High-precision atmospheric oxygen measurement comparisons between a newly built CRDS analyzer and existing measurement techniques

Abstract

Abstract. Carbon dioxide and oxygen are tightly coupled in land biosphere CO2–O2 exchange processes, whereas they are not coupled in oceanic exchange. For this reason, atmospheric oxygen measurements can be used to constrain the global carbon cycle, especially oceanic uptake. However, accurately quantifying small (∼1–100 ppm) variations in O2 is analytically challenging due to the very large atmospheric background which constitutes about 20.9 % (∼209 500 ppm) of atmospheric air. Here we present a detailed description of a newly developed high-precision oxygen mixing ratio and isotopic composition analyzer (Picarro G2207) that is based on cavity ring-down spectroscopy (CRDS) as well as to its operating principles; we also demonstrate comprehensive laboratory and field studies using the abovementioned instrument. From the laboratory tests, we calculated a short-term precision (standard error of 1 min O2 mixing ratio measurements) of < 1 ppm for this analyzer based on measurements of eight standard gases analyzed for 2 h, respectively. In contrast to the currently existing techniques, the instrument has an excellent long-term stability; therefore, calibration every 12 h is sufficient to get an overall uncertainty of < 5 ppm. Measurements of ambient air were also conducted at the Jungfraujoch high-altitude research station and the Beromünster tall tower in Switzerland. At both sites, we observed opposing and diurnally varying CO2 and O2 profiles due to different processes such as combustion, photosynthesis, and respiration. Based on the combined measurements at Beromünster tower, we determined height-dependent O2:CO2 oxidation ratios varying between −0.98 and −1.60; these ratios increased with the height of the tower inlet, possibly due to different source contributions such as natural gas combustion, which has a high oxidation ratio, and biological processes, which have oxidation ratios that are relatively lower.