Quality assurance of hydrocarbon measurements for the German Tropospheric Research Focus (TFS)

In the German Focus on Tropospheric Research (TFS) independent quality assurance procedures were implemented in order to obtain information on data quality and comparability of the different measurements made in the different field campaigns. This paper describes the results for measurements of hydrocarbons using in-situ gas chromatographic techniques and off line analysis of samples collected in canisters (analysed by two central laboratories CL-1 and CL-2) and samples collected on adsorption tubes. The QA-procedures included comparisons with synthetic standards (prepared by EN 45001 certified laboratories), absolute calibration with a diffusion source, and an instrument/methodology comparison in ambient air. Harmonisation of the ambient measurements was achieved with a complex mixture (NCAR/BERLIOZ) containing 70 commonly observed hydrocarbons at mixing ratios of 0.2 to 10 ppb (mole fraction) in nitrogen, which was calibrated by referencing to hydrocarbon standards of the National Institute for Standards and Technology (NIST). For the certified synthetic standards, the experienced groups agreed to within +/-20% for most compounds. Much larger discrepancies were observed for the new Airmotec HC2010 instruments due to problems with identification, co-elution and blanks/memory effects. The results in ambient air were similar: Reasonable agreement was found for the results from the experienced groups with well characterised in situ instruments and for the charcoal tubes, whereas larger discrepancies were observed for the results from new groups and instruments. For the latter, only selected compounds met the data quality objectives (DQO). The canister samples analysed by CL-2 were in good agreement with the reference instrument, whereas large deviations were found for a number of compounds in the analysis of the same canisters by CL-1. The results of the comparison provided the final basis for flagging and harmonising the data from all participants prior to their submission to the TFS central data bank.