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Technical Note: Formal blind intercomparison of HO2 measurements in the atmosphere simulation chamber SAPHIR during the HOxComp campaign

Author(s): H. Fuchs | T. Brauers | H.-P. Dorn | H. Harder | R. Häseler | A. Hofzumahaus | F. Holland | Y. Kanaya | Y. Kajii | D. Kubistin | S. Lou | M. Martinez | K. Miyamoto | S. Nishida | M. Rudolf | E. Schlosser | A. Wahner | A. Yoshino | U. Schurath

Journal: Atmospheric Chemistry and Physics Discussions
ISSN 1680-7367

Volume: 10;
Issue: 9;
Start page: 21189;
Date: 2010;
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Hydroperoxy radical (HO2) concentrations were measured during the formal blind intercomparison campaign HOxComp carried out in Jülich, Germany. Three instruments detected HO2 via chemical conversion to hydroxyl radicals (OH) and subsequent detection of the sum of OH and HO2 by laser induced fluorescence (LIF). Instruments sampled ambient air for three days and were attached to the atmosphere simulation chamber SAPHIR during the second part of the campaign. Six experiments of one day each were conducted in SAPHIR, where air masses were homogeneously mixed, in order to investigate the performance of instruments and to determine potential interferences of measurements under well-controlled conditions. Linear correlation coefficients between measurements of the LIF instruments are generally high and range from 0.82 to 0.98. However, the agreement between measurements is variable. The regression analysis of the entire data set of measurements in SAPHIR yields slopes between 0.69 to 1.26 and intercepts are smaller than typical atmospheric daytime concentrations (less than 1 pptv). The quality of fit parameters improves significantly, when data are grouped into data subsets of similar water vapor concentrations. Because measurements of LIF instruments were corrected for a well-characterized water dependence of their sensitivities, this indicates that an unknown factor related to water vapor affected measurements in SAPHIR. Measurements in ambient air are also well correlated, but regression parameters differ from results obtained from SAPHIR experiments. This is most likely caused by sampling different air masses at the slightly distant locations of instruments.

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