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Top-down greenhouse gas measurements can be used to independently assess the accuracy of bottom-up emission estimates. We report atmospheric methane (CH4) mole fractions and δ13CH4 measurements from Imperial College London from early 2018 onwards using a Picarro G2201-i analyser. Measurements from March 2018 to October 2020 were compared to simulations of CH4 mole fractions and δ13CH4 produced using the NAME (Numerical Atmospheric-dispersion Modelling Environment) dispersion model coupled with the UK National Atmospheric Emissions Inventory, UK NAEI, and a global inventory, the Emissions Database for Global Atmospheric Research (EDGAR), with model spatial resolutions of ∼ 2, ∼ 10, and ∼ 25 km. Simulation–measurement comparisons are used to evaluate London emissions and the source apportionment in the global (EDGAR) and UK national (NAEI) emission inventories. Observed mole fractions were underestimated by 30 %–35 % in the NAEI simulations. In contrast, a good correspondence between observations and EDGAR simulations was seen. There was no correlation between the measured and simulated δ13CH4 values for either NAEI or EDGAR, however, suggesting the inventories' sectoral attributions are incorrect. On average, natural gas sources accounted for 20 %–28 % of the above background CH4 in the NAEI simulations and only 6 %–9 % in the EDGAR simulations. In contrast, nearly 84 % of isotopic source values calculated by Keeling plot analysis (using measurement data from the afternoon) of individual pollution events were higher than −45 ‰, suggesting the primary CH4 sources in London are actually natural gas leaks. The simulation–observation comparison of CH4 mole fractions suggests that total emissions in London are much higher than the NAEI estimate (0.04 Tg CH4 yr−1) but close to, or slightly lower than, the EDGAR estimate (0.10 Tg CH4 yr−1). However, the simulation–observation comparison of δ13CH4 and the Keeling plot results indicate that emissions due to natural gas leaks in London are being underestimated in both the UK NAEI and EDGAR.

Assessment of bottom-up greenhouse gas emissions estimates through independent methods is needed to demonstrate whether reported values are accurate or if bottom-up methodologies need to be refined. We report atmospheric methane (CH4) mole fractions and δ13CH4 measurements from Imperial College London since early 2018 using a Picarro G2201-i analyser. Measurements from March 2018 to October 2020 were compared to simulations of CH4 mole fractions and δ13CH4 produced using the NAME dispersion model coupled with the UK National Atmospheric Emissions Inventory, UK NAEI, and the global inventory, EDGAR, with model spatial resolutions of ~2 km, ~10 km, and ~25 km. Observed mole fractions were underestimated by 30–35 % in the NAEI simulations. In contrast, a good correspondence between observations and EDGAR simulations was seen. There was no correlation between the measured and simulated δ13CH4 values for either NAEI or EDGAR, however, suggesting the inventories’ sectoral attributions are incorrect. On average, natural gas sources accounted for 20–28 % of the above background CH4 in the NAEI simulations, and only 6–9 % in the EDGAR simulations. In contrast, nearly 84 % of isotopic source values calculated by Keeling plot analysis (using measurement data from the afternoon) of individual pollution events were higher than −45 ‰, suggesting the primary CH4 sources in London are actually natural gas leaks. The simulation-observation comparison of CH4 mole fractions suggests that total emissions in London are much higher than the NAEI estimate (0.04 Tg CH4 yr−1) but close to, or slightly lower than the EDGAR estimate (0.10 Tg CH4 yr−1). However, the simulation-observation comparison of δ13CH4 and the Keeling plot results indicate that emissions due to natural gas leaks in London are being underestimated in both the UK NAEI and EDGAR.

Atmospheric CO at Egham in SE England has shown a marked and progressive decline since 1997, following adoption of strict controls on emissions. The Egham site is uniquely positioned to allow both assessment and comparison of ‘clean Atlantic background’ air and CO-enriched air downwind from the London conurbation. The decline is strongest (approximately 50 ppb per year) in the 1997–2003 period but continues post 2003. A ‘local CO increment’ can be identified as the residual after subtraction of contemporary background Atlantic CO mixing ratios from measured values at Egham. This increment, which is primarily from regional sources (during anticyclonic or northerly winds) or from the European continent (with easterly air mass origins), has significant seasonality, but overall has declined steadily since 1997. On many days of the year CO measured at Egham is now not far above Atlantic background levels measured at Mace Head (Ireland). The results are consistent with MOPITT satellite observations and ‘bottom-up’ inventory results. Comparison with urban and regional background CO mixing ratios in Hong Kong demonstrates the importance of regional, as opposed to local reduction of CO emission. The Egham record implies that controls on emissions subsequent to legislation have been extremely successful in the UK. ISSN:2045-2322

High-precision analyses of the isotopic composition of methane in ambient air can potentially be used to discriminate between different source categories. Due to the complexity of isotope ratio measurements, such analyses have generally been performed in the laboratory on air samples collected in the field. This poses a limitation on the temporal resolution at which the isotopic composition can be monitored with reasonable logistical effort. Here we present the performance of a dual isotope ratio mass spectrometric system (IRMS) and a quantum cascade laser absorption spectroscopy (QCLAS)-based technique for in situ analysis of the isotopic composition of methane under field conditions. Both systems were deployed at the Cabauw Experimental Site for Atmospheric Research (CESAR) in the Netherlands and performed in situ, high-frequency (approx. hourly) measurements for a period of more than 5 months. The IRMS and QCLAS instruments were in excellent agreement with a slight systematic offset of (+0.25 ± 0.04) ‰ for δ13C and (−4.3 ± 0.4) ‰ for δD. This was corrected for, yielding a combined dataset with more than 2500 measurements of both δ13C and δD. The high-precision and high-temporal-resolution dataset not only reveals the overwhelming contribution of isotopically depleted agricultural CH4 emissions from ruminants at the Cabauw site but also allows the identification of specific events with elevated contributions from more enriched sources such as natural gas and landfills. The final dataset was compared to model calculations using the global model TM5 and the mesoscale model FLEXPART-COSMO. The results of both models agree better with the measurements when the TNO-MACC emission inventory is used in the models than when the EDGAR inventory is used. This suggests that high-resolution isotope measurements have the potential to further constrain the methane budget when they are performed at multiple sites that are representative for the entire European domain.

Atmospheric CO at Egham in SE England has shown a marked and progressive decline since 1997, following adoption of strict controls on emissions. The Egham site is uniquely positioned to allow both assessment and comparison of ‘clean Atlantic background’ air and CO-enriched air downwind from the London conurbation. The decline is strongest (approximately 50 ppb per year) in the 1997–2003 period but continues post 2003. A ‘local CO increment’ can be identified as the residual after subtraction of contemporary background Atlantic CO mixing ratios from measured values at Egham. This increment, which is primarily from regional sources (during anticyclonic or northerly winds) or from the European continent (with easterly air mass origins), has significant seasonality, but overall has declined steadily since 1997. On many days of the year CO measured at Egham is now not far above Atlantic background levels measured at Mace Head (Ireland). The results are consistent with MOPITT satellite observations and ‘bottom-up’ inventory results. Comparison with urban and regional background CO mixing ratios in Hong Kong demonstrates the importance of regional, as opposed to local reduction of CO emission. The Egham record implies that controls on emissions subsequent to legislation have been extremely successful in the UK., Scientific Reports, 6, ISSN:2045-2322