Analysis of non-methane hydrocarbons in air samples collected aboard the CARIBIC passenger aircraft

The CARIBIC project (Civil Aircraft for the Regular Investigation of the atmosphere Based on an Instrument Container) is a long-term monitoring program making regular atmospheric measurements from an instrument container installed monthly aboard a passenger aircraft. Typical cruising altitudes of the aircraft allow for the study of the free troposphere and the extra-tropical upper troposphere as well as the lowermost stratosphere. CARIBIC measurements include a number of real time analyses as well as the collection of aerosol and whole air samples. These whole air samples are analyzed post-flight for a suite of trace gases, which includes non-methane hydrocarbons (NMHC). The NMHC measurement system and its analytical performance are described here. Precision was found to vary slightly by compound, and is less than 2% for the C(2)-C(6) alkanes and ethyne, and between 1% and 6% for C(7)-C(8) alkanes and aromatic compounds. Preliminary results from participation in a Global Atmospheric Watch (WMO) VOC audit indicate accuracies within the precision of the system. Limits of detection are 1 pptv for most compounds, and up to 3 pptv for some aromatics. These are sufficiently low to measure mixing ratios typically observed in the upper troposphere and lowermost stratosphere for the longer-lived NMHC, however, in air samples from these regions many of the compounds with shorter lifetimes (<5 days) were frequently below the detection limit. Observed NMHC concentrations span several orders of magnitude, dependent on atmospheric region and air mass history, with concentrations typically decreasing with shorter chemical lifetimes.