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Trifluoromethane (CHF 3 , 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 (CHClF 2 , 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 actual regions 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. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

Nitrous oxide is a potent greenhouse gas (GHG) and ozone-depleting substance, whose atmospheric abundance has risen throughout the contemporary record. In this work, we carry out the first global hierarchical Bayesian inversion to solve for nitrous oxide emissions, which includes prior emissions with truncated Gaussian distributions and Gaussian model errors, in order to examine the drivers of the atmospheric surface growth rate. We show that both emissions and climatic variability are key drivers of variations in the surface nitrous oxide growth rate between 2011 and 2020. We derive increasing global nitrous oxide emissions, which are mainly driven by emissions between 0 and 30 ∘ N, with the highest emissions recorded in 2020. Our mean global total emissions for 2011–2020 of 17.2 (16.7–17.7 at the 95 % credible intervals) Tg N yr -1 , comprising of 12.0 (11.2–12.8) Tg N yr -1 from land and 5.2 (4.5–5.9) Tg N yr -1 from ocean, agrees well with previous studies, but we find that emissions are poorly constrained for some regions of the world, particularly for the oceans. The prior emissions used in this and other previous work exhibit a seasonal cycle in the extra-tropical Northern Hemisphere that is out of phase with the posterior solution, and there is a substantial zonal redistribution of emissions from the prior to the posterior. Correctly characterizing the uncertainties in the system, for example in the prior emission fields, is crucial for deriving posterior fluxes that are consistent with observations. In this hierarchical inversion, the model-measurement discrepancy and the prior flux uncertainty are informed by the data, rather than solely through "expert judgement". We show cases where this framework provides different plausible adjustments to the prior fluxes compared to inversions using widely adopted, fixed uncertainty constraints. [ABSTRACT FROM AUTHOR]

Global emissions of the ozone-depleting gas HCFC-141b (1,1-dichloro-1-fluoroethane, CH 3 CCl 2 F) derived from measurements of atmospheric mole fractions increased between 2017 and 2021 despite a fall in reported production and consumption of HCFC-141b for dispersive uses. HCFC-141b is a controlled substance under the Montreal Protocol, and its phase-out is currently underway, after a peak in reported consumption and production in developing (Article 5) countries in 2013. If reported production and consumption are correct, our study suggests that the 2017–2021 rise is due to an increase in emissions from the bank when appliances containing HCFC-141b reach the end of their life, or from production of HCFC-141b not reported for dispersive uses. Regional emissions have been estimated between 2017–2020 for all regions where measurements have sufficient sensitivity to emissions. This includes the regions of northwestern Europe, east Asia, the United States and Australia, where emissions decreased by a total of 2.3 ± 4.6 Gg yr -1 , compared to a mean global increase of 3.0 ± 1.2 Gg yr -1 over the same period. Collectively these regions only account for around 30 % of global emissions in 2020. We are not able to pinpoint the source regions or specific activities responsible for the recent global emission rise. [ABSTRACT FROM AUTHOR]

Methyl bromide (CH3Br) is a potent ozone-depleting substance (ODS) that has both natural and anthropogenic sources. CH3Br has been used mainly for preplant soil fumigation, post-harvest grain and timber fumigation, and structural fumigation. Most non-quarantine and pre-shipment (non-QPS) uses were phased out by 2005 for non-Article 5 (developed) countries and by 2015 for Article 5 (developing) countries under the Montreal Protocol on Substances that Deplete the Ozone Layer; some uses have continued under critical-use exemptions (CUEs). Under the protocol, individual nations are required to report annual data on CH3Br production and consumption for quarantine–pre-shipment (QPS) uses, non-QPS uses, and CUEs to the United Nations Environment Programme (UNEP). In this study, we analyzed high-precision, in situ measurements of atmospheric mole fractions of CH3Br obtained at the Gosan station on Jeju Island, South Korea, from 2008 to 2019. The background mole fractions of CH3Br in the atmosphere at Gosan declined from 8.5±0.8 ppt (parts per trillion) in 2008 to 7.4±0.6 ppt in 2019 at a rate of -0.13±0.02 ppt yr -1. At Gosan, we also observed periods of persistent mole fractions (pollution events) elevated above the decreasing background in continental air masses from China. Statistical back-trajectory analyses showed that these pollution events are predominantly traced back to CH3Br emissions from eastern China. Using an interspecies correlation (ISC) method with the reference trace species CFC-11 (CCl3F), we estimate anthropogenic CH3Br emissions from eastern China at an average of 4.1±1.3 Gg yr -1 in 2008–2019, approximately 2.9±1.3 Gg yr -1 higher than the bottom-up emission estimates reported to UNEP. Possible non-fumigation CH3Br sources – rapeseed production and biomass burning – were assessed, and it was found that the discrepancy is most likely due to unreported or incorrectly reported QPS and non-QPS fumigation uses. These unreported anthropogenic emissions of CH3Br are confined to eastern China and account for 30 %–40 % of anthropogenic global CH3Br emissions. They are likely due to delays in the introduction of CH3Br alternatives, such as sulfuryl fluoride (SO2F2), heat, and irradiation, and a possible lack of industry awareness of the need for regulation of CH3Br production and use. [ABSTRACT FROM AUTHOR]

Emissions of the potent greenhouse gas perfluorocyclobutane (c -C 4 F 8 , PFC-318, octafluorocyclobutane) into the global atmosphere inferred from atmospheric measurements have been increasing sharply since the early 2000s. We find that these inferred emissions are highly correlated with the production of hydrochlorofluorocarbon-22 (HCFC-22, CHClF 2) for feedstock (FS) uses, because almost all HCFC-22 FS is pyrolyzed to produce (poly)tetrafluoroethylene ((P)TFE) and hexafluoropropylene (HFP), a process in which c -C 4 F 8 is a known by-product, causing a significant fraction of global c -C 4 F 8 emissions. We find a global emission factor of ∼0.003 kg c -C 4 F 8 per kilogram of HCFC-22 FS pyrolyzed. Mitigation of these c -C 4 F 8 emissions, e.g., through process optimization, abatement, or different manufacturing processes, such as refined methods of electrochemical fluorination and waste recycling, could reduce the climate impact of this industry. While it has been shown that c -C 4 F 8 emissions from developing countries dominate global emissions, more atmospheric measurements and/or detailed process statistics are needed to quantify c -C 4 F 8 emissions at country to facility levels. [ABSTRACT FROM AUTHOR]

Emissions of the potent greenhouse gas perfluorocyclobutane (c-C4F8, PFC-318, octafluorocyclobutane) into the global atmosphere inferred from atmospheric measurements have been increasing sharply since the early 2000s. We find that these inferred emissions are highly correlated with the production of hydrochlorofluorocarbon-22 (HCFC-22, CHClF2) for feedstock (FS) uses, because almost all HCFC-22 FS is pyrolyzed to produce (poly)tetrafluoroethylene ((P)TFE, Teflon) and hexafluoropropylene (HFP), a process in which c-C4F8 is a known by-product, causing a significant fraction of global c-C4F8 emissions. We find a global emission factor of ~0.003 kg c-C4F8 per kg of HCFC-22 FS pyrolyzed. Mitigation of these c-C4F8 emissions, e.g., through process optimization, abatement, or different manufacturing processes, such as electrochemical fluorination, could reduce the climate impact of this industry. While it has been shown that c-C4F8 emissions from developing countries dominate global emissions, more atmospheric measurements and/or detailed process statistics are needed to quantify country to facility level c-C4F8 emissions. [ABSTRACT FROM AUTHOR]

Methyl bromide (CH3Br) is a potent ozone-depleting substance (ODS) that has both natural and anthropogenic sources. CH3Br has been used mainly for preplant soil fumigation, post-harvest grain and timber fumigation and structural fumigation. Most non-quarantine/pre-shipment (non-QPS) uses have been phased-out in 2005 for non-Article 5 (developed) countries and in 2015 for Article 5 (developing) countries under the Montreal Protocol on Substances that Deplete the Ozone Layer; some uses have continued under critical use exemptions (CUEs). Under the Protocol, individual nations are required to report annual data on CH3Br production and consumption for quarantine/pre-shipment (QPS) uses, non-QPS uses and CUEs to the United Nations Environment Programme (UNEP). In this study, we analyzed high precision, in situ measurements of atmospheric concentrations of CH3Br obtained at the Gosan station on Jeju island, Korea, from 2008 to 2019. The background concentrations of CH3Br in the atmosphere at Gosan declined from 8.5 ± 0.8 ppt in 2008 to 7.4 ± 0.6 ppt in 2019 at a rate of -- 0.13 ± 0.02 ppt yr1. At Gosan, we also observed periods of persistent concentrations (pollution events) elevated above the decreasing background in continental air masses from China. Statistical back trajectory analyses showed that these pollution events predominantly trace back to CH3Br emissions from eastern China. Using an inter-species correlation (ISC) method with the reference trace species CFC-11 (CCbF), we estimate anthropogenic CH3Br emissions from eastern China at 4.1 ± 1.3 Gg yr-1 in 2008-2019, approximately 2.9 ± 1.3 Gg yr-1 higher than the bottom-up emission estimates reported to UNEP. Possible non-fumigation CH3Br sources -- rapeseed production and biomass burning -- were assessed and it was found that the discrepancy is more likely due to unreported or incorrectly reported QPS and non-QPS fumigation uses. These largely-unreported anthropogenic emissions of CH3Br are confined to eastern China and account for 30-40% of anthropogenic global CH3Br emissions. They are likely due to delays in the introduction of CH3Br alternatives, such as sulfuryl fluoride (SO2F2), heat, irradiation and a possible lack of industry awareness of the need for regulation of CH3Br production and use. [ABSTRACT FROM AUTHOR]

We have developed a procedure for retrieving atmospheric abundances of HFC-23 (CHF3) with a ground-based Fourier transform infrared (FTIR) spectrometer and analyzed the spectra observed at Rikubetsu, Japan (43.5 ∘ N, 143.8 ∘ E), and at Syowa Station, Antarctica (69.0 ∘ S, 39.6 ∘ E). The FTIR retrievals were carried out with the SFIT4 retrieval program, and the two spectral windows of 1138.5–1148.0 cm-1 and 1154.0–1160.0 cm-1 in the overlapping ν2 and ν5 vibrational–rotational transition bands of HFC-23 were used to avoid strong H2O absorption features. We considered O3 , N2O , CH4 , H2O , HDO, CFC-12 (CCl2F2), HCFC-22 (CHClF2), peroxyacetyl nitrate (PAN) (CH3C(O)OONO2), HCFC-141b (CH3CCl2F), and HCFC-142b (CH3CClF2) to be interfering species. Vertical profiles of H2O , HDO, and CH4 are preliminarily retrieved with other independent spectral windows because these profiles may induce large uncertainties in the HFC-23 retrieval. Each HFC-23 retrieval has only one piece of vertical information with sensitivity to HFC-23 in the troposphere and the lower stratosphere. Retrieval errors mainly arise from the systematic uncertainties of the spectroscopic parameters used to obtain HFC-23 , H2O , HDO, and CH4 abundances. For comparison between FTIR-retrieved HFC-23 total columns and surface dry-air mole fractions provided by AGAGE (Advanced Global Atmospheric Gases Experiment), FTIR-retrieved HFC-23 dry-air column-averaged mole fractions (XHFC-23) were calculated. The FTIR-retrieved XHFC-23 values at Rikubetsu and Syowa Station have negative biases of - 15 % to - 20 % and - 25 % compared to the AGAGE datasets, respectively. These negative biases might mainly come from systematic uncertainties of HFC-23 spectroscopic parameters. The trend of the FTIR-retrieved XHFC-23 data at Rikubetsu was derived for December to February (DJF) observations, which are considered to represent the background values when an air mass reaching Rikubetsu has the least influence by transport of HFC-23 emissions from nearby countries. The DJF trend of Rikubetsu over the 1997–2009 period is 0.810 ± 0.093 ppt yr-1 (ppt: parts per trillion), which is in good agreement with the trend derived from the annual global mean datasets of the AGAGE 12-box model for the same period (0.820 ± 0.013 pptyr-1). The DJF trend of Rikubetsu over the 2008–2019 period is 0.928 ± 0.108 pptyr-1 , which is consistent with the trend in the AGAGE in situ measurements at Trinidad Head (41.1 ∘ N, 124.2 ∘ W) for the same period (0.994 ± 0.001 pptyr-1). The trend of the FTIR-retrieved XHFC-23 data at Syowa Station over the 2007–2016 period is 0.819 ± 0.071 pptyr-1 , which is consistent with that derived from the AGAGE in situ measurements at Cape Grim (40.7 ∘ S, 144.7 ∘ E) for the same period (0.874 ± 0.002 pptyr-1). Although there are systematic biases in the FTIR-retrieved XHFC-23 at both sites, these results indicate that ground-based FTIR observations have the capability to monitor the long-term trend of atmospheric HFC-23. If this FTIR measurement technique were extended to other Network for the Detection of Atmospheric Composition Change (NDACC) ground-based FTIR sites around world, the measurements reported from these sites would complement the global AGAGE observations by filling spatial and temporal gaps and may lead to improved insights about changes in regional and global emissions of HFC-23 and its role in global warming. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

We report a 40-year history of SF 6 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 SF 6 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 SF 6 -insulated switchgear, circuit breakers, and transformers. The large bank of SF 6 sequestered in this electrical equipment provides a substantial source of emissions from maintenance, replacement, and continuous leakage. Other emissive sources of SF 6 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 SF 6 in Annex-1 countries due to economic growth, as well as continuing emissions from older equipment and additional emissions from newly installed SF 6 -insulated electrical equipment, although at low emission rates. In addition, in the non-Annex-1 countries, SF 6 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 SF 6. We also investigate regional emissions in East Asia (China, S. Korea) and western Europe and their respective contributions to the global atmospheric SF 6 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 SF 6 emissions estimate. [ABSTRACT FROM AUTHOR]

Perfluorocarbons (PFCs) are potent greenhouse gases with global warming potentials up to several thousand times greater than CO2 on a 100-year time horizon. The lack of any significant sinks for PFCs means that they have long atmospheric lifetimes of the order of thousands of years. Anthropogenic production is thought to be the only source for most PFCs. Here we report an update on the global atmospheric abundances of the following PFCs, most of which have for the first time been analytically separated according to their isomers: c-octafluorobutane (c- C4F8), n-decafluorobutane (n- C4F10), n-dodecafluoropentane (n- C5F12), n-tetradecafluorohexane (n- C6F14), and n-hexadecafluoroheptane (n- C7F16). Additionally, we report the first data set on the atmospheric mixing ratios of perfluoro-2-methylpentane (i- C6F14). The existence and significance of PFC isomers have not been reported before, due to the analytical challenges of separating them. The time series spans a period from 1978 to the present. Several data sets are used to investigate temporal and spatial trends of these PFCs: time series of air samples collected at Cape Grim, Australia, from 1978 to the start of 2018; a time series of air samples collected between July 2015 and April 2017 at Tacolneston, UK; and intensive campaign-based sampling collections from Taiwan. Although the remote "background" Southern Hemispheric Cape Grim time series indicates that recent growth rates of most of these PFCs are lower than in the 1990s, we continue to see significantly increasing mixing ratios that are between 6 % and 27 % higher by the end of 2017 compared to abundances measured in 2010. Air samples from Tacolneston show a positive offset in PFC mixing ratios compared to the Southern Hemisphere baseline. The highest mixing ratios and variability are seen in air samples from Taiwan, which is therefore likely situated much closer to PFC sources, confirming predominantly Northern Hemispheric emissions for most PFCs. Even though these PFCs occur in the atmosphere at levels of parts per trillion molar or less, their total cumulative global emissions translate into 833 million metric tonnes of CO2 equivalent by the end of 2017, 23 % of which has been emitted since 2010. Almost two-thirds of the CO2 equivalent emissions within the last decade are attributable to c- C4F8 , which currently also has the highest emission rates that continue to grow. Sources of all PFCs covered in this work remain poorly constrained and reported emissions in global databases do not account for the abundances found in the atmosphere. [ABSTRACT FROM AUTHOR]

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 1978-2018. Previously we reported a global emission rate of 7.3 ± 0.6 Gigagrams (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, electronics industries and more minor industrial applications. More recently, reported emissions, including those from electrical equipment and metal industries, primarily in the Annex-1 countries, have steadily declined through substitution of alternative blanketing gases and technological improvements in less emissive equipment and more efficient industrial practices. Conversely, 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 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, 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. [ABSTRACT FROM AUTHOR]

Perfluorocarbons (PFCs) are potent greenhouse gases with Global Warming Potentials up to several thousand times greater than CO2 on a 100-year time horizon. The lack of any significant sinks for PFCs means that they have long atmospheric lifetimes on the order of thousands of years. Anthropogenic production is thought to be the only source for most PFCs. Here we report an update on the global atmospheric abundances of the following PFCs, most of which have for the first time been separated according to their isomers: c-octafluorobutane (c-C4F8), n-decafluorobutane (n-C4F10), n-dodecafluoropentane (n-C5F12), n-tetradecafluorohexane (n-C6F14), and n-hexadecafluoroheptane (n-C7F16). Additionally, we report the first data set on the atmospheric mixing ratios of perfluoro(2-methylpentane) (i-C6F14). The existence and significance of PFC isomers has not been reported before, due to the analytical challenges of separating them. The time series spans a period from 1978 to the present. Several datasets are used to investigate temporal and spatial trends of these PFCs: time series of air samples collected at Cape Grim, Australia, from 1978 to the start of 2018; a time series of air samples collected between July 2015 and April 2017 at Tacolneston, UK; and intensive campaign-based sampling collections from Taiwan. Although the remote background Southern Hemispheric Cape Grim time series indicates that recent growth rates of most of these PFCs are lower than in the 1990s, we continue to see significantly increasing mixing ratios that are between 6% to 27% higher by the end of 2017 compared to abundances measured in 2010. Air samples from Tacolneston show a positive offset in PFC mixing ratios compared to the Southern Hemisphere baseline. The highest mixing ratios and variability are seen in air samples from Taiwan, which is therefore likely situated much closer to PFC sources, confirming predominantly Northern Hemispheric emissions for most PFCs. Even though these PFCs occur in the atmosphere at levels of parts per trillion molar or less, their total cumulative global emissions translate into 833 million metric tonnes of CO2 equivalent by the end of 2017, 23% of which has been emitted in the last eight years. Almost two-thirds of the CO2 equivalent emissions are attributable to c-C4F8, which currently also has the highest emission rates that continue to grow. Despite this, the sources of all PFCs covered in this work remain poorly constrained and reported emissions in global databases do not account for the abundances found in the atmosphere. [ABSTRACT FROM AUTHOR]

The first atmospheric observations of octafluorooxolane (octafluorotetrahydrofuran, c - C4F8O), a persistent greenhouse gas, are reported. In addition, a complementary laboratory study of its most likely atmospheric loss processes, its infrared absorption spectrum, and global warming potential (GWP) are reported. First atmospheric measurements of c - C4F8O are provided from the Cape Grim Air Archive (41 ∘ S, Tasmania, Australia, 1978–present), supplemented by two firn air samples from Antarctica, in situ measurements of ambient air at Aspendale, Victoria (38 ∘ S), and a few archived air samples from the Northern Hemisphere. The atmospheric abundance in the Southern Hemisphere has monotonically grown over the past decades and leveled at 74 ppq (parts per quadrillion, femtomole per mole in dry air) by 2015–2018. The growth rate of c - C4F8O has decreased from a maximum in 2004 of 4.0 to <0.25 ppq yr -1 in 2017 and 2018. Using a 12-box atmospheric transport model, globally averaged yearly emissions and abundances of c - C4F8O are calculated for 1951–2018. Emissions, which we speculate to derive predominantly from usage of c - C4F8O as a solvent in the semiconductor industry, peaked at 0.15 (±0.04 , 2 σ) kt yr -1 in 2004 and have since declined to <0.015 kt yr -1 in 2017 and 2018. Cumulative emissions over the full range of our record amount to 2.8 (2.4–3.3) kt, which correspond to 34 Mt of CO2 -equivalent emissions. Infrared and ultraviolet absorption spectra for c - C4F8O as well as the reactive channel rate coefficient for the O(1D) + c - C4F8O reaction were determined from laboratory studies. On the basis of these experiments, a radiative efficiency of 0.430 W m -2 ppb -1 (parts per billion, nanomol mol -1) was determined, which is one of the largest found for synthetic greenhouse gases. The global annually averaged atmospheric lifetime, including mesospheric loss, is estimated to be >3 000 years. GWPs of 8975, 12 000, and 16 000 are estimated for the 20-, 100-, and 500-year time horizons, respectively. [ABSTRACT FROM AUTHOR]

We present consistent annual mean atmospheric histories and growth rates for the mainly anthropogenic halogenated compounds HCFC-22, HCFC-141b, HCFC-142b, HFC-134a, HFC-125, HFC-23, PFC-14 and PFC-116, which are all potentially useful oceanic transient tracers (tracers of water transport within the ocean), for the Northern and Southern Hemisphere with the aim of providing input histories of these compounds for the equilibrium between the atmosphere and surface ocean. We use observations of these halogenated compounds made by the Advanced Global Atmospheric Gases Experiment (AGAGE), the Scripps Institution of Oceanography (SIO), the Commonwealth Scientific and Industrial Research Organization (CSIRO), the National Oceanic and Atmospheric Administration (NOAA) and the University of East Anglia (UEA). Prior to the direct observational record, we use archived air measurements, firn air measurements and published model calculations to estimate the atmospheric mole fraction histories. The results show that the atmospheric mole fractions for each species, except HCFC-141b and HCFC-142b, have been increasing since they were initially produced. Recently, the atmospheric growth rates have been decreasing for the HCFCs (HCFC-22, HCFC-141b and HCFC-142b), increasing for the HFCs (HFC-134a, HFC-125, HFC-23) and stable with little fluctuation for the PFCs (PFC-14 and PFC-116) investigated here. The atmospheric histories (source functions) and natural background mole fractions show that HCFC-22, HCFC-141b, HCFC-142b, HFC-134a, HFC-125 and HFC-23 have the potential to be oceanic transient tracers for the next few decades only because of the recently imposed bans on production and consumption. When the atmospheric histories of the compounds are not monotonically changing, the equilibrium atmospheric mole fraction (and ultimately the age associated with that mole fraction) calculated from their concentration in the ocean is not unique, reducing their potential as transient tracers. Moreover, HFCs have potential to be oceanic transient tracers for a longer period in the future than HCFCs as the growth rates of HFCs are increasing and those of HCFCs are decreasing in the background atmosphere. PFC-14 and PFC-116, however, have the potential to be tracers for longer periods into the future due to their extremely long lifetimes, steady atmospheric growth rates and no explicit ban on their emissions. In this work, we also derive solubility functions for HCFC-22, HCFC-141b, HCFC-142b, HFC-134a, HFC-125, HFC-23, PFC-14 and PFC-116 in water and seawater to facilitate their use as oceanic transient tracers. These functions are based on the Clark–Glew–Weiss (CGW) water solubility function fit and salting-out coefficients estimated by the poly-parameter linear free-energy relationships (pp-LFERs). Here we also provide three methods of seawater solubility estimation for more compounds. Even though our intention is for application in oceanic research, the work described in this paper is potentially useful for tracer studies in a wide range of natural waters, including freshwater and saline lakes, and, for the more stable compounds, groundwaters. [ABSTRACT FROM AUTHOR]

The first observations of octafluorooxolane (octafluorotetrahydrofuran, c-C4F8O), a persistent greenhouse gas, in the atmosphere are reported. In addition, a complimentary laboratory study of its most likely atmospheric loss processes and infrared absorption spectrum and global warming potential (GWP) are reported. First atmospheric measurements of c-C4F8O are provided from the Cape Grim Air Archive (41° S, Tasmania, Australia, 1978-present), supplemented by two firn air samples from Antarctica, in situ measurements of ambient air at Aspendale, Victoria (38° S), and a few archived air samples from the Northern Hemisphere. Atmospheric abundances in the Southern Hemisphere have reached 74 ppq (parts per quadrillion, femtomol mol-1 in dry air) by 2017. However its growth rate has decreased from a maximum in 2004 of 4.3 ppq yr-1 to < 0.15 ppq yr-1 in 2017. Using a 12-box atmospheric transport model, globally averaged yearly emissions and abundances of c-C4F8O are calculated for 1951-2017. Emissions, which we speculate to derive predominantly from usage of c-C4F8O as a solvent in the semiconductor industry, peaked at 0.16 (±0.04, 2σ) kt yr-1 in 2004 and have after declined to < 0.01 kt yr-1 in 2017. Cumulative emissions over the full range of our record amount to 2.8 (2.6-3.2) kt, which correspond to 34 Mt of CO2-equivalent emissions. Infrared and ultraviolet absorption spectra for c-C4F8O as well as the reactive channel rate coefficient for the O(¹D) + c-C4F8O reaction was determined from laboratory studies. On the basis of these experiments, a radiative efficiency of 0.430 W m-2 ppb-1 (parts per billion, nanomol mol-1) was determined, which is one of the largest found for synthetic greenhouse gases. The global annually averaged atmospheric lifetime, including mesospheric loss, is estimated to be > 3000 years. GWPs of 8975, 12000, and 16000 are estimated for the 20, 100, and 500-year time-horizons, respectively. [ABSTRACT FROM AUTHOR]

Atmospheric measurements of the ozonedepleting substance CFC-113a (CCl3CF3) are reported from ground-based stations in Australia, Taiwan, Malaysia and the United Kingdom, together with aircraft-based data for the upper troposphere and lower stratosphere. Building on previous work, we find that, since the gas first appeared in the atmosphere in the 1960s, global CFC-113a mixing ratios have been increasing monotonically to the present day. Mixing ratios of CFC-113a have increased by 40% from 0.50 to 0.70 ppt in the Southern Hemisphere between the end of the previously published record in December 2012 and February 2017. We derive updated global emissions of 1.7 Gg yr-1 on average between 2012 and 2016 using a two-dimensional model. We compare the long-term trends and emissions of CFC-113a to those of its structural isomer, CFC-113 (CClF2CCl2F), which still has much higher mixing ratios than CFC-113a, despite its mixing ratios and emissions decreasing since the 1990s. The continued presence of northern hemispheric emissions of CFC-113a is confirmed by our measurements of a persistent interhemispheric gradient in its mixing ratios, with higher mixing ratios in the Northern Hemisphere. The sources of CFC-113a are still unclear, but we present evidence that indicates large emissions in East Asia, most likely due to its use as a chemical involved in the production of hydrofluorocarbons. Our aircraft data confirm the interhemispheric gradient as well as showing mixing ratios consistent with ground-based observations and the relatively long atmospheric lifetime of CFC-113a. CFC-113a is the only known CFC for which abundances are still increasing substantially in the atmosphere. [ABSTRACT FROM AUTHOR]

High frequency measurements of trifluoromethane (HFC-23, CHF3), a potent hydrofluorocarbon greenhouse gas, largely emitted to the atmosphere as a by-product of the production of the hydrochlorofluorocarbon HCFC-22 (CHClF2), at five core stations of the Advanced Global Atmospheric Gases Experiment (AGAGE) network, combined with measurements on firn air, old Northern Hemisphere air samples and Cape Grim Air Archive (CGAA) air samples, are used to explore the current and historic changes in the atmospheric abundance of HFC-23. These measurements are used in combination with the AGAGE 2-D atmospheric 12-box model and a Bayesian inversion methodology to determine model atmospheric mole fractions and the history of global HFC-23 emissions. The global modelled annual mole fraction of HFC-23 in the background atmosphere was 28.9±0.6 pmol mol-1 at the end of 2016, representing a 28% increase from 22.6±0.4 pmol mol-1 in 2009. Over the same time frame, the modelled mole fraction of HCFC-22 increased by 19% from 199±2 to 237±2 pmol mol-1. However, unlike HFC-23, the annual average HCFC-22 growth rate slowed from 2009 to 2016 at an annual average rate of -0.5 pmol mol-1 yr-2. This slowing atmospheric growth is consistent with HCFC-22 moving from dispersive (high fractional emissions) to feedstock (low fractional emissions) uses, with HFC-23 emissions remaining as a consequence of incomplete mitigation from all HCFC-22 production. Our results demonstrate that, following a minimum in HFC-23 global emissions in 2009 of 9.6±0.6, emissions increased to a maximum in 2014 of 14.5±0.6 Gg yr-1 and then declined to 12.7±0.6 Gg yr-1 (157 MtCO2 eq. yr-1/in 2016. The 2009 emissions minimum is consistent with estimates based on national reports and is likely a response to the implementation of the Clean Development Mechanism (CDM) to mitigate HFC-23 emissions by incineration in developing (non-Annex 1) countries under the Kyoto Protocol. Our derived cumulative emissions of HFC-23 during 2010-2016 were 89±2 Gg (1.1±0.2 GtCO2 eq.), which led to an increase in radiative forcing of 1.0±0.1mWm-2 over the same period. Although the CDM had reduced global HFC-23 emissions, it cannot now offset the higher emissions from increasing HCFC-22 production in non-Annex 1 countries, as the CDM was closed to new entrants in 2009. We also find that the cumulative European HFC-23 emissions from 2010 to 2016 were ~1.3 Gg, corresponding to just 1.5% of cumulative global HFC-23 emissions over this same period. The majority of the increase in global HFC-23 emissions since 2010 is attributed to a delay in the adoption of mitigation technologies, predominantly in China and East Asia. However, a reduction in emissions is anticipated, when the Kigali 2016 amendment to the Montreal Protocol, requiring HCFC and HFC production facilities to introduce destruction of HFC-23, is fully implemented. [ABSTRACT FROM AUTHOR]

In a changing climate, potential stratospheric circulation changes require long-term monitoring. Stratospheric trace gas measurements are often used as a proxy for stratospheric circulation changes via the "mean age of air" values derived from them. In this study, we investigated five potential age of air tracers -- the perfluorocarbons CF4, C2F6 and C3F8 and the hydrofluorocarbons CHF3 (HFC-23) and HFC- 125 -- and compare them to the traditional tracer SF6 and a (relatively) shorter-lived species, HFC-227ea. A detailed uncertainty analysis was performed on mean ages derived from these "new" tracers to allow us to confidently compare their efficacy as age tracers to the existing tracer, SF6. Our results showed that uncertainties associated with the mean age derived from these new age tracers are similar to those derived from SF6, suggesting that these alternative compounds are suitable in this respect for use as age tracers. Independent verification of the suitability of these age tracers is provided by a comparison between samples analysed at the University of East Anglia and the Scripps Institution of Oceanography. All five tracers give younger mean ages than SF6, a discrepancy that increases with increasing mean age. Our findings qualitatively support recent work that suggests that the stratospheric lifetime of SF6 is significantly less than the previous estimate of 3200 years. The impact of these younger mean ages on three policy-relevant parameters -- stratospheric lifetimes, fractional release factors (FRFs) and ozone depletion potentials -- is investigated in combination with a recently improved methodology to calculate FRFs. Updates to previous estimations for these parameters are provided. [ABSTRACT FROM AUTHOR]

We present the organization, instrumentation, datasets, data interpretation, modeling, and accomplishments of the multinational, global atmospheric measurement program AGAGE (Advanced Global Atmospheric Gases Experiment). AGAGE is distinguished by its capability to measure globally, at high frequency and multiple sites, all the important species in the Montreal Protocol and all the important non-carbon dioxide (CO2) gases assessed by the Intergovernmental Panel on Climate Change (CO2 is also measured at several sites). The scientific objectives of AGAGE are important in furthering understanding of global chemical and climatic phenomena. They are to: (1) measure accurately the temporal and spatial distributions of anthropogenic gases that contribute the majority of reactive halogen to the stratosphere and/or are strong infrared absorbers [chlorocarbons, chlorofluorocarbons (CFCs), bromocarbons, hydrochlorofluorocarbons (HCFCs), hydrofluorocarbons (HFCs) and polyfluorinated compounds (perfluorocarbons (PFCs), nitrogen trifluoride (NF3), sulfuryl fluoride (SO2F2), and sulfur hexafluoride (SF6)), and use these measurements to determine the global rates of their emission and/or destruction (i.e. lifetimes); (2) measure accurately the global distributions and temporal behaviors and determine sources and sinks of non-CO2 biogenic-anthropogenic gases important to climate change and/or ozone depletion [methane (CH4), nitrous oxide (N2O), carbon monoxide (CO), molecular hydrogen (H2), methyl chloride (CH3Cl) and methyl bromide (CH3Br); (3) identify new long-lived greenhouse and ozone-depleting gases [e.g. SO2F2, NF3, heavy PFCs (C4F10, C5F12, C6F14, C7F16, and C8F18) and hydrofluoro-olefins (HFOs, e.g. CH2 = CFCF3) have been identified in AGAGE], initiate real-time monitoring of these new gases, and reconstruct their past histories from AGAGE, air-archive and firn-air measurements; (4) determine the average concentrations and trends of tropospheric hydroxyl radicals (OH) from the rates of destruction of atmospheric trichloroethane (CH3CCl3), HFCs and HCFCs, and estimates of their emissions; (5) determine from atmospheric observations and estimates of their destruction rates, the magnitudes, and distributions by region of surface sources/sinks of all measured gases; (6) provide accurate data on the global accumulation of many of these trace gases, that are used to test the synoptic/regional/global-scale circulations predicted by three-dimensional models; and (7) provide global and regional measurements of methane, carbon monoxide and molecular hydrogen, and estimates of hydroxyl levels, to test primary atmospheric oxidation pathways at mid-latitudes and the tropics. [ABSTRACT FROM AUTHOR]

Atmospheric measurements of the ozone depleting substance CFC-113a (CCl3CF3) are reported from ground-based stations in Australia, Taiwan, Malaysia and the United Kingdom, and aircraft-based measurements in the upper troposphere and stratosphere. Building on previous work we find that, since the gas first appeared in the atmosphere in the 1960s, global CFC-113a mixing ratios have been increasing monotonically to the present day. Mixing ratios of CFC-113a have increased by 40 % (percent) from 0.50 to 0.70 ppt (parts per trillion) in the Southern Hemisphere between the end of the previously published record in December 2012 and February 2017. We derive updated global emissions of 1.7 Gg yr-1 (1.3-2.4 Gg yr-1) on average between 2012 and 2016 using a two-dimensional model. We compare the long-term trends and emissions of CFC-113a to those of its structural isomer, CFC-113 (CClF2CCl2F), which still has much higher mixing ratios than CFC-113a, despite its mixing ratios and emissions decreasing since the 1990s. The continued presence of Northern Hemispheric emissions of CFC-113a is confirmed by our measurements of a persistent interhemispheric gradient in its mixing ratios, with higher mixing ratios in the Northern Hemisphere. The sources of CFC-113a are still unclear, but we present evidence that indicates large emissions in East Asia, most likely due to its use as a chemical involved in the production of hydrofluorocarbons. Our aircraft data confirm the interhemispheric gradient as well as showing mixing ratios consistent with ground-based observations and the relatively long atmospheric lifetime of CFC-113a. CFC-113a is the only known CFC for which abundances are still substantially increasing in the atmosphere. [ABSTRACT FROM AUTHOR]

High frequency measurements of the potent hydrofluorocarbon greenhouse gas CHF3 (HFC-23), a by-product of production of the hydrochlorofluorocarbon HCFC-22 (CHClF2), at five core stations of the Advanced Global Atmospheric Gases Experiment (AGAGE) network, combined with measurements of firn and Cape Grim Air Archive (CGAA) air samples, are used to explore the changing atmospheric abundance of HFC-23. These measurements are used in combination with the AGAGE 2-D atmospheric 12-box model and a Bayesian inversion methodology to determine model atmospheric mole fractions and the atmospheric history of global HFC-23 emissions. The global modelled annual mole fraction of HFC-23 in the background atmosphere was 28.9 ± 0.6 pmol mol-1 at the end of 2016, representing a 28% increase from 22.6 ± 0.4 pmol mol-1 in 2009. Over the same time frame, the modelled mole fraction of HCFC-22 increased by 19% from 199 ± 2 pmol mol-1 to 237 ± 2 pmol mol-1. However, the annual average HCFC-22 growth rate decelerated from 2009 to 2016 at an annual average rate of 0.5 pmol mol-1 yr-2. Our results demonstrate that, following a minimum in HFC-23 global emissions in 2009 of 9.6 ± 0.6 Gg yr-1, emissions increased to a maximum in 2014 of 14.5 ± 0.6 Gg yr-1, declining to 12.7 ± 0.6 Gg yr-1 (157 Mt CO2-eq. yr-1) in 2016. The 2009 emissions minimum is consistent with estimates based on national reports and is likely a response to the implementation of the Clean Development Mechanism (CDM) to mitigate HFC-23 emissions by incineration in developing (Non-Annex 1) countries under the Kyoto Protocol. Our derived cumulative emissions of HFC-23 during 2010-2016 were 89 ± 2 Gg (1.1 ± 0.2 Gt CO2-eq), which led to an increase in radiative forcing of 1.0 ± 0.1 mW m-2. Although the CDM had reduced global HFC-23 emissions, it cannot now offset the radiative forcing of higher emissions from increasing HCFC-22 production in Non-Annex 1 countries, as the CDM was closed to new entrants in 2009. We also find that the cumulative European HFC-23 emissions from 2010 to 2016 were ~1.3-Gg, corresponding to just 1.5% of cumulative global HFC-23 emissions over this same period. [ABSTRACT FROM AUTHOR]

In a changing climate, potential stratospheric circulation changes require long-term monitoring. Stratospheric trace gas measurements are often used as a proxy for stratospheric circulation changes via the mean age of air values derived from them. In this study, we investigated five potential age of air tracers - the perfluorocarbons CF4, C2F6 and C3F8 and the hydrofluorocarbons CHF3 (HFC-23) and HFC-125 - and compare them to the traditional tracer SF6 and a (relatively) shorter-lived species, HFC-227ea. A detailed uncertainty analysis was performed on mean ages derived from these new tracers to allow us to confidently compare their efficacy as age tracers to the existing tracer, SF6. Our results showed that uncertainties associated with the mean age derived from these new age tracers are similar to those derived from SF6, suggesting these alternative compounds are suitable, in this respect, for use as age tracers. Independent verification of the suitability of these age tracers is provided by a comparison between samples analysed at the University of East Anglia and the Scripps Institution of Oceanography. All five tracers give younger mean ages than SF6, a discrepancy that increases with increasing mean age. Our findings qualitatively support recent work that suggests the stratospheric lifetime of SF6 is significantly less than the previous estimate of 3200 years. The impact of these younger mean ages on three policy-relevant parameters - stratospheric lifetimes, Fractional Release Factors (FRFs), and Ozone Depletion Potentials - is investigated in combination with a recently improved methodology to calculate FRFs. Updates to previous estimations for these parameters are provided. [ABSTRACT FROM AUTHOR]

High-frequency, in situ global observations of HCFC-22 (CHClF2), HCFC-141b (CH3CCl2F), HCFC-142b (CH3CClF2) and HCFC-124 (CHClFCF3) and their main HFC replacements, HFC-134a (CH2FCF3), HFC-125 (CHF2CF3), HFC-143a (CH3CF3) and HFC-32 (CH2F2), have been used to determine their changing global growth rates and emissions in response to the Montreal Protocol and its recent amendments. Global mean mole fractions of HCFC-22, -141b, and -142b have increased throughout the observation period, reaching 234, 24.3 and 22.4 pmol mol-1, respectively, in 2015. HCFC-124 reached a maximum global mean mole fraction of 1.48 pmol mol-1 in 2007 and has since declined by 23 % to 1.14 pmol mol-1 in 2015. The HFCs all show increasing global mean mole fractions. In 2015 the global mean mole fractions (pmol mol-1) were 83.3 (HFC-134a), 18.4 (HFC-125), 17.7 (HFC-143a) and 10.5 (HFC-32). The 2007 adjustment to the Montreal Protocol required the accelerated phase-out of emissive uses of HCFCs with global production and consumption capped in 2013 to mitigate their environmental impact as both ozone-depleting substances and important greenhouse gases. We find that this change has coincided with a stabilisation, or moderate reduction, in global emissions of the four HCFCs with aggregated global emissions in 2015 of 449 ± 75 Gg yr-1, in CO2 equivalent units (CO2 eq.) 0.76 ± 0.1 Gt yr-1, compared with 483 ± 70 Gg yr-1(0.82 ± 0.1 Gt yr-1 CO2 eq.) in 2010 (uncertainties are 1σ throughout this paper). About 79 % of the total HCFC atmospheric burden in 2015 is HCFC-22, where global emissions appear to have been relatively similar since 2011, in spite of the 2013 cap on emissive uses. We attribute this to a probable increase in production and consumption of HCFC-22 in Montreal Protocol Article 5 (developing) countries and the continuing release of HCFC-22 from the large banks which dominate HCFC global emissions. Conversely, the four HFCs all show increasing mole fraction growth rates with aggregated global HFC emissions of 327 ± 70 Gg yr-1 (0.65 ± 0.12 Gt yr-1 CO2 eq.) in 2015 compared to 240 ± 50 Gg yr-1(0.47 ± 0.08 Gt yr-1 CO2 eq.) in 2010. We also note that emissions of HFC-125 and HFC-32 appear to have increased more rapidly averaged over the 5-year period 2011-2015, compared to 2006-2010. As noted by Lunt et al. (2015) this may reflect a change to refrigerant blends, such as R-410A, which contain HFC-32 and -125 as a 50 : 50 blend. [ABSTRACT FROM AUTHOR]

Carbon tetrachloride (CCl4) is an ozone-depleting substance, which is controlled by the Montreal Protocol and for which the atmospheric abundance is decreasing. However, the current observed rate of this decrease is known to be slower than expected based on reported CCl4 emissions and its estimated overall atmospheric lifetime. Here we use a three-dimensional (3-D) chemical transport model to investigate the impact on its predicted decay of uncertainties in the rates at which CCl4 is removed from the atmosphere by photolysis, by ocean uptake and by degradation in soils. The largest sink is atmospheric photolysis (74% of total), but a reported 10% uncertainty in its combined photolysis cross section and quantum yield has only a modest impact on the modelled rate of CCl4 decay. This is partly due to the limiting effect of the rate of transport of CCl4 from the main tropospheric reservoir to the stratosphere, where photolytic loss occurs. The model suggests large interannual variability in the magnitude of this stratospheric photolysis sink caused by variations in transport. The impact of uncertainty in the minor soil sink (9%of total) is also relatively small. In contrast, the model shows that uncertainty in ocean loss (17%of total) has the largest impact on modelled CCl4 decay due to its sizeable contribution to CCl4 loss and large lifetime uncertainty range (147 to 241 years). With an assumed CCl4 emission rate of 39 Gg year-1, the reference simulation with the best estimate of loss processes still underestimates the observed CCl4 (overestimates the decay) over the past 2 decades but to a smaller extent than previous studies. Changes to the rate of CCl4 loss processes, in line with known uncertainties, could bring the model into agreement with in situ surface and remote-sensing measurements, as could an increase in emissions to around 47 Gg year-1. Further progress in constraining the CCl4 budget is partly limited by systematic biases between observational datasets. For example, surface observations from the National Oceanic and Atmospheric Administration (NOAA) network are larger than from the Advanced Global Atmospheric Gases Experiment (AGAGE) network but have shown a steeper decreasing trend over the past 2 decades. These differences imply a difference in emissions which is significant relative to uncertainties in the magnitudes of the CCl4 sinks. [ABSTRACT FROM AUTHOR]

Chlorofluorocarbons (CFCs) are ozone-depleting substances as well as strong greenhouse gases, and the control of their production and use under the Montreal Protocol has had demonstrable benefits to both mitigation of increasing surface UV radiation and climate forcing. A global ban on consumption came into force in 2010, but there is evidence of continuing emissions of certain CFCs from a range of sources. One compound has received little attention in the literature, namely CFC-114 (C2Cl2F4). Of particular interest here is the differentiation between CFC-114 (CClF2CClF2) and its asymmetric isomeric form CFC-114a (CF3CCl2F) as atmospheric long-term measurements in the peer-reviewed literature to date have been assumed to represent the sum of both isomers with a time-invariant isomeric speciation. Here we report the first long-term measurements of the two isomeric forms separately, and find that they have different origins and trends in the atmosphere. Air samples collected at Cape Grim (41°S), Australia, during atmospheric background conditions since 1978, combined with samples collected from deep polar snow (firn) enable us to obtain a near-complete record of both gases since their initial production and release in the 1940s. Both isomers were present in the unpolluted atmosphere in comparably small amounts before 1960. The mixing ratio of CFC-114 doubled from 7.9 to 14.8 parts per trillion (ppt) between the start of the Cape Grim record in 1978 and the end of our record in 2014, while over the same time CFC-114a trebled from 0.35 to 1.03ppt. Mixing ratios of both isomers are slowly decreasing by the end of this period. This is consistent with measurements of recent aircraft-based samples showing no significant interhemispheric mixing ratio gradient. We also find that the fraction of CFC-114a mixing ratio relative to that of CFC-114 increased from 4.2 to 6.9% over the 37-year period. This contradicts the current tacit assumption used in international climate change and ozone depletion assessments that both isomers have been largely co-emitted and that their atmospheric concentration ratio has remained approximately constant in time. Complementary observations of air collected in Taiwan indicate a persisting source of CFC-114a in South East Asia which may have been contributing to the changing balance between the two isomers. [ABSTRACT FROM AUTHOR]

High frequency, in situ global observations of HCFC-22 (CHClF2), HCFC-141b (CH3CCl2F), HCFC-142b (CH3CClF2) and HCFC-124 (CHClFCF3) and their main HFC replacements HFC-134a (CH2FCF3), HFC-125 (CHF2CF3), HFC-143a (CH3CF3), and HFC-32 (CH2F2) have been used to determine their changing global growth rates and emissions in response to the Montreal Protocol and its recent amendments. The 2007 adjustment to the Montreal Protocol required the accelerated phase-out of HCFCs with global production and consumption capped in 2013, to mitigate their environmental impact as both ozone depleting substances and important greenhouse gases. We find that this change has coincided with a reduction in global emissions of the four HCFCs with aggregated global emissions in 2015 of 444 ± 75 Gg/yr, in CO2 equivalent units (CO2 e) 0.75 ± 0.1 Gt/yr, compared with 483 ± 70 Gg/yr (0.82 ± 0.1 Gt/yr CO2 e) in 2010. (All quoted uncertainties in this paper are 1 sigma). About 80% of the total HCFC atmospheric burden in 2015 is HCFC-22, where global HCFC emissions appear to have been relatively constant in spite of the 2013 cap on global production and consumption. We attribute this to a probable increase in production and consumption of HCFC-22 in Montreal Protocol Article 5 (developing) countries and the continuing release of HCFC-22 from the large banks which dominate HCFC global emissions. Conversely, the four HFCs all show increasing annual growth rates with aggregated global HFCs emissions in 2015 of 329 ± 70 Gg/yr (0.65 ± 0.12 Gt/yr CO2 e) compared to 2010 with 240 ± 50 Gg/yr (0.47 ± 0.08 Gt/yr CO2 e). As HCFCs are replaced by HFCs we investigate the impact of the shift to refrigerant blends which have lower global warming potentials (GWPs). We also note that emissions of HFC-125 and HFC-32 appear to have increased more rapidly during the 2011-2015 5-yr period compared to 2006-2010. [ABSTRACT FROM AUTHOR]

Perfluorocarbons (PFCs) are very potent and longlived greenhouse gases in the atmosphere, released predominantly during aluminium production and semiconductor manufacture. They have been targeted for emission controls under the United Nations Framework Convention on Climate Change. Here we present the first continuous records of the atmospheric abundance of CF4 (PFC-14), C2F6 (PFC-116) and C3F8 (PFC-218) from 1800 to 2014. The records are derived from high-precision measurements of PFCs in air extracted from polar firn or ice at six sites (DE08, DE08-2, DSSW20K, EDML, NEEM and South Pole) and air archive tanks and atmospheric air sampled from both hemispheres. We take account of the age characteristics of the firn and ice core air samples and demonstrate excellent consistency between the ice core, firn and atmospheric measurements. We present an inversion for global emissions from 1900 to 2014. We also formulate the inversion to directly infer emission factors for PFC emissions due to aluminium production prior to the 1980s. We show that 19th century atmospheric levels, before significant anthropogenic influence, were stable at 34:1±0:3 ppt for CF4 and below detection limits of 0.002 and 0.01 ppt for C2F6 and C3F8, respectively. We find a significant peak in CF4 and C2F6 emissions around 1940, most likely due to the high demand for aluminium during World War II, for example for construction of aircraft, but these emissions were nevertheless much lower than in recent years. The PFC emission factors for aluminium production in the early 20th century were significantly higher than today but have decreased since then due to improvements and better control of the smelting process. Mitigation efforts have led to decreases in emissions from peaks in 1980 (CF4) or early-to-mid-2000s (C2F6 and C3F8) despite the continued increase in global aluminium production; however, these decreases in emissions appear to have recently halted. We see a temporary reduction of around 15% in CF4 emissions in 2009, presumably associated with the impact of the global financial crisis on aluminium and semiconductor production. [ABSTRACT FROM AUTHOR]