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Fluxes of oxygen (O 2) and carbon dioxide (CO 2) in and out of the atmosphere are strongly coupled for terrestrial biospheric exchange processes and fossil fuel combustion but are uncoupled for oceanic air–sea gas exchange. High-precision measurements of both species can therefore provide constraints on the carbon cycle and can be used to quantify fossil fuel CO 2 (ffCO 2) emission estimates. In the case of O 2 , however, due to its large atmospheric mole fraction (∼20.9 %) it is very challenging to measure small variations to the degree of precision and accuracy required for these applications. We have tested an atmospheric O 2 analyser based on the principle of cavity ring-down spectroscopy (Picarro Inc., model G2207- i), both in the laboratory and at the Weybourne Atmospheric Observatory (WAO) field station in the UK, in comparison to well-established, pre-existing atmospheric O 2 and CO 2 measurement systems. In laboratory tests analysing dry air in high-pressure cylinders, we found that the best precision was achieved with 30 min averaging and was ±0.5 ppm (∼±2.4 per meg). Also from continuous measurements from a cylinder of dry air, we found the 24 h peak-to-peak range of hourly averaged values to be 1.2 ppm (∼5.8 per meg). These results are close to atmospheric O 2 compatibility goals as set by the UN World Meteorological Organization. However, from measurements of ambient air conducted at WAO we found that the built-in water correction of the G2207- i does not sufficiently correct for the influence of water vapour on the O 2 mole fraction. When sample air was dried and a 5-hourly baseline correction with a reference gas cylinder was employed, the G2207- i 's results showed an average difference from the established O 2 analyser of 13.6±7.5 per meg (over 2 weeks of continuous measurements). Over the same period, based on measurements of a so-called "target tank", analysed for 12 min every 7 h, we calculated a repeatability of ±5.7±5.6 per meg and a compatibility of ±10.0±6.7 per meg for the G2207- i. To further examine the G2207- i 's performance in real-world applications we used ambient air measurements of O 2 together with concurrent CO 2 measurements to calculate ffCO 2. Due to the imprecision of the G2207- i , the ffCO 2 calculated showed large differences from that calculated from the established measurement system and had a large uncertainty of ±13.0 ppm, which was roughly double that from the established system (±5.8 ppm). [ABSTRACT FROM AUTHOR]

Fluxes of oxygen (O2) and carbon dioxide (CO2) in and out of the atmosphere are strongly coupled for terrestrial biospheric exchange processes and fossil fuel combustion but are uncoupled for oceanic air-sea gas exchange. High-precision measurements of both species can therefore provide constraints on the carbon cycle and can be used to quantify fossil fuel CO2 (ffCO2) emission estimates. In the case of O2, however, due to its large atmospheric mole fraction of O2 (~20.9 %) it is very challenging to measure small variations to the degree of precision and accuracy required for these applications. We have tested an atmospheric O2 analyser based on the principle of cavity ring-down spectroscopy (Picarro Inc., model G2207- i), both in the laboratory and at the Weybourne Atmospheric Observatory (WAO) field station in the UK, in comparisons to well-established, pre-existing atmospheric O2 and CO2 measurement systems. In laboratory tests analysing air in high-pressure cylinders, from the Allan deviation we calculated a precision of ± 1 ppm (1σ standard deviation of 300 seconds mean), and a 24-hour peak-to-peak range of hourly averaged values of 1.2 ppm. These results are close to atmospheric O2 compatibility goals as set by the UN World Meteorological Organization. From measurements of ambient air conducted at WAO we found that the built-in water correction of the G2207-i does not sufficiently correct for the influence of water vapour on the O2 mole fraction. When sample air was pre-dried and employing a 5-hourly baseline correction with a reference gas cylinder, the G2207-i’s results showed an average difference from the established O2 analyser of 13.6 ± 7.5 per meg (over two weeks of continuous measurements). Over the same period, based on measurements of a so-called “target tank” (sometimes known as a “surveillance tank”), analysed for 12 minutes every 7 hours, we calculated a repeatability of ± 5.7 ± 5.6 per meg and a compatibility of ± 10.0 ± 6.7 per meg for the G2207-i . To further examine the G2207-i’s performance in real-world applications we used ambient air measurements of O2 together with concurrent CO2 measurements to calculate ffCO2. Due to the imprecision of the G2207-i, the ffCO2 calculated showed large differences from that calculated from the established system, and had a large uncertainty of ± 13.0 ppm, which was roughly double that from the established system (± 5.8 ppm). [ABSTRACT FROM AUTHOR]

We present 20-year flask sample records of atmospheric CO2, δO2/N2 and APO from the stations Lutjewad (the Netherlands) and Mace Head (Ireland) and a 3-year record from Halley station (Antarctica), including details of the extensive calibration procedure and its stability over time. The results of our inter-comparison involving gas cylinders from various research laboratories worldwide also show that our calibration is of high quality and compatible with the internationally recognised Scripps scale. The measurement records from Lutjewad and Mace Head show similar long-term trends during the period 2002-2018 of 2.31 ± 0.07 ppm yr−1 for CO2 and −21.2 ± 0.8 per meg yr−1 for δO2/N2 at Lutjewad, and 2.22 ± 0.04 ppm yr−1 for CO2 and −21.3 ± 0.9 per meg yr−1 for δO2/N2 at Mace Head. They also show a similar δO2/N2 seasonal cycle with an amplitude of 54 ± 4 per meg at Lutjewad and 61 ± 5 per meg at Mace Head, while CO2 seasonal amplitude at Lutjewad (16.8 ± 0.5 ppm) is slightly higher than that at Mace Head (14.8 ± 0.3 ppm). We show that the observed trends and seasonal cycles are compatible with the measurements from various stations, especially the measurements from Weybourne Atmospheric Observatory (United Kingdom). However, there are remarkable differences in the progression of annual trends between the Mace Head and Lutjewad records for δO2/N2 and APO, which might in part be caused by sampling differences, but also by environmental effects, such as the North Atlantic Ocean oxygen ventilation changes to which Mace Head is more sensitive. The Halley record shows clear trends and seasonality in δO2/N2 and APO, where especially APO agrees well with the continuous measurements at Halley by the University of East Anglia, while CO2 and δO2/N2 present slight disagreements, most likely caused by small leakages during sampling. From our 2002-2018 records, we find good agreement for the global ocean sink: 2.0 ± 0.8 PgC yr−1 and 2.2 ± 0.9 PgC yr−1, based on Lutjewad and Mace Head, respectively. The data presented in this work are available at https://doi.org/10.18160/qq7d-t060 (Nguyen et al., 2021). [ABSTRACT FROM AUTHOR]