is consistent with the loss of nocturnal NOx being dominated by the reaction of NO3 with volatile organic compounds in this forested region, with N2O5 uptake to aerosols of secondary importance. Analysis of a limited dataset obtained at high relative humidity indicated that the loss of N2O5 by reaction with water vapour is less efficient (>factor 3) than derived using laboratory kinetic data. The fraction of NOx present as NO3 and N2O5 reached ~20% on some nights, with night-time losses of NOx competing with daytime losses.

References 1

Aldener, M., Brown, S. S., Stark, H., Williams, E. J., Lerner, B. M., Kuster, W. C., Goldan, P. D., Quinn, P. K., Bates, T. S., Fehsenfeld, F. C., and Ravishankara, A. R.: Reactivity and loss mechanisms of NO3 and N2O$_5$ in a polluted marine environment: Results from in situ measurements during New England Air Quality Study 2002, J. Geophys. Res., 111, D23S73, doi:10.1029/2006JD007252, 2006.

Allan, B. J., Carslaw, N., Coe, H., Burgess, R. A., and Plane, J. M. C.: Observations of the nitrate radical in the marine boundary layer, J. Atmos. Chem., 33, 129–154, 1999.

Allan, B. J., McFiggans, G., Plane, J. M. C., Coe, H., and McFadyen, G. G.: The nitrate radical in the remote marine boundary layer, J. Geophys. Res., 105, 24191–24204, 2000.

Ambrose, J. L., Mao, H., Mayne, H. R., Stutz, J., Talbot, R., and Sive, B. C.: Night-time nitrate radical chemistry at Appledore island, Maine during the 2004 international consortium for atmospheric research on transport and transformation, J. Geophys. Res., 112, D21302, doi:101.1029/2007JD008756, 2007.

Apodaca, R. L., Simpson, W. R., Brauers, T., Brown, S. S., Cohen, R. C., Crowley, J., Dorn, H. P., Dubé, W. P., Fry, J., Fuchs, H., Haseler, R., Heitmann, U., Kato, S., Kajii, Y., Kiendler-Scharr, A., Labazan, I., Matsumoto, J., Nishida, S., Tillmann, R., Rohrer, F., Rollings, A.W., Schlosser, E., Schuster, G., Tillmann, R., Wahner, A., Wegener, R., and Wooldridge, P. J.: Intercomparison of N2O$_5$ sensors using the SAPHIR reaction chamber, Atmos. Chem. Phys. Discusss., in preparation, 2010.

Atkinson, R. and Arey, J.: Atmospheric degradation of volatile organic compounds, Chem. Rev., 103, 4605–4638, 2003.

Atkinson, R., Baulch, D. L., Cox, R. A., Crowley, J. N., Hampson, R. F., Hynes, R. G., Jenkin, M. E., Rossi, M. J., and Troe, J.: Evaluated kinetic and photochemical data for atmospheric chemistry: Volume I – gas phase reactions of Ox, HOx, NOx and SOx species, Atmos. Chem. Phys., 4, 1461–1738, 2004.

Berden, G., Peeters, R., and Meijer, G.: Cavity ring-down spectroscopy: Experimental schemes and applications, Int. Rev. Phys. Chem., 19, 565–607, 2000.

Brown, S. S., Dube, W. P., Fuchs, H., Ryerson, T. B., Wollny, A. G., Brock, C. A., Bahreini, R., Middlebrook, A. M., Neuman, J. A., Atlas, E., Roberts, J. M., Osthoff, H. D., Trainer, M., Fehsenfeld, F. C., and Ravishankara, A. R.: Reactive uptake coefficients for N2O$_5$ determined from aircraft measurements during the Second Texas Air Quality Study: Comparison to current model parameterizations, J. Geophys. Res., 114, D00F10, doi:10.1029/2008JD011679, 2009.

Brown, S. S., Dubé, W. P., Osthoff, H. D., Wolfe, D. E., Angevine, W. M., and Ravishankara, A. R.: High resolution vertical distributions of NO3 and N2O$_5$ through the nocturnal boundary layer, Atmos. Chem. Phys., 7, 139–149, 2007.

Brown, S. S., Ryerson, T. B., Wollny, A. G., Brock, C. A., Peltier, R., Sullivan, A. P., Weber, R. J., Dube, W. P., Trainer, M., Meagher, J. F., Fehsenfeld, F. C., and Ravishankara, A. R.: Variability in nocturnal nitrogen oxide processing and its role in regional air quality, Science, 311, 67–70, 2006.

Brown, S. S., Stark, H., and Ravishankara, A. R.: Applicability of the steady state approximation to the interpretation of atmospheric observations of NO3 and N2O$_5$, J. Geophys. Res., 108, 4539, doi:10.1029/2003JD003407, 2003a.

Brown, S. S., Stark, H., Ryerson, T. B., Williams, E. J., Nicks, D. K., Trainer, M., Fehsenfeld, F. C., and Ravishankara, A. R.: Nitrogen oxides in the nocturnal boundary layer: Simultaneous in situ measurements of NO3, N2O$_5$, NO2, NO, and O3, J. Geophys. Res., 108, 4299, doi:10.1029/2002JD002917, 2003b.

Curtis, A. R. and Sweetenham, W. P.: Facsimile, AERE, Report R-12805, 1987.

Dorn, H. P., Apodaca, R. L., Ball, S. M., Brauers, T., Brown, S. S., Crowley, J. N., Dube, W. P., Fuchs, H., Häseler, R., Heitmann, U., Jones, R. L., Labazan, I., Langridge, J., Meinen, J., Platt, U., Pöhler, D., Rohrer, F., Ruth, A. A., Schlosser, E., Schuster, G., Shillings, A., Simpson, W., Thieser, J., Varma, R., Venables, D., and Wahner, A.: Intercomparison of NO3 radical detection instruments in the Atmosphere Simulation Chamber SAPHIR., Atmos. Chem. Phys. Discuss., in preparation, 2010.

Ehhalt, D. H. and Rohrer, F.: Dependence of the OH concentration on solar UV, J. Geophys. Res., 105, 3565–3571, 2000.

Fehsenfeld, F., Calvert, J., Fall, R., Goldan, P., Guenther, A., Hewitt, C.N., Lamb, B., Liu, S., Trainer, M., Westberg, H., and Zimmerman, P.: Emissions of volatile organic compounds from vegetation and the implications for atmospheric chemistry, Global Biogeochem. Cycles, 6, 389–430, 1992.

Folkers, M., Mentel, T. F., and Wahner, A.: Influence of an organic coating on the reactivity of aqueous aerosols probed by the heterogeneous hydrolysis of N2O$_5$, Geophys. Res. Lett., 30, 1644, doi:10.1029/2003GL017168, 2003.

Fontijn, A., Sabadell, A. J., and Ronco, R. J.: Homogeneous chemiluminescent measurement of nitric oxide with ozone – Implications for continuous selective monitoring of gaseous air pollutants, Anal. Chem., 42, 575–579, 1970.

Fuzzi, S., Facchini, M. C., Schell, D., Wobrock, W., Winkler, P., Arends, B. G., Kessel, M., Mols, J. J., Pahl, S., Schneider, T., Berner, A., Solly, I., Kruisz, C., Kalina, M., Fierlinger, H., Hallberg, A., Vitali, P., Santoli, L., and Tigli, G.: Multiphase Chemistry and Acidity of Clouds at Kleiner-Feldberg, J. Atmos. Chem., 19, 87–106, 1994.

Geyer, A., Alicke, B., Konrad, S., Schmitz, T., Stutz, J., and Platt, U.: Chemistry and oxidation capacity of the nitrate radical in the continental boundary layer near Berlin, J. Geophys. Res., 106, 8013–8025, 2001.

Geyer, A. and Platt, U.: Temperature dependence of the NO3 loss frequency: A new indicator for the contribution of NO3 to the oxidation of monoterpenes and NOx removal in the atmosphere, J. Geophys. Res., 107, 4431, doi:10.1029/2001JD001215, 2002.

Hallquist, M., Stewart, D. J., Baker, J., and Cox, R. A.: Hydrolysis of N2O$_5$ on submicron sulfuric acid aerosols, J. Phys. Chem. A, 104, 3984–3990, 2000.

Handisides, G. M.: The influence of peroxy radicals on ozone production, PhD thesis, Johann Wolfgang Goethe Universität, Fachbereich Geowissenschaften, Frankfurt am Main, 2001.

Handisides, G. M., Plass-D�lmer, C., Gilge, S., Bingemer, H., and Berresheim, H.: Hohenpeissenberg Photochemical Experiment (HOPE 2000): Measurements and photostationary state calculations of OH and peroxy radicals, Atmos. Chem. Phys., 3, 1565–1588, 2003.

Heintz, F., Platt, U., Flentje, H., and Dubois, R.: Long-term observation of nitrate radicals at the tor station, Kap Arkona (Rugen), J. Geophys. Res., 101, 22891–22910, 1996.

IUPAC, Subcommittee for gas kinetic data evaluation (Ammann, M., Atkinson, R., Cox, R. A., Crowley, J. N., Hynes, R. G., Jenkin, M. E., Mellouki, W., Rossi, M. J., Troe, J., and Wallington, T. J.): Evaluated kinetic data: http://www.iupac-kinetic.ch.cam.ac.uk/, 2009.

Kley, D. and McFarland, M.: Chemiluminescence detector for NO and NO2, Atmos. Technol., 12, 63–69, 1980.

Kraus, A. and Hofzumahaus, A.: Field measurements of atmospheric photolysis frequencies for O3, NO2, HCHO, CH3CHO, hooh, and HONO by UV spectroradiometry, J. Atmos. Chem. 31, 161–180, 1998.

Mazurenka, M., Orr-Ewing, A. J., Peverall, R., and Ritchie, G. A. D.: Cavity ring-down and cavity enhanced spectroscopy using diode lasers, Annu. Rep. Prog. Chem., Sect C, 101, 100–142, 2005.

Orphal, J., Fellows, C. E., and Flaud, P. M.: The visible absorption spectrum of NO3 measured by high-resolution Fourier transform spectroscopy, J. Geophys. Res., 108, 4077, doi:10.1029/2002JD002489, 2003.

Osthoff, H. D., Pilling, M. J., Ravishankara, A. R., and Brown, S. S.: Temperature dependence of the NO3 absorption cross-section above 298 K and determination of the equilibrium constant for NO3+NO$_2<->$N2O$_5$ at atmospherically relevant conditions, Phys. Chem. Chem. Phys., 9, 5785–5793, 2007.

Ridley, B. A., Grahek, F. E., and Walega, J. G.: A small, high-sensitivity, medium-response ozone detector suitable for measurements from light aircraft, J. Atmos. Ocean. Technol., 9, 142–148, 1992.

Sander, S. P., Friedl, R. R., Golden, D. M., Kurylo, M. J., Huie, R. E., Orkin, V. L., Moortgat, G. K., Ravishankara, A. R., Kolb, C. E., Molina, M. J., and Finlayson-Pitts, B. J.: Chemical Kinetics and Photochemical Data for Use in Atmospheric Studies, Evaluation Number 14, Jet Propulsion Laboratory, National Aeronautics ans Space Administration/Jet Propulsion Laboratory/California Institute of Technology, Pasadena, CA, 2003.

Sander, S. P., Friedl, R. R., Golden, D. M., Kurylo, M. J., Huie, R. E., Orkin, V. L., Moortgat, G. K., Ravishankara, A. R., Kolb, C. E., Molina, M. J., and Finlayson-Pitts, B. J.: Chemical kinetics and photochemical data for use in atmospheric studies: Evaluation Number 15, Jet Propulsion Laboratory, National Aeronautics and Space Administration/Jet Propulsion Laboratory/California Institute of Technology, Pasadena, CA, 2006.

Schuster, G., Labazan, I., and Crowley, J. N.: A cavity ring down/cavity enhanced absorption device for measurement of ambient NO3 and N2O$_5$, Atmos. Meas. Tech., 2, 1–13, 2009.

Trebs, I., Bohn, B., Ammann, C., Rummel, U., Blumthaler, M., Königstedt, R., Meixner, F. X., Fan, S., and Andreae, M. O.: Relationship between the NO2 photolysis frequency and the solar global irradiance, Atmos. Meas. Tech., 2, 725–739, 2009.

Wayne, R. P., Barnes, I., Biggs, P., Burrows, J. P., Canosa-Mas, C. E., Hjorth, J., Le Bras, G., Moortgat, G. K., Perner, D., Poulet, G., Restelli, G., and Sidebottom, H.: The nitrate radical: Physics, chemistry, and the atmosphere, Atmos. Environ., 25A, 1–206, 1991.

Wetter, T.: Eine Untersuchung zur Charakterisierung der Zeitlichen Variabilität det luftchemischen Bedingungen am Taunus-Observatorium: Messungen des CO und H2 Mischverhältnises im Winter 1996/7, Johan Wolfgang Goethe-Universität, Fachbereich Geowissenschaft, Frankfurt am Main, 1998.

Yokelson, R. J., Burkholder, J. B., Fox, R. W., Talukdar, R. K., and Ravishankara, A. R.: Temperature-dependence of the NO3 absorption-Spectrum, J. Phys. Chem., 98, 13144–13150, 1994.