UK greenhouse gas measurements at two new tall towers for aiding emissions verification

Under the UK-focused Greenhouse gAs and Uk and Global Emissions (GAUGE) project, two new tall tower greenhouse gas (GHG) observation sites were established in the 2013/2014 Northern Hemispheric winter. These sites, located at existing telecommunications towers, utilized a combination of cavity ring-down spectroscopy (CRDS) and gas chromatography (GC) to measure key GHGs (CO2, CH4, CO, N2O and SF6). Measurements were made at multiple intake heights on each tower. CO2 and CH4 dry mole fractions were calculated from either CRDS measurements of wet air, which were post-corrected with an instrument-specific empirical correction, or samples dried to between 0.05% H2O and 0.3% H2O using a Nafion (R) dryer, with a smaller correction applied for the residual H2O. The impact of these two drying strategies was examined. Drying with a Nafion (R) dryer was not found to have a significant effect on the observed CH4 mole fraction; however, Nafion (R) drying did cause a 0.02 mu mol mol(-1) CO2 bias. This bias was stable for sample CO2 mole fractions between 373 and 514 mu mol mol(-1) and for sample H2O up to 3.5 %. As the calibration and standard gases are treated in the same manner, the 0.02 mu mol mol(-1) CO2 bias is mostly calibrated out with the residual error (similar to 0.01 mu mol mol(-1) CO2) well below the World Meteorological Organization (WMO) reproducibility requirements. Of more concern was the error associated with the empirical instrument-specific water correction algorithms. These corrections are relatively stable and reproducible for samples with H2O between 0.2% and 2.5 %, CO2 between 345 and 449 mu mol mol(-1), and CH4 between 1743 and 2145 nmol mol(-1). However, the residual errors in these corrections increase to > 0.05 mu mol mol(-1) for CO2 and > 1 nmol mol(-1) for CH4 (greater than the WMO internal reproducibility guidelines) at higher humidities and for samples with very low (< 0.5 %) water content. These errors also scale with the absolute magnitude of the CO2 and CH4 mole fractions. As such, water corrections calculated in this manner are not suitable for samples with low (< 0.5 %) or high (> 2.5 %) water contents and either alternative correction methods should be used or partial drying or humidification considered prior to sample analysis.