1Forschungszentrum Jülich, ICG-2: Troposphäre, 52425 Jülich, Germany
2Frontier Research Center for Global Change (currently Research Institute for Global Change), Japan Agency for Marine-Earth Science and Technology, Yokohama 236-0001, Japan
3Tokyo Metropolitan University, Department of Applied Chemistry, Tokyo 192-0397, Japan
4Max Planck Institute for Chemistry, Atmospheric Chemistry Dept., 55020 Mainz, Germany
5Deutscher Wetterdienst, Meteorol. Observatorium, 82383 Hohenpeissenberg, Germany
6Forschungszentrum Karlsruhe, IMK-AAF, 76021 Karlsruhe, Germany
*now at: National University of Ireland Galway, Department of Physics, Galway, Ireland
Received: 26 May 2009 – Published in Atmos. Chem. Phys. Discuss.: 26 Jun 2009
Abstract. Hydroxyl radicals (OH) are the major oxidizing species in the troposphere. Because of their central importance, absolute measurements of their concentrations are needed to validate chemical mechanisms of atmospheric models. The extremely low and highly variable concentrations in the troposphere, however, make measurements of OH difficult. Three techniques are currently used worldwide for tropospheric observations of OH after about 30~years of technical developments: Differential Optical Laser Absorption Spectroscopy (DOAS), Laser-Induced Fluorescence Spectroscopy (LIF), and Chemical Ionisation Mass Spectrometry (CIMS). Even though many measurement campaigns with OH data were published, the question of accuracy and precision is still under discussion.
Revised: 16 Sep 2009 – Accepted: 23 Sep 2009 – Published: 22 Oct 2009
Here, we report results of the first formal, blind intercomparison of these techniques. Six OH instruments (4~LIF, 1~CIMS, 1~DOAS) participated successfully in the ground-based, international HOxComp campaign carried out in Jülich, Germany, in summer 2005. Comparisons were performed for three days in ambient air (3~LIF, 1 CIMS) and for six days in the atmosphere simulation chamber SAPHIR (3~LIF, 1~DOAS). All instruments were found to measure tropospheric OH concentrations with high sensitivity and good time resolution. The pairwise correlations between different data sets were linear and yielded high correlation coefficients (r2=0.75−0.96). Excellent absolute agreement was observed for the instruments at the SAPHIR chamber, yielding slopes between 1.01 and 1.13 in the linear regressions. In ambient air, the slopes deviated from unity by factors of 1.06 to 1.69, which can partly be explained by the stated instrumental accuracies. In addition, sampling inhomogeneities and calibration problems have apparently contributed to the discrepancies. The absolute intercepts of the linear regressions did not exceed 0.6×106 cm−3, mostly being insignificant and of minor importance for daytime observations of OH. No relevant interferences with respect to ozone, water vapour, NOx and peroxy radicals could be detected. The HOxComp campaign has demonstrated that OH can be measured reasonably well by current instruments, but also that there is still room for improvement of calibrations.
Schlosser, E., Brauers, T., Dorn, H.-P., Fuchs, H., Häseler, R., Hofzumahaus, A., Holland, F., Wahner, A., Kanaya, Y., Kajii, Y., Miyamoto, K., Nishida, S., Watanabe, K., Yoshino, A., Kubistin, D., Martinez, M., Rudolf, M., Harder, H., Berresheim, H., Elste, T., Plass-Dülmer, C., Stange, G., and Schurath, U.: Technical Note: Formal blind intercomparison of OH measurements: results from the international campaign HOxComp, Atmos. Chem. Phys., 9, 7923-7948, doi:10.5194/acp-9-7923-2009, 2009.