Substantial increase in perfluorocarbons CF4 (PFC-14) and C2F6 (PFC-116) emissions in China.

The perfluorocarbons tetrafluoromethane (CF4, PFC-14) and hexafluoroethane (C2F6, PFC-116) are potent greenhouse gases with near-permanent atmospheric lifetimes relative to human timescales and global warming potentials thousands of times that of CO2. Using long-term atmospheric observations from a Chinese network and an inverse modeling approach (top-down method), we determined that CF4 emissions in China increased from 4.7 (4.2-5.0, 68% uncertainty interval) Gg y-1 in 2012 to 8.3 (7.7-8.9) Gg y-1 in 2021, and C2F6 emissions in China increased from 0.74 (0.66-0.80) Gg y-1 in 2011 to 1.32 (1.24-1.40) Gg y-1 in 2021, both increasing by approximately 78%. Combined emissions of CF4 and C2F6 in China reached 78 Mt CO2-eq in 2021. The absolute increase in emissions of each substance in China between 2011-2012 and 2017-2020 was similar to (for CF4), or greater than (for C2F6), the respective absolute increase in global emissions over the same period. Substantial CF4 and C2F6 emissions were identified in the less-populated western regions of China, probably due to emissions from the expanding aluminum industry in these resource-intensive regions. It is likely that the aluminum industry dominates CF4 emissions in China, while the aluminum and semiconductor industries both contribute to C2F6 emissions. Based on atmospheric observations, this study validates the emission magnitudes reported in national bottom-up inventories and provides insights into detailed spatial distributions and emission sources beyond what is reported in national bottom-up inventories.

Historical trend of ozone-depleting substances and hydrofluorocarbon concentrations during 2004-2020 derived from satellite observations and estimates for global emissions.

Global concentrations (or mole fractions) and emissions of ozone-depleting substances (ODSs) and their hydrofluorocarbon (HFCs) substitutes that are controlled by the Montreal Protocol and its Amendments and adjustments (MP) are of great interest to both the scientific community and public. Previous studies on global concentrations and emissions have mostly relied on ground-based observations. Here, we assess the global concentrations and emissions of eight MP controlled substances and methyl chloride from ACE-FTS (Atmospheric Chemistry Experiment high-resolution infrared Fourier transform spectrometer) satellite observations: CFC-11 (CFCl3), CFC-12 (CF2Cl2), CCl4, HCFC-22 (CHClF2), HCFC-141b (C2H3Cl2F), HCFC-142b (C2H3ClF2), HFC-23 (CHF3), HFC-134a (C2H2F4), and CH3Cl. Results show that the ACE-FTS satellite observations can be used to derive the concentrations and emissions of these ODSs, HFCs, and CH3Cl, as they are consistent with those derived from the ground-based observations. Our findings imply that the changes in the concentrations and emissions of the ODSs and HFCs closely match the regulatory status of the MP, and satellite observations can be used to monitor the past and future progress of the MP.

A decline in global CFC-11 emissions during 2018-2019.

The atmospheric concentration of trichlorofluoromethane (CFC-11) has been in decline since the production of ozone-depleting substances was phased out under the Montreal Protocol1,2. Since 2013, the concentration decline of CFC-11 slowed unexpectedly owing to increasing emissions, probably from unreported production, which, if sustained, would delay the recovery of the stratospheric ozone layer1-12. Here we report an accelerated decline in the global mean CFC-11 concentration during 2019 and 2020, derived from atmospheric concentration measurements at remote sites around the world. We find that global CFC-11 emissions decreased by 18 ± 6 gigagrams per year (26 ± 9 per cent; one standard deviation) from 2018 to 2019, to a 2019 value (52 ± 10 gigagrams per year) that is similar to the 2008-2012 mean. The decline in global emissions suggests a substantial decrease in unreported CFC-11 production. If the sharp decline in unexpected global emissions and unreported production is sustained, any associated future ozone depletion is likely to be limited, despite an increase in the CFC-11 bank (the amount of CFC-11 produced, but not yet emitted) by 90 to 725 gigagrams by the beginning of 2020.

A decline in emissions of CFC-11 and related chemicals from eastern China.

Emissions of ozone-depleting substances, including trichlorofluoromethane (CFC-11), have decreased since the mid-1980s in response to the Montreal Protocol1,2. In recent years, an unexpected increase in CFC-11 emissions beginning in 2013 has been reported, with much of the global rise attributed to emissions from eastern China3,4. Here we use high-frequency atmospheric mole fraction observations from Gosan, South Korea and Hateruma, Japan, together with atmospheric chemical transport-model simulations, to investigate regional CFC-11 emissions from eastern China. We find that CFC-11 emissions returned to pre-2013 levels in 2019 (5.0 ± 1.0 gigagrams per year in 2019, compared to 7.2 ± 1.5 gigagrams per year for 2008-2012, ±1 standard deviation), decreasing by 10 ± 3 gigagrams per year since 2014-2017. Furthermore, we find that in this region, carbon tetrachloride (CCl4) and dichlorodifluoromethane (CFC-12) emissions-potentially associated with CFC-11 production-were higher than expected after 2013 and then declined one to two years before the CFC-11 emissions reduction. This suggests that CFC-11 production occurred in eastern China after the mandated global phase-out, and that there was a subsequent decline in production during 2017-2018. We estimate that the amount of the CFC-11 bank (the amount of CFC-11 produced, but not yet emitted) in eastern China is up to 112 gigagrams larger in 2019 compared to pre-2013 levels, probably as a result of recent production. Nevertheless, it seems that any substantial delay in ozone-layer recovery has been avoided, perhaps owing to timely reporting3,4 and subsequent action by industry and government in China5,6.

Unexpected nascent atmospheric emissions of three ozone-depleting hydrochlorofluorocarbons.

Global and regional atmospheric measurements and modeling can play key roles in discovering and quantifying unexpected nascent emissions of environmentally important substances. We focus here on three hydrochlorofluorocarbons (HCFCs) that are restricted by the Montreal Protocol because of their roles in stratospheric ozone depletion. Based on measurements of archived air samples and on in situ measurements at stations of the Advanced Global Atmospheric Gases Experiment (AGAGE) network, we report global abundances, trends, and regional enhancements for HCFC-132b ([Formula: see text]), which is newly discovered in the atmosphere, and updated results for HCFC-133a ([Formula: see text]) and HCFC-31 ([Formula: see text]ClF). No purposeful end-use is known for any of these compounds. We find that HCFC-132b appeared in the atmosphere 20 y ago and that its global emissions increased to 1.1 Gg⋅y-1 by 2019. Regional top-down emission estimates for East Asia, based on high-frequency measurements for 2016-2019, account for ∼95% of the global HCFC-132b emissions and for ∼80% of the global HCFC-133a emissions of 2.3 Gg⋅y-1 during this period. Global emissions of HCFC-31 for the same period are 0.71 Gg⋅y-1 Small European emissions of HCFC-132b and HCFC-133a, found in southeastern France, ceased in early 2017 when a fluorocarbon production facility in that area closed. Although unreported emissive end-uses cannot be ruled out, all three compounds are most likely emitted as intermediate by-products in chemical production pathways. Identification of harmful emissions to the atmosphere at an early stage can guide the effective development of global and regional environmental policy.

Emissions of Tetrafluoromethane (CF4) and Hexafluoroethane (C2F6) From East Asia: 2008 to 2019.

The perfluorocarbons (PFCs), tetrafluoromethane (CF4) and hexafluoroethane (C2F6), are potent greenhouse gases with very long atmospheric lifetimes. They are emitted almost entirely from industrial sources, including the aluminum and rare earth metal smelting industries that emit them as by-products, and the semiconductor and flat panel display manufacturing industries that use them and vent unutilized amounts to the atmosphere. Despite extensive industrial efforts to quantify and curb these emissions, "top-down" PFC emission estimates derived from atmospheric measurements continue to rise and are significantly greater than reported process- and inventory-based "bottom-up" emissions. In this study, we estimate emissions of CF4 and C2F6 from East Asia, where PFC emitting industries are heavily concentrated, using a top-down approach (a Bayesian inversion) with high-frequency atmospheric measurements at Gosan (Jeju Island, South Korea) for 2008-2019. We also compile and analyze the available bottom-up CF4 and C2F6 emissions in East Asia from industrial and government reports. Our results suggest that the observed increases in global PFC emissions since 2015 are driven primarily by China's aluminum industry, with significant contributions from Japan's and Korea's semiconductor industry. Our analysis suggests that Chinese emissions occur predominantly from the aluminum industry, although their emissions per production ratio may be improving. Our results for Japan and Korea find significant discrepancies between top-down and bottom-up emissions estimates, suggesting that the effectiveness of emission reduction systems (abatement) used in their semiconductor industries may be overestimated. Overall, our top-down results for East Asia contribute significantly to reducing the gap in the global PFC emission budgets.

Minimal geological methane emissions during the Younger Dryas-Preboreal abrupt warming event.

Methane (CH4) is a powerful greenhouse gas and plays a key part in global atmospheric chemistry. Natural geological emissions (fossil methane vented naturally from marine and terrestrial seeps and mud volcanoes) are thought to contribute around 52 teragrams of methane per year to the global methane source, about 10 per cent of the total, but both bottom-up methods (measuring emissions) and top-down approaches (measuring atmospheric mole fractions and isotopes) for constraining these geological emissions have been associated with large uncertainties. Here we use ice core measurements to quantify the absolute amount of radiocarbon-containing methane (14CH4) in the past atmosphere and show that geological methane emissions were no higher than 15.4 teragrams per year (95 per cent confidence), averaged over the abrupt warming event that occurred between the Younger Dryas and Preboreal intervals, approximately 11,600 years ago. Assuming that past geological methane emissions were no lower than today, our results indicate that current estimates of today's natural geological methane emissions (about 52 teragrams per year) are too high and, by extension, that current estimates of anthropogenic fossil methane emissions are too low. Our results also improve on and confirm earlier findings that the rapid increase of about 50 per cent in mole fraction of atmospheric methane at the Younger Dryas-Preboreal event was driven by contemporaneous methane from sources such as wetlands; our findings constrain the contribution from old carbon reservoirs (marine methane hydrates, permafrost and methane trapped under ice) to 19 per cent or less (95 per cent confidence). To the extent that the characteristics of the most recent deglaciation and the Younger Dryas-Preboreal warming are comparable to those of the current anthropogenic warming, our measurements suggest that large future atmospheric releases of methane from old carbon sources are unlikely to occur.

Role of atmospheric oxidation in recent methane growth.

The growth in global methane (CH4) concentration, which had been ongoing since the industrial revolution, stalled around the year 2000 before resuming globally in 2007. We evaluate the role of the hydroxyl radical (OH), the major CH4 sink, in the recent CH4 growth. We also examine the influence of systematic uncertainties in OH concentrations on CH4 emissions inferred from atmospheric observations. We use observations of 1,1,1-trichloroethane (CH3CCl3), which is lost primarily through reaction with OH, to estimate OH levels as well as CH3CC3 emissions, which have uncertainty that previously limited the accuracy of OH estimates. We find a 64-70% probability that a decline in OH has contributed to the post-2007 methane rise. Our median solution suggests that CH4 emissions increased relatively steadily during the late 1990s and early 2000s, after which growth was more modest. This solution obviates the need for a sudden statistically significant change in total CH4 emissions around the year 2007 to explain the atmospheric observations and can explain some of the decline in the atmospheric 13CH4/12CH4 ratio and the recent growth in C2H6 Our approach indicates that significant OH-related uncertainties in the CH4 budget remain, and we find that it is not possible to implicate, with a high degree of confidence, rapid global CH4 emissions changes as the primary driver of recent trends when our inferred OH trends and these uncertainties are considered.

Reconciling reported and unreported HFC emissions with atmospheric observations.

We infer global and regional emissions of five of the most abundant hydrofluorocarbons (HFCs) using atmospheric measurements from the Advanced Global Atmospheric Gases Experiment and the National Institute for Environmental Studies, Japan, networks. We find that the total CO2-equivalent emissions of the five HFCs from countries that are required to provide detailed, annual reports to the United Nations Framework Convention on Climate Change (UNFCCC) increased from 198 (175-221) Tg-CO2-eq ⋅ y(-1) in 2007 to 275 (246-304) Tg-CO2-eq ⋅ y(-1) in 2012. These global warming potential-weighted aggregated emissions agree well with those reported to the UNFCCC throughout this period and indicate that the gap between reported emissions and global HFC emissions derived from atmospheric trends is almost entirely due to emissions from nonreporting countries. However, our measurement-based estimates of individual HFC species suggest that emissions, from reporting countries, of the most abundant HFC, HFC-134a, were only 79% (63-95%) of the UNFCCC inventory total, while other HFC emissions were significantly greater than the reported values. These results suggest that there are inaccuracies in the reporting methods for individual HFCs, which appear to cancel when aggregated together.

Comparison of halocarbon measurements in an atmospheric dry whole air sample.

The growing awareness of climate change/global warming, and continuing concerns regarding stratospheric ozone depletion, will require continued measurements and standards for many compounds, in particular halocarbons that are linked to these issues. In order to track atmospheric mole fractions and assess the impact of policy on emission rates, it is necessary to demonstrate measurement equivalence at the highest levels of accuracy for assigned values of standards. Precise measurements of these species aid in determining small changes in their atmospheric abundance. A common source of standards/scales and/or well-documented agreement of different scales used to calibrate the measurement instrumentation are key to understanding many sets of data reported by researchers. This report describes the results of a comparison study among National Metrology Institutes and atmospheric research laboratories for the chlorofluorocarbons (CFCs) dichlorodifluoromethane (CFC-12), trichlorofluoromethane (CFC-11), and 1,1,2-trichlorotrifluoroethane (CFC-113); the hydrochlorofluorocarbons (HCFCs) chlorodifluoromethane (HCFC-22) and 1-chloro-1,1-difluoroethane (HCFC-142b); and the hydrofluorocarbon (HFC) 1,1,1,2-tetrafluoroethane (HFC-134a), all in a dried whole air sample. The objective of this study is to compare calibration standards/scales and the measurement capabilities of the participants for these halocarbons at trace atmospheric levels. The results of this study show agreement among four independent calibration scales to better than 2.5% in almost all cases, with many of the reported agreements being better than 1.0%.

Nitrogen trifluoride global emissions estimated from updated atmospheric measurements.

Nitrogen trifluoride (NF(3)) has potential to make a growing contribution to the Earth's radiative budget; however, our understanding of its atmospheric burden and emission rates has been limited. Based on a revision of our previous calibration and using an expanded set of atmospheric measurements together with an atmospheric model and inverse method, we estimate that the global emissions of NF(3) in 2011 were 1.18 ± 0.21 Gg⋅y(-1), or ∼20 Tg CO(2)-eq⋅y(-1) (carbon dioxide equivalent emissions based on a 100-y global warming potential of 16,600 for NF(3)). The 2011 global mean tropospheric dry air mole fraction was 0.86 ± 0.04 parts per trillion, resulting from an average emissions growth rate of 0.09 Gg⋅y(-2) over the prior decade. In terms of CO(2) equivalents, current NF(3) emissions represent between 17% and 36% of the emissions of other long-lived fluorinated compounds from electronics manufacture. We also estimate that the emissions benefit of using NF(3) over hexafluoroethane (C(2)F(6)) in electronics manufacture is significant-emissions of between 53 and 220 Tg CO(2)-eq⋅y(-1) were avoided during 2011. Despite these savings, total NF(3) emissions, currently ∼10% of production, are still significantly larger than expected assuming global implementation of ideal industrial practices. As such, there is a continuing need for improvements in NF(3) emissions reduction strategies to keep pace with its increasing use and to slow its rising contribution to anthropogenic climate forcing.

Automated measurement of nitrogen trifluoride in ambient air.

We present an analytical method for the in situ measurement of atmospheric nitrogen trifluoride (NF(3)), an anthropogenic gas with a 100-year global warming potential of over 16,000. This potent greenhouse gas has a rising atmospheric abundance due to its emission from a growing number of manufacturing processes and an expanding end-use market. Here we present a modified version of the "Medusa" preconcentration gas chromatography/mass spectrometry (GC/MS) system of Miller, B. R.; Weiss, R. F.; Salameh, P. K.; Tanhua, T.; Greally, B. R.; Mühle, J.; Simmonds, P. G. Anal. Chem.2008, 80 (5), 1536-1545. By altering the techniques of gas separation and chromatography after initial preconcentration, we are now able to make atmospheric measurements of NF(3) with relative precision <2% (1σ) for current background clean air samples. Importantly, this method augments the currently operational Medusa system, so that the quality of data for species already being measured is not compromised and NF(3) is measured from the same preconcentrated sample. We present the first in situ measurements of NF(3) from La Jolla, California made 11 times daily, illustrating how global deployment of this technique within the AGAGE (Advanced Global Atmospheric Gases Experiment) network could facilitate estimation of global and regional NF(3) emissions over the coming years.

Emissions of halogenated compounds in East Asia determined from measurements at Jeju Island, Korea.

High-frequency in situ measurements at Gosan (Jeju Island, Korea) during November 2007 to December 2008 have been combined with interspecies correlation analysis to estimate national emissions of halogenated compounds (HCs) in East Asia, including the chlorofluorocarbons (CFCs), halons, hydrochlorofluorocarbons (HCFCs), hydrofluorocarbons (HFCs), perfluorocarbons (PFCs), sulfur hexafluoride (SF(6)), and other chlorinated and brominated compounds. Our results suggest that overall China is the dominant emitter of HCs in East Asia, however significant emissions are also found in South Korea, Japan and Taiwan for HFC-134a, HFC-143a, C(2)F(6), SF(6), CH(3)CCl(3), and HFC-365mfc. The combined emissions of CFCs, halon-1211, HCFCs, HFCs, PFCs, and SF(6) from all four countries in 2008 are 25.3, 1.6, 135, 42.6, 3.6, and 2.0 kt/a, respectively. They account for approximately 15%, 26%, 29%, 16%, 32%, and 26.5% of global emissions, respectively. Our results show signs that Japan has successfully phased out CFCs and HCFCs in compliance with the Montreal Protocol (MP), Korea has started transitioning from HCFCs to HFCs, while China still significantly consumes HCFCs. Taiwan, while not directly regulated under the MP, is shown to have adapted the use of HFCs. Combined analysis of emission rates and the interspecies correlation matrix presented in this study proves to be a powerful tool for monitoring and diagnosing changes in consumption of HCs in East Asia.