Skip to main content
Log in

Simultaneous measurements of peroxy and nitrate radicals at Schauinsland

  • Published:
Journal of Atmospheric Chemistry Aims and scope Submit manuscript

    We’re sorry, something doesn't seem to be working properly.

    Please try refreshing the page. If that doesn't work, please contact support so we can address the problem.

Abstract

We present simultaneous field measurements of NO3 and peroxy radicals made at night in a forested area (Schauinsland, Black Forest, 48° N, 8° N, 1150 ASL), together with measurements of CO, O3, NO x , NO y , and hydrocarbons, as well as meteorological parameters. NO2, NO3, HO2, and ∑(RO2) radicals are detected with matrix isolation/electron spin resonance (MIESR). NO3 and HO2 were found to be present in the range of 0–10 ppt, whilst organic peroxy radicals reached concentrations of 40 ppt. NO3, RO2, and HO2 exhibited strong variations, in contrast to the almost constant values of the longer lived trace gases. The data suggest anticorrelation between NO3 and RO2 radical concentrations at night.

The measured trace gas set allows the calculation of NO3 and peroxy radical concentrations, using a chemical box model. From these simulations, it is concluded that the observed anthropogenic hydrocarbons are not sufficient to explain the observed RO2 concentrations. The chemical budget of both NO3 and RO2 radicals can be understood if emissions of monoterpenes are included. The measured HO2 can only be explained by the model, when NO concentrations at night of around 5 ppt are assumed to be present. The presence of HO2 radicals implies the presence of hydroxyl radicals at night in concentrations of up to 105 cm−3.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Similar content being viewed by others

References

  • Anastasi, C., Hopkinson, L., and Simson, V. J., 1991, Natural hydrocarbon emission in the United Kingdom,Atmos. Environ. 25, 1403–1408.

    Google Scholar 

  • Anderson, I. C. and Levine, J. S., 1987, Simultaneous field measurements of biogenic emissions of nitric oxide and nitrous oxide,J. Geophys. Res. 92, 965–976.

    Google Scholar 

  • Arnts, R. R., Petersen, W. B., Seila, R. L., and Gay, B. W. Jr., 1982, Estimates of α-pinene emissions from a loblolly pine forest using an atmospheric diffusion model,Atmos. Environ. 16, 2127–2137.

    Google Scholar 

  • Atkinson, R. and Lloyd, A. C., 1984, Evaluation of kinetic and mechanistic data for modeling of photochemical smog,J. Phys. Chem. Ref. Data 13, 315–444.

    Google Scholar 

  • Atkinson, R., Baulch, D. L., Cox, R. A., Hampson, R. F. Jr., Kerr, J. A., and Troe, J., 1989, Evaluated kinetic and photochemical data for atmospheric chemistry: Supplement III,J. Phys. Chem. Ref. Data 18, 881–1097.

    Google Scholar 

  • Atkinson, R., 1991, Kinetics and mechanisms of the gas-phase reactions of the NO3 radical with organic compounds,J. Phys. Chem. Ref. Data 20, 449–507.

    Google Scholar 

  • Atkinson, R., Aschmann, S. M., Arey, J., and Shorees, B., 1992, Formation of OH radicals in the gas phase reactions of O3 with a series of terpenes,J. Geophys. Res. 97, 6065–6073.

    Google Scholar 

  • Brauers, T., Dorn, H.-P., and Platt, U., 1990, Spectroscopic measurements of NO2, O3, SO2, IO and NO3 in maritime air, in G. Restelli and G. Angeletti (eds.),Physico-Chemical Behaviour of Atmospheric Pollutants, Proc. 5th European Symposium, Varesse, Italia, Kluwer Academic Publishers, Dordrecht, pp. 237–242.

    Google Scholar 

  • Cantrell, C. A., Stockwell, W. R., Anderson, L. G., Busarow, K. L., Perner, D., Schmeltekopf, A., Calvert, C. A., and Johnston, H. S., 1985, Kinetic study of the NO3-CH2O reaction and its possible role in the night-time tropospheric chemistry,J. Phys. Chem. 89, 139–146.

    Google Scholar 

  • Crowley, J. N., Burrows, J. P., Moortgat, G. K., Poulet, G., and LeBrass, G., 1990a, Room temperature rate coefficient for the reaction between CH3O2 and NO3,Int. J. Chem. Kin. 22, 673–681.

    Google Scholar 

  • Crowley, J. N., Bauer, D., Burrows, J. P., Moortgat, G. K., Poulet, G., and LeBrass, G., 1990b, Laboratory studies of the gas phase reaction between NO3 and simple peroxy radicals,XIth Int. Symp. Gas Kinetics, Assisi, Italy, 2–7 September.

  • Davidson, J. A., Cantrell, C. A., Shetter, R. E., McDaniel, A. H., and Calvert, C. A., 1990, The NO3 radical decomposition and NO3 scavenging in the troposphere,J. Geophys. Res. 95, 13963–13969.

    Google Scholar 

  • Flocke, F., Volz-Thomas, A., and Kley, D., 1988, Kopplung eines Chemilumineszenzdetektors mit einem Gaschromatographen zur selektiven Messung oxidierter Stickstoffverbindungen in der Atmosphäre, Berichte der KFA Jülich, Jül-2217.

  • Flocke, F., Volz-Thomas, A., and Kley, D., 1991, Measurement of alkyl nitrates in rural and polluted air masses,Atmos. Environ. 25, 1951–1960.

    Google Scholar 

  • Geiß, H., 1992, in preparation.

  • Hanson, P. J. and Lindberg, S. E., 1991, Dry deposition of reactive nitrogen compounds: a review of leaf, canopy and non-foliar measurements,Atmos. Environ. 25, 1615–1634.

    Google Scholar 

  • Heikes, B. G. and Thomson, A. M., 1983, Effects of heterogeneous processes on NO3, HONO and HNO3 chemistry in the troposphere,J. Geophys. Res. 88, 10883–10895.

    Google Scholar 

  • Herrmann, H., Exner, M., and Zellner, R., 1992, Laser-based studies of reactions of the nitrate radical in aqueous solution, subm. toBer. Bunsenges. Phys. Chem.

  • Hjorth, J., Lohse, C., Nielsen, C. J., Skov, H., and Restelli, G., 1990, Products and mechanisms of the gas-phase reactions between NO3 and a series of alkenes,J. Phys. Chem. 94, 7494–7500.

    Google Scholar 

  • Isidorov, V. A., Zenkevich, I. G., and Ioffe, B. V., 1985, Volatile organic compounds in the atmosphere of forests,Atmos. Environ. 19, 1–8.

    Google Scholar 

  • Jonston, H. S., Cantrell, C. A., and Calvert, J. G., 1986, Unimolecular decomposition of NO3 to form NO and O2 and review of N2O5/NO3 kinetics,J. Geophys. Res. 91, 1159–5172.

    Google Scholar 

  • Kirchner, W., Welter, F., Bongartz, A., Kames, J., Schweighofer, S., and Schurath, U., 1990, Trace gas exchange kinetics at the air/water surface,J. Atmos. Chem. 10, 427–449.

    Google Scholar 

  • Klemp, D., 1992, (unpublished results).

  • Lamb, B., Guenther, A., Gay, D., and Westberg, H., 1987, A national inventory of biogenic hydrocarbons emissions,Atmos. Environ. 21, 1695–1705.

    Google Scholar 

  • Mellouki, A., LeBras, G., and Poulet, G., 1988, Kinetics of the reactions of NO3 with OH and HO2,J. Phys. Chem. 92, 2229–2234.

    Google Scholar 

  • Madronich, S., and Calvert, J. G., 1990, Permutation reaction of organic peroxy radicals in the troposphere,J. Geophys. Res. 95, 5697–5715.

    Google Scholar 

  • Mihelcic, D., Müsgen, P., and Ehhalt, D. H., 1985, An improved method of measuring tropospheric NO2 and RO2 by matrix isolation and electron spin resonance,J. Atmos. Chem. 3, 341–361.

    Google Scholar 

  • Mihelcic, D., Volz-Thomas, A., Pätz, H. W., Kley, D., and Mihelcic, M., 1990, Numerical analysis of ESR spectra from atmospheric samples,J. Atmos. Chem. 11, 271–297.

    Google Scholar 

  • Mozurkewich, M. and Calvert, J. G., 1988, Reaction probability of N2O5 on aqueous aerosols,J. Geophys. Res. 93, 15889–15896.

    Google Scholar 

  • Morris, E. D. Jr. and Niki, H., 1974, Reaction of the nitrate radical with acetaldehyde and propylene,J. Phys. Chem. 78, 1337–1338.

    Google Scholar 

  • Neta, P. and Huie, R. E., 1986, Rate constant for reactions of NO3 radicals in aqueous solutions,J. Phys. Chem. 90, 4644–4648.

    Google Scholar 

  • Noxon, J. F., Norton, R. B., and Henderson, W. R., 1978, Observation of atmospheric NO3,Geophys. Res. Lett. 5, 675–678.

    Google Scholar 

  • Noxon, J. F., Norton, R. B., and Marovich, E., 1980, NO3 in the troposphere,Geophys. Res. Lett. 7, 125–128.

    Google Scholar 

  • Noxon, J. F., 1983, NO3 and NO2 in the mid-Pacific troposphere,J. Geophys. Res. 88, 11017–11021.

    Google Scholar 

  • Parrish, D. D., Williams, E. J., Fahey, D. W., Liu, S. C., and Fehsenfeld, F. C., 1987, Simultaneous field measurements of biogenic emissions of nitric oxide and nitrous oxide,J. Geophys. Res. 92, 2165–2171.

    Google Scholar 

  • Platt, U., Perner, D., Winer, A. M., Harris, G. W., and Pitts, J. N. Jr., 1980, Detection of NO3 in polluted atmosphere by differential optical absorption,Geophys. Res. Lett. 7, 89–92.

    Google Scholar 

  • Platt, U., Perner, D., Schröder, J., Kessler, C., and Toenissen, A., 1981, The diurnal variation of NO3,J. Geophys. Res. 86, 11965–11970.

    Google Scholar 

  • Platt, U., Winer, A. M., Biermann, H. W., Atkinson, R., and Pitts, J. N. Jr., 1984, Measurement of nitrate radical concentration in continental air,Environ. Sci. Technol. 18, 365–369.

    Google Scholar 

  • Platt, U., Rateike, M., Junkermann, W., Rudolph, J., and Ehhalt, D. H., 1988, New tropospheric OH measurements,J. Geophys. Res. 93, 5159–5166.

    Google Scholar 

  • Platt, U., LeBrass, G., Poulet, G., Burrows, J. P., and Moortgat, G. K., 1990, Peroxy radicals from night-time reactions of NO3 with organics compounds,Nature 348, 147–149.

    Google Scholar 

  • Roberts, J. M., Hahn, C. J., Fehsenfeld, F. C., Warnock, J. M., Albritton, D. L., and Sievers, R. E., 1985, Monoterpene hydrocarbons in the night-time troposphere,Environ. Sci. Technol. 19, 364–369.

    Google Scholar 

  • Rudolph, J., Johnen, F. J., Khedim, A., and Pilwat, G., 1990, The use of automated ‘on line’ gaschromatography for the monitoring of organic trace gases in the atmosphere at low levels,Int. J. Environ. Anal. Chem. 38, 143–155.

    Google Scholar 

  • Russell, A. G., McRae, G. J., and Cass, G. R., 1985, The dynamics of nitric acid production and the fate of nitrogen oxides,Atmos. Environ. 19, 893–903.

    Google Scholar 

  • Russell, A. G., Cass, G. R., and Seinfeld, J. H., 1986, On some aspects of night-time atmospheric chemistry,Environ. Sci. Technol. 20, 1167–1172.

    Google Scholar 

  • Slemr, F., and Seiler, W., 1984, Field measurements of NO and NO2 emissions from fertilized and unfertilized soils,J. Atmos. Chem. 2, 1–24.

    Google Scholar 

  • Sverdrup, G. M., Spicer, C. W., and Ward, G., 1987, Investigation of gas phase reaction of dinitrogen pentoxide with water vapor,Int. J. Chem. Kin. 19, 191–205.

    Google Scholar 

  • Thomas, K., 1992, PhD Thesis, Univ. Wuppertal.

  • Thomas, K., Kley, D., Mihelcic, D., and Volz-Thomas, A., 1989, Mass accommodation coefficient for NO3 radicals on Water: Implication for atmospheric oxidation processes, International Conference on the generation of oxidants on regional and global scales, Norwich, 3–7 July 1989.

  • Volz, A., Geiß, H., McKeen, St., and Kley, D., 1989, Correlation of ozone and solar radiation at Montsouris and Hohenpeißenberg: Indications for photochemical influence, in R. D. Bojkov and P. Fabian (eds.), Ozone in the atmosphere,Proc. Quadrennial Ozone Symposium 1988, Deepak Publishing, Hampton, pp. 447–450.

    Google Scholar 

  • Volz-Thomas, A., Kley, D., Pätz, H. W., Pilwat, G., Mihelcic, D., Flocke, F., and Smit, H. G. J., 1990, Local and regional ozone production: Chemistry and Transport: A contribution to the EUROTRAC subproject TOR, EUROTRAC Annual Report 1989, Part 9, pp. 57–62. International Scientific Secretariat Fraunhofer Institute IFU Garmisch-Partenkirchen.

  • Volz-Thomas, A., Smit, H. G. J., Kley, D., Aschmutat, U., Buers, H. J., Flocke, F., Garthe, H. J., Geiß, H., Gilge, S., Heil, T., Houben, N., Klemp, D., Loup, H., Mihelcic, D., Müsgen, P., Pätz, H. W., Pilwat, G., Sträter, W., and Su, Y., 1991, Local and regional ozone production: Chemistry and Transport: A contribution to the EUROTRAC subproject TOR, EUROTRAC Annual Report 1990, Part 9, pp. 83–94. International Scientific Secretariat Fraunhofer Institute IFU Garmisch-Partenkirchen.

  • Williams, E. J., Parrish, D. D., Buhr, M. P., Fehsenfeld, F. C., and Fall, R., 1988, Measurements of soil NO x emissions in central Pennsylvania,J. Geophys. Res. 93, 9539–9546.

    Google Scholar 

  • Williams, E. J., Parrish, D. D., and Fehsenfeld, F. C., 1987, Determination of nitrogen oxide emissions from soils: results from a grassland site in Colorado, United States,J. Geophys. Res. 92, 2173–2179.

    Google Scholar 

  • Yokouchi, Y., Okaniwa, M., Ambe, A., and Fuwa, K., 1983, Seasonal variation of monoterpenes in the atmosphere of a pine forest,Atmos. Environ. 17, 743–750.

    Google Scholar 

Download references

Author information

Authors and Affiliations

Authors

Rights and permissions

Reprints and permissions

About this article

Cite this article

Mihelcic, D., Klemp, D., Müsgen, P. et al. Simultaneous measurements of peroxy and nitrate radicals at Schauinsland. J Atmos Chem 16, 313–335 (1993). https://doi.org/10.1007/BF01032628

Download citation

  • Received:

  • Issue Date:

  • DOI: https://doi.org/10.1007/BF01032628

Key words

Navigation