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Technical Note: Intercomparison of formaldehyde measurements at the atmosphere simulation chamber SAPHIR

by a. Wisthaler, E.C. Apel, J. Bossmeyer, a. Hansel, W. Junkermann, R. Koppmann, R. Meier, K. Müller, S. J. Solomon, R. Steinbrecher, R. Tillmann, T. Brauers show all authors
Atmospheric Chemistry and Physics Discussions ()
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The atmosphere simulation chamber SAPHIR at the Research Centre J¨ ulich was used to test the suitability of state-of-the-art analytical instruments for the measurement of gas-phase formaldehyde (HCHO) in air. Five analyzers based on four different sensing principles were deployed: a differential optical absorption spectrometer (DOAS), car- tridges for 2,4-dinitrophenylhydrazine (DNPH) derivatiza- tion followed by off-line high pressure liquid chromatogra- phy (HPLC) analysis, two different types of commercially available wet chemical sensors based on Hantzsch fluorime- try, and a proton-transfer-reaction mass spectrometer (PTR- MS). A new optimized mode of operation was used for the PTR-MS instrument which significantly enhanced its perfor- mance for online HCHO detection at low absolute humidi- ties. The instruments were challenged with typical ambient lev- els of HCHO ranging from zero to several ppb. Synthetic air of high purity and particulate-filtered ambient air were used as sample matrices in the atmosphere simulation chamber onto which HCHO was spiked under varying levels of hu- midity and ozone. Measurements were compared to mixing ratios calculated from the chamber volume and the known amount of HCHO injected into the chamber; measurements were also compared between the different instruments. The formal and blind intercomparison exercise was conducted under the control of an independent referee. A number of analytical problems associated with the experimental set-up and with individual instruments were identified, the overall agreement between the methods was fair.

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