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Atmospheric CO2 growth is the primary driver of the global warming and the rate of this growth is a valuable indicator of the interannual changes in carbon cycle. Despite atmospheric CO2 growth rate had been considered as the well-known quantity, the latest findings indicated that CO2 models can considerably disagree in reproducing this rate. This study is aimed to advance our knowledge about temporal and spatial variations of annual CO2 growth rate (AGR) by using CO2 observations from the Total Column Observing Network (TCCON), CO2 simulations from Carbon Tracker (CT) and Copernicus Atmospheric Monitoring System (CAMS) models being compared with the previously-reported global references of AGR from Global Carbon Budget (GCB) and satellite observations (SAT) for 2004–2019 years. TCCON and the CO2 models revealed temporal AGR variations (AGRTCCON = 1.71–3.35 ppm, AGRCT = 1.64–3.15 ppm, AGRCAMS = 1.66–3.13 ppm) of very similar magnitude to the global CO2 growth references (AGRGCB = 1.59–3.23 ppm, AGRSAT = 1.55–2.92 ppm). However, AGRTCCON estimates agree well with the references only during the 2010s (correlation coefficient, r = 0.68 vs GCB and r = 0.75 vs SAT) as the TCCON observational coverage has been substantially expanded since 2009. Moreover, AGRTCCON reasonably agrees (r = 0.67) with the strength of El-Nino Southern Oscillations (ENSO) in the 2010s. The highest atmospheric CO2 growth (2015–2016) driven by the very strong El-Nino was accurately reproduced by TCCON which provided AGR of 2015–2016 years (3.29 ± 0.98 ppm) in very close agreement to the AGRSAT reference (3.23 ± 0.50 ppm). We further validated AGR simulations (CT and CAMS) versus the newly-acquired AGRTCCON (as point-location reference) for every TCCON site and found low agreement between the models and TCCON (r  0.98). From spatial perspective, the highest AGR estimates (> 20 % from the median) were observed in the regions of intense fossil fuel combustion (East Asia) or biomass burning (Amazon, Central Africa). Lack of ideal correlation and small disagreement between CT and CAMS (2 inverse model, alongside with the current setup of a priori biomass burning fluxes, an alternative setup is assembled (multiple independent estimates of burned area and fire-dependent emission factors for various type of tropical fires can be used). In overall, our study showed that the current estimates of global atmospheric growth rate of CO2 are consistent across a wide range of the different data sources and strengthening of carbon observational infrastructure (like covering more developing countries with ground-based CO2 observations and providing more satellite CO2 observations from cloudy and hazy regions) should improve the accuracy of CO2 growth rate estimates on both local and global scales.

Decadal trends in the atmospheric abundances of carbon tetrafluoride (CF4) and nitrogen trifluoride (NF3) have been well characterised and have provided a time series of global total emissions. Information on locations of emissions contributing to the global total, however, is currently poor. We use a unique set of measurements between 2008 and 2015 from the Gosan station, Jeju Island, South Korea (part of the Advanced Global Atmospheric Gases Experiment network), together with an atmospheric transport model, to make spatially disaggregated emission estimates of these gases in East Asia. Due to the poor availability of good prior information for this study, our emission estimates are largely influenced by the atmospheric measurements. Notably, we are able to highlight emission hotspots of NF3 and CF4 in South Korea due to the measurement location. We calculate emissions of CF4 to be quite constant between the years 2008 and 2015 for both China and South Korea, with 2015 emissions calculated at 4.3±2.7 and 0.36±0.11 Gg yr-1, respectively. Emission estimates of NF3 from South Korea could be made with relatively small uncertainty at 0.6±0.07 Gg yr-1 in 2015, which equates to ∼ 1.6 % of the country's CO2 emissions. We also apply our method to calculate emissions of CHF3 (HFC-23) between 2008 and 2012, for which our results find good agreement with other studies and which helps support our choice in methodology for CF4 and NF3..

Carbon tetrachloride (CCl4) is a first-generation ozone-depleting substance, and its emissive use and production were globally banned by the Montreal Protocol with a 2010 phase-out; however, production and consumption for non-dispersive use as a chemical feedstock and as a process agent are still allowed. This study uses the high frequency and magnitude of CCl4 pollution events from an 8-year real-time atmospheric measurement record obtained at Gosan station (a regional background monitoring site in East Asia) to present evidence of significant unreported emissions of CCl4. Top-down emissions of CCl4 amounting to 23.6±7.1 Gg yrĝ'1 from 2011 to 2015 are estimated for China, in contrast to the most recently reported, post-2010, Chinese bottom-up emissions of 4.3-5.2 Gg yrĝ'1. The missing emissions ( ĝ1/4 19 Gg yrĝ'1) for China contribute to approximately 54 % of global CCl4 emissions. It is also shown that 89ĝ€†% ± 6 % of CCl4 enhancements observed at Gosan are related to CCl4 emissions from the production of CH3Cl, CH2Cl2, CHCl3 and C2Cl4 and its usage as a feedstock and process agent in chemical manufacturing industries. Specific sources and processes are identified using statistical methods, and it is considered highly unlikely that CCl4 is emitted by dispersive uses such as old landfills, contaminated soils and solvent usage. It is thus crucial to implement technical improvements and better regulation strategies to reduce evaporative losses of CCl4 occurring at the factory and/or process levels.

Based on observations of three chlorofluorocarbons, CFC-13 (chlorotrifluoromethane), CFC-114 (dichlorotetrafluoroethane) and CFC-115 (chloropentafluoroethane) in atmospheric and firn samples, we reconstruct records of their tropospheric histories spanning nearly eight decades. These compounds were measured in polar firn air samples, in ambient air archived in canisters, and in-situ at the AGAGE (Advanced Global Atmospheric Gases Experiment) network and affiliated sites. Global emissions to the atmosphere are derived from these observations using an inversion based on a 12-box atmospheric transport model. For CFC-13, we provide the first comprehensive global analysis. This compound increased monotonically from its first appearance in the atmosphere in the late 1950s to a mean global abundance of 3.18 ppt (dry air mole fraction in parts-per-trillion, pmol mol−-1) in 2016. Its growth rate has decreased since the mid 1980s but has remained at a surprisingly high level of 0.02 ppt yr−1 since the late 2000s. CFC-114 increased from its appearance in the 1950s to a maximum of 16.6 ppt in the early 2000s, and has since slightly declined to 16.3 ppt in 2016. CFC-115 increased monotonically from its first appearance in the 1960s and reached a global mean mole fraction of 8.52 ppt in 2016. Growth rates of all three compounds over the past years are significantly larger than would be expected from zero emissions. Under the assumption of unaltered lifetimes and atmospheric transport patterns, we derive global emissions from our measurements, which have remained unexpectedly high in recent years: Mean yearly emissions for the last decade (2007–2016) of CFC-13 are at 0.48 ± 0.15 kt yr−1 (> 15 % of past peak emissions), of CFC-114 at 1.90 ± 0.84 kt yr−1 (~ 10 % of peak emissions), and of CFC-115 at 0.80 ± 0.50 kt yr−1 (> 5 % of peak emissions). Mean yearly emissions of CFC-115 for 2014–2016 are 1.08 ± 0.50 kt yr−1 and have more than doubled compared to 2009. Cumulative global emissions for CFC-114 derived from observations through 2016 exceed the global cumulative production derived from reported inventory data by > 10 % while those for CFC-115 agree well. We find CFC-13 emissions from aluminum smelters and impurities of CFC-115 in the refrigerant HFC-125 (CHF2CF3) but if extrapolated to global emissions neither of them can account for the lingering global emissions determined from the atmospheric observations. We also conduct regional inversions for the years 2012–2016 for the north-east Asian area using observations from the Korean Gosan AGAGE site and find significant emissions for CFC-114 and CFC-115, suggesting that a large fraction of their global emissions currently occur in north-eastern Asia and more specifically on the Chinese mainland.

Based on observations of the chlorofluorocarbons CFC-13 (chlorotrifluoromethane), ΣCFC-114 (combined measurement of both isomers of dichlorotetrafluoroethane), and CFC-115 (chloropentafluoroethane) in atmospheric and firn samples, we reconstruct records of their tropospheric histories spanning nearly 8 decades. These compounds were measured in polar firn air samples, in ambient air archived in canisters, and in situ at the AGAGE (Advanced Global Atmospheric Gases Experiment) network and affiliated sites. Global emissions to the atmosphere are derived from these observations using an inversion based on a 12-box atmospheric transport model. For CFC-13, we provide the first comprehensive global analysis. This compound increased monotonically from its first appearance in the atmosphere in the late 1950s to a mean global abundance of 3.18 ppt (dry-air mole fraction in parts per trillion, pmol mol1) in 2016. Its growth rate has decreased since the mid-1980s but has remained at a surprisingly high mean level of 0.02 ppt yr⁻¹ since 2000, resulting in a continuing growth of CFC-13 in the atmosphere. ΣCFC-114 increased from its appearance in the 1950s to a maximum of 16.6 ppt in the early 2000s and has since slightly declined to 16.3 ppt in 2016. CFC-115 increased monotonically from its first appearance in the 1960s and reached a global mean mole fraction of 8.49 ppt in 2016. Growth rates of all three compounds over the past years are significantly larger than would be expected from zero emissions. Under the assumption of unchanging lifetimes and atmospheric transport patterns, we derive global emissions from our measurements, which have remained unexpectedly high in recent years: mean yearly emissions for the last decade (2007–2016) of CFC-13 are at 0.48 ± 0.15 kt yr⁻¹ (> 15 % of past peak emissions), of ΣCFC-114 at 1.90 ± 0.84 kt yr⁻¹ (∼ 10 % of peak emissions), and of CFC-115 at 0.80 ± 0.50 kt yr⁻¹(> 5 % of peak emissions). Mean yearly emissions of CFC-115 for 2015–2016 are 1.14 ± 0.50 kt yr⁻¹ and have doubled compared to the 2007–2010 minimum. We find CFC-13 emissions from aluminum smelters but if extrapolated to global emissions, they cannot account for the lingering global emissions determined from the atmospheric observations. We find impurities of CFC-115 in the refrigerant HFC-125 (CHF₂CF₃) but if extrapolated to global emissions, they can neither account for the lingering global CFC-115 emissions determined from the atmospheric observations nor for their recent increases. We also conduct regional inversions for the years 2012–2016 for the northeastern Asian area using observations from the Korean AGAGE site at Gosan and find significant emissions for ΣCFC-114 and CFC-115, suggesting that a large fraction of their global emissions currently occur in northeastern Asia and more specifically on the Chinese mainland.