Skip to main content
Log in

Intercomparison of Tropospheric OH Measurements by Different Laser Techniques during the POPCORN Campaign 1994

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

Abstract

In-situ OH measurements by laser-induced fluorescence (LIF) spectroscopy and folded long-path differential optical absorption spectroscopy (DOAS) were carried out in a rural environment in North-East Germany as part of the field experiment POPCORN in August 1994. The large set of OH data obtained allowed an intercomparison of both techniques based on relative diurnal profiles and simultaneously measured absolute concentrations. Most of the time the two OH instruments encountered the same air and agreed well in the measured relative diurnal variations. Only on a few occasions the measurements significantly disagreed due to a perturbation of the DOAS measurements by a local OH source in the north-western wind sector. Excluding data from this wind direction, the statistical analysis of 137 data pairs yields a correlation coefficient of r = 0.90 and a weighted linear fit with a slope of 1.09 ± 0.12. The correlations are carefully analyzed. The comparison of both instruments is discussed in the light of newly published effective absorption cross-sections for H2O and O2 that affect the calibration of LIF.

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

  • Aschmutat, U., Heßling, M., Holland, F., and Hofzumahaus, A., 1994: A tunable source of hydroxyl (OH) and hydroperoxy (HO2) radicals: In the range between 106 and 109 cm-3, in G. Angeletti and G. Restelli (eds), Physico-Chemical Behaviour of Atmospheric Pollutants 2, Proc. EUR 15609, pp. 811-816.

  • Beck, S. M., Bendura, R. J., McDougal, D. S., Hoell Jr., J. M., Gregory, G. L., Curfman Jr., H. J., Davis, D. D., Bradshaw, J., Rodgers, M. O., Wang, C. C., Davis, L. I., Campbell, M. J., Torres, A. L., Carroll, M. A., Ridley, B. A., Sachse, G. W., Hill, G. F., Condon, E. P., and Rasmussen, R. A., 1996: Operational overview of NASA GTE/CITE 1 airborne instrument intercomparisons: Carbon monoxide, nitric oxide, and hydroxyl instrumentation, J. Geophys. Res. 92, 1977-1985.

    Google Scholar 

  • Brandenburger, U., Brauers, T., Dorn, H.-P., Hausmann, M., and Ehhalt, D. H., 1998: In situmeasurement of tropospheric hydroxyl radicals by folded long-path laser absorption during the field campaign POPCORN, J. Atmos. Chem. 31, 181-204.

    Google Scholar 

  • Brauers, T., Aschmutat, U., Brandenburger, U., Dorn, H.-P., Hausmann, M., Heßling, M., Hofzumahaus, A., Holland, F., Plass-Dülmer, C., and Ehhalt, D. H., 1996: Intercomparison of tropospheric OH radical measurements by multiple folded long-path laser absorption and laser induced fluorescence, Geophys. Res. Lett. 23, 2545-2548.

    Google Scholar 

  • Brauers, T., Dorn, H.-P., Koch, H., Kraus, A. B., and Plass-Dülmer, C., 1998: Meteorological aspects, ozone, and solar radiation measurements during POPCORN 1994, J. Atmos. Chem. 31, 33-52.

    Google Scholar 

  • Campbell, M. J., Hall, B. D., Sheppard, J. C., Utley, P. L., O'Brien, R. J., Hard, T. M., and George, L. A., 1995: Intercomparison of local hydroxyl measurements by radiocarbon and FAGE techniques, J. Atmos. Sci. 52, 3421-3427.

    Google Scholar 

  • Cantrell, C. A., Zimmer, A., and Tyndall, G. S., 1997: Absorption cross sections for water vapor from 183 to 193 nm, Geophys. Res. Lett. 24, 2195-2198.

    Google Scholar 

  • Creasey, D. J., Halford-Maw, P. A., Heard, D. E., Pilling, M. J., and Whitaker, B. J., 1997: Implementation and initial deployment of a field instrument for measurement of OH and HO2 in the troposphere by laser-induced fluorescence, J. Chem. Soc. Farad. Trans. 93, 2907-2913.

    Google Scholar 

  • Crutzen, P. J., and Zimmermann, P. H., 1991: The changing photochemistry of the troposphere, Tellus 43AB, 136-151.

    Google Scholar 

  • DeMore, W. B., Sander, S. P., Golden, D. M., Hampson, R. F., Kurylo, M. J., Howard, C. J., Ravishankara, A. R., Kolb, C. E., and Molina, M. J., 1997: Chemical kinetics and photochemical data for use in stratospheric modeling, Evaluation number 12, JPL Publication 97-4.

  • Dorn, H.-P., Brandenburger, U., Brauers, T., and Hausmann, M., 1995: A new in situlaser longpath absorption instrument for the measurement of tropospheric OH radicals, J. Atmos. Sci. 52, 3373-3380.

    Google Scholar 

  • Dorn, H.-P., Neuroth, R., and Hofzumahaus, A., 1995: Investigation of OH absorption cross sections of rotational transitions in the A2+,υ ′ = 0 ← X 2П, υ″ band under atmospheric conditions. Implications for tropospheric long-path absorption measurements, J. Geophys. Res. D100, 7397-7409.

    Google Scholar 

  • Ehhalt, D. H., Dorn, H.-P., and Poppe, D., 1991: The chemistry of the hydroxyl radical in the troposphere, Proc. Royal Soc. Edinburgh 97B, 17-34.

    Google Scholar 

  • Eisele, F. L., Mount, G. H., Fehsenfeld, F. C., Harder, J., Marovich, E., Parrish, D. D., Roberts, J., Trainer, M., and Tanner, D., 1994: Intercomparison of tropospheric OH and ancillary trace gas measurements at Fritz Peak Observatory, Colarado, J. Geophys. Res. D99, 18605-18626.

    Google Scholar 

  • Hausmann, M., Brandenburger, U., Brauers, T., and Dorn, H.-P., 1997: Detection of tropospheric OH radicals by long-path differential optical absorption spectroscopy: Experimental setup, accuracy, and precision, J. Geophys. Res. 102, 16011-16022.

    Google Scholar 

  • Hofzumahaus, A., Aschmutat, U., Heßling, M., Holland, F., and Ehhalt, D. H., 1996: The measurement of tropospheric OH radicals by laser-induced fluorescence spectroscopy during the POPCORN field campaign, Geophys. Res. Lett. 23, 2541-2544.

    Google Scholar 

  • Hofzumahaus, A., Brauers, T., Aschmutat, U., Brandenburger, U., Dorn, H.-P., Hausmann, M., Heßling, M., Holland, F., Plass-Dülmer, C., and Ehhalt, D. H., 1997: Reply, Geophys. Res. Lett. 24, 3039-3040.

    Google Scholar 

  • Holland, F., Heßling, M., and Hofzumahaus, A., 1995: In situmeasurement of tropospheric OH radicals by laser-induced fluorescence - a description of the KFA instrument, J. Atmos. Sci. 52, 3393-3401.

    Google Scholar 

  • Holland, F., Aschmutat, U., Heßling, M., Hofzumahaus, A., and Ehhalt, D. H., Highly time resolved measurements of OH during POPCORN using laser-induced fluorescence spectroscopy, J. Atmos. Chem., this issue.

  • Hudson, R. D. and Kieffer, L. J., 1975: Absorption cross sections of stratospheric molecules, The Natural Stratosphere of 1974, CIAP Monograph 1, pp. 5156-5194.

  • Lanzendorf, E. J., Hanisco, T. F., Donahue, N. M., and Wennberg, P. O., 1997: Comment on: The measurement of tropospheric OH radicals by laser-induced fluorescence spectroscopy during the POPCORN field campaign, by Hofzumahaus et al.and Intercomparison of tropospheric OH radical measurements by multiple folded long-path laser absorption and laser induced fluorescence, by Brauers et al., Geophys. Res. Lett. 24, 3037-3038.

    Google Scholar 

  • Leonard, C., 1990: Entwicklung eines UV-laserspektroskopischen Nachweisverfahrens für OH-Radikale und spektroskopische Untersuchungen an Spurengasen unter troposphärischen Bedingungen, Ph-D Thesis, Universität Hannover.

  • Mather, J. H., Stevens, P. S., and Brune, W. H., 1997: OH and HO2 measurements using laser-induced fluorescence, J. Geophys. Res. 102, 6427-6436.

    Google Scholar 

  • Mount, G. H., Eisele, F. L., Tanner, D. J., Brault, J. W., Johnston, P. V., Harder, J. W., Williams, E. J., Fried, A., and Shetter, R., 1997: An intercomparison of spectroscopic laser long-path and ion-assisted in situmeasurements of hydroxyl concentrations during the Tropospheric OH Photochemistry Experiment, fall 1993, J. Geophys. Res. 102, 6437-6455.

    Google Scholar 

  • Plass-Dülmer, C., Brauers, T., and Rudolph, J., 1998: POPCORN - A field study of photochemistry in North-Eastern Germany, J. Atmos. Chem. 31, 5-31.

    Google Scholar 

  • Press, W. H., Teukolsky, S. A., Vetterling, W. T., and Flannery, B. P., 1992: Numerical Recipes in C: The Art of Scientific Computing, 2nd. ed., Cambridge University Press, pp. 656-670.

  • Rohrer, F., Brüning, D., Grobler, E. S., Weber, M., Ehhalt, D. H., Neubert, R., Schüßler, W., and Levin, I., 1998: Mixing ratios and photostationary state of NO and NO2 observed during the POPCORN field campaign at a rural site in Germany, J. Atmos. Chem. 31, 119-137.

    Google Scholar 

  • Schultz, M., Heitlinger, M., Mihelcic, D., and Volz-Thomas, A., 1995: Calibration source for peroxy radicals with built-in actinometry using H2O andO2 photolysis at 185 nm, J. Geophys. Res. 100, 18,811-18,816.

    Google Scholar 

  • Tanner, D. J., Jefferson, A., and Eisele, F. L., 1997: Selected ion chemical ionization mass spectrometric measurement of OH, J. Geophys. Res. 102, 6415-6425.

    Google Scholar 

  • Washida, N., Mori, Y., and Tanaka, I., 1971: Quantum yield of ozone formation from photolysis of the oxygen molecule at 1849 and 1931 Å, J. Chem. Phys. 54, 1119-1122.

    Google Scholar 

  • Yoshino, K., Esmond, J. R., Parkinson, W. H., Ito, K., and Matsui, T., 1996: Absorption cross section measurements of water vapor in the wavelength region 120 to 188 nm, Chem. Phys. 211, 387-391.

    Google Scholar 

Download references

Author information

Authors and Affiliations

Authors

Rights and permissions

Reprints and permissions

About this article

Cite this article

Hofzumahaus, A., Aschmutat, U., Brandenburger, U. et al. Intercomparison of Tropospheric OH Measurements by Different Laser Techniques during the POPCORN Campaign 1994. Journal of Atmospheric Chemistry 31, 227–246 (1998). https://doi.org/10.1023/A:1006014707617

Download citation

  • Issue Date:

  • DOI: https://doi.org/10.1023/A:1006014707617

Navigation