In a 3.5-year long study, the long-term performance of a mobile, solar absorption Bruker EM27/SUN spectrometer, used for greenhouse gas observations, is checked with respect to a co-located reference Bruker IFS 125HR spectrometer, which is part of the Total Carbon Column Observing Network (TCCON). We find that the EM27/SUN is stable on timescales of several years; the drift per year between the EM27/SUN and the official TCCON product is 0.02 ppmv for XCO₂ and 0.9 ppbv for XCH₄, which is within the 1σ precision of the comparison, 0.6 ppmv for XCO₂ and 4.3 ppbv for XCH₄. The bias between the two data sets is 3.9 ppmv for XCO₂ and 13.0 ppbv for XCH₄. In order to avoid sensitivity-dependent artifacts, the EM27/SUN is also compared to a truncated IFS 125HR data set derived from full-resolution TCCON interferograms. The drift is 0.02 ppmv for XCO₂ and 0.2 ppbv for XCH₄ per year, with 1σ precisions of 0.4 ppmv for XCO₂ and 1.4 ppbv for XCH₄, respectively. The bias between the two data sets is 0.6 ppmv for XCO₂ and 0.5 ppbv for XCH₄. With the presented long-term stability, the EM27/SUN qualifies as an useful supplement to the existing TCCON network in remote areas. To achieve consistent performance, such an extension requires careful testing of any spectrometers involved by application of common quality assurance measures. One major aim of the COllaborative Carbon Column Observing Network (COCCON) infrastructure is to provide these services to all EM27/SUN operators. In the framework of COCCON development, the performance of an ensemble of 30 EM27/SUN spectrometers was tested and found to be very uniform, enhanced by the centralized inspection performed at the Karlsruhe Institute of Technology prior to deployment. Taking into account measured instrumental line shape parameters for each spectrometer, the resulting average bias across the ensemble with respect to the reference EM27/SUN used in the long-term study in XCO₂ is 0.20 ppmv, while it is 0.8 ppbv for XCH₄. The average standard deviation of the ensemble is 0.13 ppmv for XCO₂ and 0.6 ppbv for XCH₄. In addition to the robust metric based on absolute differences, we calculate the standard deviation among the empirical calibration factors. The resulting 2σ uncertainty is 0.6 ppmv for XCO₂ and 2.2 ppbv for XCH₄. As indicated by the executed long-term study on one device presented here, the remaining empirical calibration factor deduced for each individual instrument can be assumed constant over time. Therefore the application of these empirical factors is expected to further improve the EM27/SUN network conformity beyond the scatter among the empirical calibration factors reported above.

The 2015 Paris Agreement of the United Nations Framework Convention on Climate Change aims to keep global average temperature increases well below 2 °C of preindustrial levels in the Year 2100. Vital to its success is achieving a decrease in the abundance of atmospheric methane (CH₄), the second most important anthropogenic greenhouse gas. If this reduction is to be achieved, individual nations must make and meet reduction goals in their nationally determined contributions, with regular and independently verifiable global stock taking. Targets for the Paris Agreement have been set, and now the capability must follow to determine whether CH₄ reductions are actually occurring. At present, however, there are significant limitations in the ability of scientists to quantify CH₄ emissions accurately at global and national scales and to diagnose what mechanisms have altered trends in atmospheric mole fractions in the past decades. For example, in 2007, mole fractions suddenly started rising globally after a decade of almost no growth. More than a decade later, scientists are still debating the mechanisms behind this increase. This study reviews the main approaches and limitations in our current capability to diagnose the drivers of changes in atmospheric CH₄ and, crucially, proposes ways to improve this capability in the coming decade. Recommendations include the following: (i) improvements to process‐based models of the main sectors of CH₄ emissions—proposed developments call for the expansion of tropical wetland flux measurements, bridging remote sensing products for improved measurement of wetland area and dynamics, expanding measurements of fossil fuel emissions at the facility and regional levels, expanding country‐specific data on the composition of waste sent to landfill and the types of wastewater treatment systems implemented, characterizing and representing temporal profiles of crop growing seasons, implementing parameters related to ruminant emissions such as animal feed, and improving the detection of small fires associated with agriculture and deforestation; (ii) improvements to measurements of CH₄ mole fraction and its isotopic variations—developments include greater vertical profiling at background sites, expanding networks of dense urban measurements with a greater focus on relatively poor countries, improving the precision of isotopic ratio measurements of ¹³CH₄, CH₃D, ¹⁴CH₄, and clumped isotopes, creating isotopic reference materials for international‐scale development, and expanding spatial and temporal characterization of isotopic source signatures; and (iii) improvements to inverse modeling systems to derive emissions from atmospheric measurements—advances are proposed in the areas of hydroxyl radical quantification, in systematic uncertainty quantification through validation of chemical transport models, in the use of source tracers for estimating sector‐level emissions, and in the development of time and space resolved national inventories. These and other recommendations are proposed for the major areas of CH₄ science with the aim of improving capability in the coming decade to quantify atmospheric CH₄ budgets on the scales necessary for the success of climate policies.

In this study, an extension on the previously reported status of the COllaborative Carbon Column Observing Network's (COCCON) calibration procedures incorporating refined methods is presented. COCCON is a global network of portable Bruker EM27/SUN FTIR spectrometers for deriving column-averaged atmospheric abundances of greenhouse gases. The original laboratory open-path lamp measurements for deriving the instrumental line shape (ILS) of the spectrometer from water vapour lines have been refined and extended to the secondary detector channel incorporated in the EM27/SUN spectrometer for detection of carbon monoxide (CO). The refinements encompass improved spectroscopic line lists for the relevant water lines and a revision of the laboratory pressure measurements used for the analysis of the spectra. The new results are found to be in good agreement with those reported by Frey et al. (2019) and discussed in detail. In addition, a new calibration cell for ILS measurements was designed, constructed and put into service. Spectrometers calibrated since January 2020 were tested using both methods for ILS characterization, open-path (OP) and cell measurements. We demonstrate that both methods can detect the small variations in ILS characteristics between different spectrometers, but the results of the cell method indicate a systematic bias of the OP method. Finally, a revision and extension of the COCCON network instrument-to-instrument calibration factors for XCO₂, XCO and XCH₄ is presented, incorporating 47 new spectrometers (of 83 in total by now). This calibration is based on the reference EM27/SUN spectrometer operated by the Karlsruhe Institute of Technology (KIT) and spectra collected by the collocated TCCON station Karlsruhe. Variations in the instrumental characteristics of the reference EM27/SUN from 2014 to 2017 were detected, probably arising from realignment and the dual-channel upgrade performed in early 2018. These variations are considered in the evaluation of the instrument-specific calibration factors in order to keep all tabulated calibration results consistent.

Cities currently covering only a very small portion ( < 3 %) of the world's land surface directly release to the atmosphere about 44 % of global energy-related CO₂, but they are associated with 71–76 % of CO₂ emissions from global final energy use. Although many cities have set voluntary climate plans, their CO₂ emissions are not evaluated by the monitoring, reporting, and verification (MRV) procedures that play a key role for market- or policy-based mitigation actions. Here we analyze the potential of a monitoring tool that could support the development of such procedures at the city scale. It is based on an atmospheric inversion method that exploits inventory data and continuous atmospheric CO₂ concentration measurements from a network of stations within and around cities to estimate city CO₂ emissions. This monitoring tool is configured for the quantification of the total and sectoral CO₂ emissions in the Paris metropolitan area (∼ 12 million inhabitants and 11.4 TgC emitted in 2010) during the month of January 2011. Its performances are evaluated in terms of uncertainty reduction based on observing system simulation experiments (OSSEs). They are analyzed as a function of the number of sampling sites (measuring at 25 m a.g.l.) and as a function of the network design. The instruments presently used to measure CO₂ concentrations at research stations are expensive (typically ∼ EUR 50 k per sensor), which has limited the few current pilot city networks to around 10 sites. Larger theoretical networks are studied here to assess the potential benefit of hypothetical operational lower-cost sensors. The setup of our inversion system is based on a number of diagnostics and assumptions from previous city-scale inversion experiences with real data. We find that, given our assumptions underlying the configuration of the OSSEs, with 10 stations only the uncertainty for the total city CO₂ emission during 1 month is significantly reduced by the inversion by ∼ 42 %. It can be further reduced by extending the network, e.g., from 10 to 70 stations, which is promising for MRV applications in the Paris metropolitan area. With 70 stations, the uncertainties in the inverted emissions are reduced significantly over those obtained using 10 stations: by 32 % for commercial and residential buildings, by 33 % for road transport, by 18 % for the production of energy by power plants, and by 31 % for total emissions. These results indicate that such a high number of stations would be likely required for the monitoring of sectoral emissions in Paris using this observation–model framework. They demonstrate some high potential that atmospheric inversions can contribute to the monitoring and/or the verification of city CO₂ emissions (baseline) and CO₂ emission reductions (commitments) and the advantage that could be brought by the current developments of lower-cost medium precision (LCMP) sensors.

Implication of weekly and diurnal 14 C calibration on hourly estimates of CO-based fossil fuel CO 2 at a moderately polluted site in southwestern Germany