CO2 isotope analyses using large air samples collected on intercontinental flights by the CARIBIC Boeing 767

Analytical details for C-13 and O-18 isotope analyses of atmospheric CO2 in large air samples are given. The large air samples of nominally 300 L were collected during the passenger aircraft-based atmospheric chemistry research project CARIBIC and analyzed for a large number of trace gases and isotopic composition. In the laboratory, an ultra-pure and high efficiency extraction system and high-quality isotope ratio mass spectrometry were used. Because direct comparison with other laboratories was practically impossible, the extraction and measurement procedures were tested in considerable detail. Extracted CO2 was measured twice vs. two different working reference CO2 gases of different isotopic composition. The two data sets agree well and their distributions can be used to evaluate analytical errors due to isotope measurement, ion corrections, internal calibration consistency, etc. The calibration itself is based on NBS-19 and also verified using isotope analyses on pure CO2 gases (NIST Reference Materials (RMs) and NARCIS CO2 gases). The major problem encountered could be attributed to CO2-water exchange in the air sampling cylinders. This exchange decreased over the years. To exclude artefacts due to such isotopic exchange, the data were filtered to reject negative delta O-18(CO2) values. Examples of the results are given. Copyright (C) 2009 John Wiley & Sons, Ltd.