Just under three hundred thousand hourly O3 observations from the Mace Head, Ireland atmospheric monitoring station have been assembled into a complete dataset covering the thirty five-year period from April 1, 1987 through to May 31, 2022. Of these, seventy thousand hourly observations were assigned to baseline air masses over the 422 months in the study. Annual mean baseline mixing ratios rose from 34 ppb in 1988 to a peak of 42 ppb in 1999 before declining to 39 ppb in 2021. Monthly mean baseline mixing ratios reached a peak of 53 ppb in April 1999. Baseline O3 mixing ratios exhibit a marked seasonal cycle, with maxima in April and minima in August. A detailed examination of the differences between the baseline and complete monthly mean O3 mixing ratios revealed a set of monthly differences with some striking long-term changes. Wintertime differences were dominated by a series of O3 depletion events in which, during the early years of the study, reduced ozone to near zero in long-range transport events. European NOx emission reductions have reduced significantly the number and severity of these wintertime O3 depletion events. Summertime differences were dominated by a series of regional photochemical episodes. In the early years of the record, the regional photochemical episodes were intense enough to raise the monthly means in the complete record above the baseline means. European volatile organic compound (VOC) and NOx precursor emission reductions have dramatically reduced the number and intensity of these events. Episodic peak O3 levels have also fallen steadily as a result of concerted, European action on regional VOC and NOx emissions. Subsets of the baseline and complete ozone datasets between 2017 and 2022 were scrutinised for possible COVID-19 impacts. Baseline ozone levels were lower than expected during 2020 and 2021 but the statistical significance of these impacts is difficult to judge, and reduced stratosphere-troposphere exchange rather than COVID-19 emission reductions may be the cause.

Abstract. Trifluoromethane (CHF3, HFC-23), one of the most potent greenhouse gases among HFCs, is mainly emitted to the atmosphere as a by-product in the production of the ozone depleting legacy refrigerant and chemical feedstock chlorodifluoromethane (CHClF2, HCFC-22). A recent study on global HFC-23 emissions (Stanley et al., 2020) showed significant discrepancies over 2014–2017 between the increase in the observation-derived (top-down) emissions and the 87 % emission reduction expected from capture and destruction processes of HFC-23 at HCFC-22 production facilities mandated by national phase-out plans (bottom-up). However, the actual sources of the increased emissions were not identified. Here, we estimate the regional top-down emissions of HFC-23 for East Asia based on in situ measurements at Gosan, South Korea, and show that the HFC-23 emissions from eastern China have increased from 5.0 ± 0.4 Gg yr-1 in 2008 to 9.5 ± 1.0 Gg yr-1 in 2019. The continuous rise was contrary to the large emissions reduction reported since 2015 under the Chinese hydrochlorofluorocarbons production phase-out management plan (HPPMP). The magnitude of the mismatch between top-down and bottom-up estimates for 2015–2019 in eastern China was ~23.7 ± 3.6 Gg, which accounts for 47 ± 11 % of the global mismatch. Given the location of HCFC-22 production plants in eastern China and the fraction of regional to global HCFC-22 production capacities, the HFC-23 emissions rise in eastern China is most likely associated with known HCFC-22 production facilities and thus, observed discrepancies between top-down and bottom-up emissions could be attributed to unsuccessful factory level HFC-23 abatement and inaccurate quantification of emission reductions.

Production and consumption of CFC-11 (trichlorofluoromethane, CCl3F), CFC-12 (dichlorodifluoromethane, CCl2F2) and CCl4 (carbon tetrachloride) are controlled under the regulations of the Montreal Protocol and have been phased out globally since 2010. Only CCl4 is still widely produced as a chemical feedstock. After 2010, emissions of CFC-11 and CFC-12 should therefore mostly originate from existing banks (e.g. from foams, mobile air conditioning units and refrigerators); however evidence has emerged of an increase in global emissions of CFC-11 in the last decade, some of which has not been fully accounted for. The motivation for this work was to assess the emissions of CFC-11, CFC-12 and CCl4 from western Europe. All countries in this region have been subject to the controls of the Montreal Protocol since the late 1980s and, as non-Article 5 Parties, have been prohibited from producing CFCs and CCl4 for dispersive use since 1996. Four different inverse modelling systems are used to estimate emissions of these gases from 2008 to 2021 using data from four atmospheric measurement stations: Mace Head (Ireland), Jungfraujoch (Switzerland), Monte Cimone (Italy) and Tacolneston (UK). The average of the four model studies found that western European emissions of CFC-11, CFC-12 and CCl4 between 2008 and 2021 were declining at 3.5% yr(-1) (2.7% (-1)-4.8% yr(-1)), 7.7% yr(-1) (6.3% yr(-1)-8.0% yr(-1)) and 4.4% yr(-1) (2.6% yr(-1)-6.4% yr(-1)), respectively. Even though the emissions were declining throughout the period, the area including northern France, Belgium, the Netherlands and Luxembourg showed consistently elevated emissions of CFC-11 compared with the surrounding regions. Emissions of CFC-12 were slightly elevated in the same region. CCl4 emissions were the highest in the south of France. France had the highest emissions of all three gases over the period 2008-2021. Emissions from western Europe (2008-2021) were on average 2.4 +/- 0.4 Gg (CFC-11), 1.3 +/- 0.3 Gg (CFC-12) and 0.9 +/- 0.2 Gg (CCl4). Our estimated decline in emissions of CFC-11 is consistent with a western European bank release rate of 3.4% (2.6 %-4.5 %). This study concludes that emissions of CFC-11, CFC-12 and CCl4 have all declined from 2008 to 2021 in western Europe. Therefore, no evidence is found that western European emissions contributed to the unexplained part of the global increase in atmospheric concentrations of CFC-11 observed in the last decade.

Abstract. Trifluoromethane (CHF3, HFC-23), one of the most potent greenhouse gases among hydrofluorocarbons (HFCs), is mainly emitted to the atmosphere as a by-product in the production of the ozone-depleting legacy refrigerant and chemical feedstock chlorodifluoromethane (CHClF2, HCFC-22). A recent study on atmospheric observation-based global HFC-23 emissions (top-down estimates) showed significant discrepancies over 2014–2017 between the increase in the observation-derived emissions and the 87 % emission reduction expected from capture and destruction processes of HFC-23 at HCFC-22 production facilities implemented by national phase-out plans (bottom-up emission estimates) (Stanley et al., 2020). However, the actualregions responsible for the increased emissions were not identified. Here,we estimate the regional top-down emissions of HFC-23 for eastern Asia based on in situ measurements at Gosan, South Korea, and show that the HFC-23 emissions from eastern China have increased from 5.0±0.4 Gg yr−1 in 2008 to 9.5±1.0 Gg yr−1 in 2019. The continuous rise since 2015 was contrary to the large emissions reduction reported under the Chinese hydrochlorofluorocarbons production phase-out management plan (HPPMP). The cumulative difference between top-down and bottom-up estimates for 2015–2019 in eastern China was ∼23.7±3.6 Gg, which accounts for 47±11 % of the global mismatch. Our analysis based on HCFC-22 production information suggests the HFC-23 emissions rise in eastern China is more likely associated with known HCFC-22 production facilities rather than the existence of unreported, unknown HCFC-22 production, and thus observed discrepancies between top-down and bottom-up emissions could be attributed to unsuccessful factory-level HFC-23 abatement and inaccurate quantification of emission reductions.

This study analysed just under three hundred thousand 40-min hydrogen observations taken at the Mace Head baseline station on the Atlantic Ocean coastline of Ireland between 1994 and 2022. Advection of European polluted air masses to Mace Head brought elevated hydrogen mixing ratios. Annual mean European excess mixing ratios were between 2 and 4 ppb above baseline in the 1990s but have steadily declined to about 0.2 ppb in 2021, with an e-folding time of 10 years. European excess carbon monoxide mixing ratios declined in an analogous manner, confirming the cause of the declines in both hydrogen and carbon monoxide as the fitting of exhaust gas catalysts to petrol-engined motor vehicles. The annual mean baseline hydrogen mixing ratios were constant over the 1994-2010 period, averaging about 513 ppb, before an upwards trend set in bringing the annual mean up to 532 ppb in 2021. Monthly baseline mixing ratios exhibited a seasonal cycle with an average spring maximum of 531 ppb and an autumn minimum of 497 ppb. Differences between the monthly means and the 1995-2010 averages were constant up to December 2015 when an anomalous growth trend of 2-4 ppb yr(-1) set in. A two-hemisphere two-box model was used to describe the hydrogen budget over the 1995-2022 period. This model highlighted that a 'missing' source was required to explain the anomalous growth in the Mace Head observations from 2010 onwards. Six potential candidates for this 'missing' source were characterised. However, there is a dearth of hydrogen observations with which to identify the real 'missing' source with any certainty. The anomalous growth in hydrogen since 2010 reported here may feasibly be the first evidence of the widespread seepage of natural hydrogen into the atmosphere.

Abstract. Production and consumption of CFC-11 (trichlorofluoromethane, CCl3F), CFC-12 dichlorodifluoromethane, CCl2F2) and CCl4 (carbon tetrachloride) are controlled under the regulations of the Montreal Protocol and have been phased out globally for dispersive use since 2010. Only CCl4 is still widely produced under exemption as a chemical feedstock (non-dispersive use). After 2010, emissions of CFC-11 and CFC-12 should therefore mostly originate from existing banks (e.g. foams and refrigerators), however evidence emerged of an increase in global emissions of CFC-11, which was in part attributed to eastern China. Emissions of CFC-11, CFC-12 and CCl4 have subsequently declined in this region, however the total global increase in CFC-11 was not fully accounted for. The motivation for this work was to assess the emissions of CFC-11 and the associated gases, CFC-12 and CCl4, from Western Europe. All countries in this region have been subject to the controls of the Montreal Protocol since the late 1980s, and, as non-Article-5 Parties, have been prohibited from producing CFCs and CCl4 for dispersive use since 1995. Four different inverse modelling systems are used to estimate emissions of these gases from 2008–2021 using data from four atmospheric measurement stations: Mace Head (Ireland), Jungfraujoch (Switzerland), Monte Cimone (Italy) and Tacolneston (UK). The average of the four model studies found that Western European emissions of CFC-11, CFC-12 and CCl4 between 2008 and 2021 were declining at 3.5 (2.7–4.8) %, 7.7 (6.3–8.0) % and 4.4 (2.6–6.4) % yr−1 respectively. Throughout this period, the highest CFC-11 emissions were in Northern France and Benelux (Belgium, the Netherlands and Luxembourg). Emissions of CFC-12 co-located in this region were slightly higher than elsewhere in Western Europe, and also showed some enhancement of CCl4 emissions. However for CCl4, emissions were highest in the south of France. France had the highest emissions of CFC-11, CFC-12 and CCl4 over the period 2008–2021. Emissions from Western Europe (2008–2021) were on average 2.4 ± 0.4 Gg (CFC-11), 1.3 ± 0.3 Gg (CFC-12), 0.9 ± 0.2 Gg (CCl4). This study concludes that the emissions of CFC-11 from Northern France and Benelux are unlikely to be the result of new production. Our estimated decline in emissions of CFC-11 is consistent with a Western European bank release rate of 3.4 (2.6–4.5) %, which is in the upper half of the published range.

Significance We demonstrate the need to detect and track unexpected substances in the atmosphere and to locate their sources. Here, we report on three hydrochlorofluorocarbons (HCFCs) that have no known end-uses. HCFC-132b ( C H 2 C l C C l F 2 ) is newly discovered in the global atmosphere. We identify East Asia as the dominant source region for global emissions of this compound and of HCFC-133a ( C H 2 C l C F 3 ). We also quantify global emissions of HCFC-31 ( C H 2 ClF). These compounds are most likely emitted as intermediate by-products of chemical production processes. The early discovery and identification of such unexpected emissions can identify the related industrial practices and help to develop and manage environmental policies to reduce unwanted and potentially harmful emissions before the scale of the problem becomes more costly to mitigate.

New emissions of methane and chloroform, with concurrent depositions of ozone and hydrogen were determined from the peat bogs of Ireland.

National greenhouse gas inventories (GHGIs) are submitted annually to the United Nations Framework Convention on Climate Change (UNFCCC). They are estimated in compliance with Intergovernmental Panel on Climate Change (IPCC) methodological guidance using activity data, emission factors and facility-level measurements. For some sources, the outputs from these calculations are very uncertain. Inverse modelling techniques that use high-quality, long-term measurements of atmospheric gases have been developed to provide independent verification of national GHGIs. This is considered good practice by the IPCC as it helps national inventory compilers to verify reported emissions and to reduce emission uncertainty. Emission estimates from the InTEM (Inversion Technique for Emission Modelling) model are presented for the UK for the hydrofluorocarbons (HFCs) reported to the UNFCCC (HFC-125, HFC-134a, HFC-143a, HFC-152a, HFC-23, HFC-32, HFC-227ea, HFC-245fa, HFC-43-10mee and HFC-365mfc). These HFCs have high global warming potentials (GWPs), and the global background mole fractions of all but two are increasing, thus highlighting their relevance to the climate and a need for increasing the accuracy of emission estimation for regulatory purposes. This study presents evidence that the long-term annual increase in growth of HFC-134a has stopped and is now decreasing. For HFC-32 there is an early indication, its rapid global growth period has ended, and there is evidence that the annual increase in global growth for HFC-125 has slowed from 2018. The inverse modelling results indicate that the UK implementation of European Union regulation of HFC emissions has been successful in initiating a decline in UK emissions from 2018. Comparison of the total InTEM UK HFC emissions in 2020 with the average from 2009–2012 shows a drop of 35 %, indicating progress toward the target of a 79 % decrease in sales by 2030. The total InTEM HFC emission estimates (2008–2018) are on average 73 (62–83) % of, or 4.3 (2.7–5.9) Tg CO2-eq yr−1 lower than, the total HFC emission estimates from the UK GHGI. There are also significant discrepancies between the two estimates for the individual HFCs.

Atmospheric tracers are effective tools for characterizing dispersion and for testing computational models of atmospheric transport. Atmospheric trace gas measurements are now used widely to infer geographical surface flux distributions. However, robust flux estimates critically rely on well-validated knowledge of atmospheric chemistry, loss processes and transport, without which we are not fully realizing the potential of atmospheric measurements collected on the ground, or from aircraft and satellites. This challenge has taken on renewed importance in the shadow of the Paris Agreement that will likely take advantage of atmospheric trace gas measurements to help improve national and global greenhouse gas emission budgets. We describe a wide range of existing and new potential atmospheric tracers for improving our understanding of atmospheric dispersion. We consider the investigation of atmospheric transport over two scales: (1) short-to-medium length scale (on the order of 1-1000 km) to improve our understanding of convection and boundary layer transport processes, and (2) hemisphere-to-global length scale (on the order of 1000-10,000 km), where large-scale mixing, cross hemisphere transport and stratosphere-troposphere exchange are important. Although we note the possibility of using "tracers of opportunity," our primary focus is on deliberate-release tracers, and we explore the use of cyclic perfluorocarbons, hydrofluorocarbons, hydrochlorofluorocarbons, hydrofluoroethers and novel tracers of deuterium-substituted halocarbons. We examine how we might exploit existing instrumentation already deployed at remote global monitoring sites as well as requirements for new instrumentation. To guide the discussion, we provide example scenarios for how experiments might be set up, covering regional to global spatial scales for the evaluation and improvement of atmospheric transport models. However, we stress that appropriate three-dimensional modelling studies and preliminary experiments would need to be carried out to determine the specific details of any real-world experiment.

3 Peter G. Simmonds, Matthew Rigby, Alistair J. Manning, Sunyoung Park, Kieran M. 4 Stanley, Archie McCulloch, Stephan Henne, Francesco Graziosi, Michela Maione, 5 Jgor Arduini, Stefan Reimann, Martin K. Vollmer, Jens Mühle, Simon O’Doherty, 6 Dickon Young, Paul B. Krummel, Paul J. Fraser, Ray F. Weiss, Peter K. Salameh, 7 Christina M. Harth, Mi-Kyung Park, Hyeri Park, Tim Arnold, Chris Rennick, L. Paul 8 Steele, Blagoj Mitrevski, Ray H. J. Wang, and Ronald G. Prinn. 9

We report a 40-year history of SF6 atmospheric mole fractions measured at the Advanced Global Atmospheric Gases Experiment (AGAGE) monitoring sites, combined with archived air samples, to determine emission estimates from 1978 to 2018. Previously we reported a global emission rate of 7.3±0.6 Gg yr−1 in 2008 and over the past decade emissions have continued to increase by about 24 % to 9.04±0.35 Gg yr−1 in 2018. We show that changing patterns in SF6 consumption from developed (Kyoto Protocol Annex-1) to developing countries (non-Annex-1) and the rapid global expansion of the electric power industry, mainly in Asia, have increased the demand for SF6-insulated switchgear, circuit breakers, and transformers. The large bank of SF6 sequestered in this electrical equipment provides a substantial source of emissions from maintenance, replacement, and continuous leakage. Other emissive sources of SF6 occur from the magnesium, aluminium, and electronics industries as well as more minor industrial applications. More recently, reported emissions, including those from electrical equipment and metal industries, primarily in the Annex-1 countries, have declined steadily through substitution of alternative blanketing gases and technological improvements in less emissive equipment and more efficient industrial practices. Nevertheless, there are still demands for SF6 in Annex-1 countries due to economic growth, as well as continuing emissions from older equipment and additional emissions from newly installed SF6-insulated electrical equipment, although at low emission rates. In addition, in the non-Annex-1 countries, SF6 emissions have increased due to an expansion in the growth of the electrical power, metal, and electronics industries to support their continuing development. There is an annual difference of 2.5–5 Gg yr−1 (1990–2018) between our modelled top-down emissions and the UNFCCC-reported bottom-up emissions (United Nations Framework Convention on Climate Change), which we attempt to reconcile through analysis of the potential contribution of emissions from the various industrial applications which use SF6. We also investigate regional emissions in East Asia (China, S. Korea) and western Europe and their respective contributions to the global atmospheric SF6 inventory. On an average annual basis, our estimated emissions from the whole of China are approximately 10 times greater than emissions from western Europe. In 2018, our modelled Chinese and western European emissions accounted for ∼36 % and 3.1 %, respectively, of our global SF6 emissions estimate.

A flexible approach for quantifying average long-term changes and seasonal cycles has been applied to the baseline mixing ratios of thirty-two trace gases monitored at the Atmospheric Research Station located at Mace Head, Ireland on the Atlantic Ocean coastline of Europe. Almost all these trace gases exhibit minima in their baseline seasonal cycles during a two-month period from mid-July to the end of September and maxima during a six-month period between November and May. Relative seasonal cycle amplitudes are largest for those trace gases with the shortest atmospheric lifetimes and smallest for the longest. Robust relationships were found between the timings of the seasonal maxima and minima and their relative amplitudes with the atmospheric lifetimes of the trace gases. These relationships provide a basis for understanding the reasons that the seasonal cycles of a few species (that is, H-2, CCl4 and the longest-lived gases) deviate significantly; they also have excellent potential as tools to assess global chemistry-transport model performance.

Under the Kigali Amendment to the Montreal Protocol, new controls are being implemented to reduce emissions of HFC-23 (CHF[Formula: see text]), a by-product during the manufacture of HCFC-22 (CHClF[Formula: see text]). Starting in 2015, China and India, who dominate global HCFC-22 production (75% in 2017), set out ambitious programs to reduce HFC-23 emissions. Here, we estimate that these measures should have seen global emissions drop by 87% between 2014 and 2017. Instead, atmospheric observations show that emissions have increased and in 2018 were higher than at any point in history (15.9 [Formula: see text]). Given the magnitude of the discrepancy between expected and observation-inferred emissions, it is likely that the reported reductions have not fully materialized or there may be substantial unreported production of HCFC-22, resulting in unaccounted-for HFC-23 by-product emissions. The difference between reported and observation-inferred estimates suggests that an additional ~309 Tg [Formula: see text]-equivalent emissions were added to the atmosphere between 2015 and 2017.

We reconstruct atmospheric abundances of the potent greenhouse gas c-C4F8 (perfluorocyclobutane, perfluorocarbon PFC-318) from measurements of in situ, archived, firn, and aircraft air samples with precisions of ∼1 %–2 % reported on the SIO-14 gravimetric calibration scale. Combined with inverse methods, we found near-zero atmospheric abundances from the early 1900s to the early 1960s, after which they rose sharply, reaching 1.66 ppt (parts per trillion dry-air mole fraction) in 2017. Global c-C4F8 emissions rose from near zero in the 1960s to 1.2±0.1 (1σ) Gg yr−1 in the late 1970s to late 1980s, then declined to 0.77±0.03 Gg yr−1 in the mid-1990s to early 2000s, followed by a rise since the early 2000s to 2.20±0.05 Gg yr−1 in 2017. These emissions are significantly larger than inventory-based emission estimates. Estimated emissions from eastern Asia rose from 0.36 Gg yr−1 in 2010 to 0.73 Gg yr−1 in 2016 and 2017, 31 % of global emissions, mostly from eastern China. We estimate emissions of 0.14 Gg yr−1 from northern and central India in 2016 and find evidence for significant emissions from Russia. In contrast, recent emissions from northwestern Europe and Australia are estimated to be small (≤1 % each). We suggest that emissions from China, India, and Russia are likely related to production of polytetrafluoroethylene (PTFE, “Teflon”) and other fluoropolymers and fluorochemicals that are based on the pyrolysis of hydrochlorofluorocarbon HCFC-22 (CHClF2) in which c-C4F8 is a known by-product. The semiconductor sector, where c-C4F8 is used, is estimated to be a small source, at least in South Korea, Japan, Taiwan, and Europe. Without an obvious correlation with population density, incineration of waste-containing fluoropolymers is probably a minor source, and we find no evidence of emissions from electrolytic production of aluminum in Australia. While many possible emissive uses of c-C4F8 are known and though we cannot categorically exclude unknown sources, the start of significant emissions may well be related to the advent of commercial PTFE production in 1947. Process controls or abatement to reduce the c-C4F8 by-product were probably not in place in the early decades, explaining the increase in emissions in the 1960s and 1970s. With the advent of by-product reporting requirements to the United Nations Framework Convention on Climate Change (UNFCCC) in the 1990s, concern about climate change and product stewardship, abatement, and perhaps the collection of c-C4F8 by-product for use in the semiconductor industry where it can be easily abated, it is conceivable that emissions in developed countries were stabilized and then reduced, explaining the observed emission reduction in the 1980s and 1990s. Concurrently, production of PTFE in China began to increase rapidly. Without emission reduction requirements, it is plausible that global emissions today are dominated by China and other developing countries. We predict that c-C4F8 emissions will continue to rise and that c-C4F8 will become the second most important emitted PFC in terms of CO2-equivalent emissions within a year or two. The 2017 radiative forcing of c-C4F8 (0.52 mW m−2) is small but emissions of c-C4F8 and other PFCs, due to their very long atmospheric lifetimes, essentially permanently alter Earth's radiative budget and should be reduced. Significant emissions inferred outside of the investigated regions clearly show that observational capabilities and reporting requirements need to be improved to understand global and country-scale emissions of PFCs and other synthetic greenhouse gases and ozone-depleting substances.