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We investigate the use of atmospheric oxygen (O 2) and carbon dioxide (CO 2) measurements for the estimation of the fossil fuel component of atmospheric CO 2 in the UK. Atmospheric potential oxygen (APO) – a tracer that combines O 2 and CO 2 , minimizing the influence of terrestrial biosphere fluxes – is simulated at three sites in the UK, two of which make APO measurements. We present a set of model experiments that estimate the sensitivity of APO simulations to key inputs: fluxes from the ocean, fossil fuel flux magnitude and distribution, the APO baseline, and the exchange ratio of O 2 to CO 2 fluxes from fossil fuel combustion and the terrestrial biosphere. To estimate the influence of uncertainties in ocean fluxes, we compare three ocean O 2 flux estimates from the NEMO–ERSEM, the ECCO–Darwin ocean model, and the Jena CarboScope (JC) APO inversion. The sensitivity of APO to fossil fuel emission magnitudes and to terrestrial biosphere and fossil fuel exchange ratios is investigated through Monte Carlo sampling within literature uncertainty ranges and by comparing different inventory estimates. We focus our model–data analysis on the year 2015 as ocean fluxes are not available for later years. As APO measurements are only available for one UK site at this time, our analysis focuses on the Weybourne station. Model–data comparisons for two additional UK sites (Heathfield and Ridge Hill) in 2021, using ocean flux climatologies, are presented in the Supplement. Of the factors that could potentially compromise simulated APO-derived fossil fuel CO 2 (ffCO 2) estimates, we find that the ocean O 2 flux estimate has the largest overall influence at the three sites in the UK. At times, this influence is comparable in magnitude to the contribution of simulated fossil fuel CO 2 to simulated APO. We find that simulations using different ocean fluxes differ from each other substantially. No single model estimate, or a model estimate that assumed zero ocean flux, provided a significantly closer fit than any other. Furthermore, the uncertainty in the ocean contribution to APO could lead to uncertainty in defining an appropriate regional background from the data. Our findings suggest that the contribution of non-terrestrial sources needs to be better accounted for in model simulations of APO in the UK to reduce the potential influence on inferred fossil fuel CO 2 using APO. [ABSTRACT FROM AUTHOR]

Atmospheric measurements of the O2/N2 ratio and the CO2 mole fraction (combined into the conceptual tracer "Atmospheric Potential Oxygen", APO) over continents have been proposed as a constraint on CO2 emissions from fossil-fuel burning. Here we assess the suitability of such APO data to constrain anthropogenic CO2 emissions in western Europe, with particular focus on their decadal trends. We use an inversion of atmospheric transport to estimate spatially and temporally explicit scaling factors on a bottom-up fossil-fuel emissions inventory. Based on the small number of currently available observational records, our CO2 emissions estimates show relatively large apparent year-to-year variations, exceeding the expected uncertainty of the bottom-up inventory and precluding the calculation of statistically significant trends. We were not able to trace the apparent year-to-year variations back to particular properties of the APO data. Inversion of synthetic APO data, however, confirms that data information content and degrees of freedom are sufficient to successfully correct a counterfactual prior. Larger sets of measurement stations, such as the recently started APO observations from the Integrated Carbon Observation System (ICOS) European research infrastructure, improve the constraint and may ameliorate possible problems with local signals or with measurement or model errors at the stations. We further tested the impact of uncertainties in the O2:CO2 stoichiometries of fossil-fuel burning and land biospheric exchange and found they are not fundamental obstacles to estimating decadal trends in fossil-fuel CO2 emissions, though further work on fossil-fuel O2:CO2 stoichiometries seems necessary. [ABSTRACT FROM AUTHOR]

We present a 12-year time series of continuous atmospheric measurements of O 2 and CO 2 at the Weybourne Atmospheric Observatory in the United Kingdom. These measurements are combined into the term atmospheric potential oxygen (APO), a tracer that is invariant to terrestrial biosphere fluxes. The CO 2 , O 2 and APO datasets discussed are hourly averages between May 2010 and December 2021. We include details of our measurement system and calibration procedures, and describe the main long-term and seasonal features of the time series. The 2 min repeatability of the measurement system is approximately ±3 per meg for O 2 and approximately ±0.005 ppm for CO 2. The time series shows average long-term trends of 2.40 ppm yr -1 (2.38 to 2.42) for CO 2 , -24.0 per meg yr -1 for O 2 (-24.3 to -23.8) and -11.4 per meg yr -1 (-11.7 to -11.3) for APO, over the 12-year period. The average seasonal cycle peak-to-peak amplitudes are 16 ppm for CO 2 , 134 per meg for O 2 and 68 per meg for APO. The diurnal cycles of CO 2 and O 2 vary considerably between seasons. The datasets are publicly available at 10.18160/Z0GF-MCWH (Adcock et al., 2023) and have many current and potential scientific applications in constraining carbon cycle processes, such as investigating air–sea exchange of CO 2 and O 2 and top-down quantification of fossil fuel CO 2. [ABSTRACT FROM AUTHOR]

Atmospheric measurements of the O2/N2 ratio and the CO2 mole fraction (combined into the conceptual tracer 'Atmospheric Potential Oxygen', APO) over continents have been proposed as a constraint on CO2 emissions from fossil-fuel burning. Here we assess the suitability of such APO data to constrain anthropogenic CO2 emissions in Western Europe, with particular focus on their decadal trends. We use an inversion of atmospheric transport to estimate spatially and temporally explicit scaling factors on a bottom-up fossil-fuel emissions inventory. Based on the small number of currently available observational records, our CO2 emissions estimates show relatively large apparent year-to-year variations, exceeding the expected uncertainty of the bottom-up inventory and precluding the calculation of statistically significant trends. We were not able to trace the apparent year-to-year variations back to particular properties of the APO data. Inversion of synthetic APO data, however, confirms that data information content and degrees of freedom are sufficient to successfully correct a counterfactual prior. Larger sets of measurement stations, such as the recently started APO observations from the Integrated Carbon Observation System (ICOS) European research infrastructure, improve the constraint and may ameliorate possible problems with local signals or with measurement or model errors at the stations. We further tested the impact of uncertainties in the O2:CO2 stoichiometries of fossil-fuel burning and land biospheric exchange and found they are not fundamental obstacles to estimating decadal trends in fossil-fuel CO2 emissions, though further work on fossil-fuel O2:CO2 stoichiometries seems necessary. [ABSTRACT FROM AUTHOR]

We investigate the use of oxygen (O2) and carbon dioxide (CO2) measurements for the estimation of the fossil fuel component of atmospheric CO2 in the UK. Atmospheric potential oxygen (APO) – a tracer that combines O2 and CO2, minimising the influence of terrestrial biosphere fluxes – is simulated at three sites in the UK, two of which make atmospheric APO measurements. We present a set of model experiments that estimate the sensitivity of APO simulations to key inputs: fluxes from the ocean, fossil fuel flux magnitude and distribution, the APO baseline, and the ratio of O2 to CO2 fluxes from fossil fuel combustion and the terrestrial biosphere. To estimate the influence of uncertainties in ocean fluxes, we compared three ocean O2 flux estimates, from the NEMO – ERSEM and ECCO-Darwin ocean models, and the Jena CarboScope APO inversion. The sensitivity of APO to fossil fuel emission magnitudes and to terrestrial biosphere and fossil fuel exchange ratios was investigated through Monte Carlo sampling within literature uncertainty ranges, and by comparing different inventory estimates. Of the factors that could potentially compromise APO-derived fossil fuel CO2 estimates, we find that the ocean O2 flux estimate has the largest overall influence at the three sites in the UK. At times, this influence is comparable to the contribution to APO of simulated fossil fuel CO2. We find that simulations using different ocean fluxes differ from each other substantially, with no single model estimate, or a simulation with zero ocean flux, providing a significantly closer fit to the observations. Furthermore, the uncertainty in the ocean contribution to APO could lead to uncertainty in defining an appropriate regional background from the data. Our findings suggest that the contribution of non-terrestrial sources need to be well accounted for, in order to reduce their potential influence on inferred fossil fuel CO2. [ABSTRACT FROM AUTHOR]

We present analyses of a 12-year time series of continuous atmospheric measurements of O2 and CO2 at the Weybourne Atmospheric Observatory in the United Kingdom. These measurements are combined into the term Atmospheric Potential Oxygen (APO), a tracer that is conservative with respect to terrestrial biosphere processes. The CO2, O2 and APO datasets discussed are hourly averages between May 2010 and December 2021. We include details of our measurement system and calibration procedures, and describe the main long-term and seasonal features of the time series. The 2-minute repeatability of the measurement system is approximately ±3 per meg for O2 and approximately ±0.005 ppm for CO2. The time series shows average long-term trends of 2.40 ppm yr-1 (2.38 to 2.42) for CO2, -24.0 per meg yr-1 for O2 (-24.3 to -23.8) and -11.4 per meg yr-1 (-11.7 to -11.3) for APO, over the 12-year period. The average seasonal cycle peak-to-peak amplitudes are 16 ppm for CO2, 134 per meg for O2, and 68 per meg for APO. The diurnal cycles of CO2 and O2 vary considerably between seasons. The datasets are publicly available at https://doi.org/10.18160/Z0GF-MCWH (Adcock et al., 2023) and have many current and potential scientific applications in constraining carbon cycle processes, such as investigating air-sea exchange of CO2 and O2, and top-down quantification of fossil fuel CO2. [ABSTRACT FROM AUTHOR]

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]

We present 20-year flask sample records of atmospheric CO 2 , δ (O2/N2), and atmospheric potential oxygen (APO) from the stations Lutjewad (the Netherlands) and Mace Head (Ireland), and a 3-year record from Halley station (Antarctica). We include details of our calibration procedures and the stability of our calibration scale over time, which we estimate to be 3 per meg over the 11 years of calibration, and our compatibility with the international Scripps O 2 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 CO 2 and - 21.2 ± 0.8 per meg yr -1 for δ (O2/N2) at Lutjewad, and 2.22 ± 0.04 ppm yr -1 for CO 2 and - 21.3 ± 0.9 per meg yr -1 for δ (O2/N2) at Mace Head. They also show a similar δ (O2/N2) seasonal cycle with an amplitude of 54 ± 4 per meg at Lutjewad and 61 ± 5 per meg at Mace Head, while the CO 2 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 long-term trends and seasonal cycles are in good agreement with the measurements from various other stations, especially the measurements from the Weybourne Atmospheric Observatory (United Kingdom). However, there are remarkable differences in the progression of annual trends between the Mace Head and Lutjewad records for δ (O2/N2) and APO, which might in part be caused by sampling differences, but also by environmental effects, such as North Atlantic Ocean oxygen ventilation changes to which Mace Head is more sensitive. The Halley record shows clear trends and seasonality in δ (O2/N2) and APO, the latter agreeing especially well with continuous measurements at the same location made by the University of East Anglia (UEA), while CO 2 and δ (O2/N2) present slight disagreements, most likely caused by small leakages during sampling. From our 2002–2018 records, we find a good agreement with Global Carbon Budget 2021 (Friedlingstein et al. (2021) for the global ocean carbon sink: 2.1 ± 0.8 PgC yr -1 , based on the Lutjewad record. The data presented in this work are available at 10.18160/qq7d-t060 (Nguyen et al., 2021). [ABSTRACT FROM AUTHOR]