Sustained growth of sulfur hexafluoride emissions in China inferred from atmospheric observations.

Sulfur hexafluoride (SF6) is a potent greenhouse gas. Here we use long-term atmospheric observations to determine SF6 emissions from China between 2011 and 2021, which are used to evaluate the Chinese national SF6 emission inventory and to better understand the global SF6 budget. SF6 emissions in China substantially increased from 2.6 (2.3-2.7, 68% uncertainty) Gg yr-1 in 2011 to 5.1 (4.8-5.4) Gg yr-1 in 2021. The increase from China is larger than the global total emissions rise, implying that it has offset falling emissions from other countries. Emissions in the less-populated western regions of China, which have potentially not been well quantified in previous measurement-based estimates, contribute significantly to the national SF6 emissions, likely due to substantial power generation and transmission in that area. The CO2-eq emissions of SF6 in China in 2021 were 125 (117-132) million tonnes (Mt), comparable to the national total CO2 emissions of several countries such as the Netherlands or Nigeria. The increasing SF6 emissions offset some of the CO2 reductions achieved through transitioning to renewable energy in the power industry, and might hinder progress towards achieving China's goal of carbon neutrality by 2060 if no concrete control measures are implemented.

Anthropogenic Chloroform Emissions from China Drive Changes in Global Emissions.

Emissions of chloroform (CHCl3), a short-lived halogenated substance not currently controlled under the Montreal Protocol on Substances that Deplete the Ozone Layer, are offsetting some of the achievements of the Montreal Protocol. In this study, emissions of CHCl3 from China were derived by atmospheric measurement-based "top-down" inverse modeling and a sector-based "bottom-up" inventory method. Top-down CHCl3 emissions grew from 78 (72-83) Gg yr-1 in 2011 to a maximum of 193 (178-204) Gg yr-1 in 2017, followed by a decrease to 147 (138-154) Gg yr-1 in 2018, after which emissions remained relatively constant through 2020. The changes in emissions from China could explain all of the global changes during the study period. The CHCl3 emissions in China were dominated by anthropogenic sources, such as byproduct emissions during disinfection and leakage from chloromethane industries. Had emissions continued to grow at the rate observed up to 2017, a delay of several years in Antarctic ozone layer recovery could have occurred. However, this delay will be largely avoided if global CHCl3 emissions remain relatively constant in the future, as they have between 2018 and 2020.

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.

Rapid increase in dichloromethane emissions from China inferred through atmospheric observations.

With the successful implementation of the Montreal Protocol on Substances that Deplete the Ozone Layer, the atmospheric abundance of ozone-depleting substances continues to decrease slowly and the Antarctic ozone hole is showing signs of recovery. However, growing emissions of unregulated short-lived anthropogenic chlorocarbons are offsetting some of these gains. Here, we report an increase in emissions from China of the industrially produced chlorocarbon, dichloromethane (CH2Cl2). The emissions grew from 231 (213-245) Gg yr-1 in 2011 to 628 (599-658) Gg yr-1 in 2019, with an average annual increase of 13 (12-15) %, primarily from eastern China. The overall increase in CH2Cl2 emissions from China has the same magnitude as the global emission rise of 354 (281-427) Gg yr-1 over the same period. If global CH2Cl2 emissions remain at 2019 levels, they could lead to a delay in Antarctic ozone recovery of around 5 years compared to a scenario with no CH2Cl2 emissions.

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.

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 and Marine Boundary Layer Concentrations of Unregulated Chlorocarbons Measured at Cape Point, South Africa.

Unregulated chlorocarbons, here defined as dichloromethane (CH2Cl2), perchloroethene (C2Cl4), chloroform (CHCl3), and methyl chloride (CH3Cl), are gases not regulated by the Montreal Protocol. While CH3Cl is the largest contributor of atmospheric chlorine, recent studies have shown that growth in emissions of the less abundant chlorocarbons could pose a significant threat to the recovery of the ozone layer. Despite this, there remain many regions for which no atmospheric monitoring exists, leaving gaps in our understanding of global emissions. Here, we report on a new time series of chlorocarbon measurements from Cape Point, South Africa for 2017, which represent the first published high-frequency measurements of these gases from Africa. For CH2Cl2 and C2Cl4, the majority of mole fraction enhancements were observed from the north, consistent with anthropogenically modified air from Cape Town, while for CHCl3 and CH3Cl, we found evidence for both oceanic and terrestrial sources. Using an inverse method, we estimated emissions for south-western South Africa (SWSA). For each chlorocarbon, SWSA accounted for less than 1% of global emissions. For CH2Cl2 and C2Cl4, we extrapolated using population statistics and found South African emissions of 8.9 (7.4-10.4) Gg yr-1 and 0.80 (0.64-1.04) Gg yr-1, respectively.

Atmospheric HCFC-22, HFC-125, and HFC-152a at Cape Point, South Africa.

One hydrochlorofluorocarbon and two hydrofluorocarbons (HCFC-22, HFC-125, and HFC-152a) were measured in air samples at the Cape Point observatory (CPT), South Africa, during 2017. These data represent the first such atmospheric measurements of these compounds from southwestern South Africa (SWSA). Baseline atmospheric growth rates were estimated to be 8.36, 4.10, and 0.71 ppt year-1 for HCFC-22, HFC-125, and HFC-152a, respectively. The CPT measurements were combined with an inverse model to investigate emissions from SWSA. For all three halocarbons, Cape Town was found to be the dominant source within SWSA. These estimates were extrapolated, based on population statistics, to estimate emissions for the whole of South Africa. We estimate South Africa's 2017 emissions to be 3.0 (1.6-4.4), 0.8 (0.5-1.2), and 1.1 (0.6-1.6) Gg year-1 for HCFC-22, HFC-125, and HFC-152a, respectively. For all three halocarbons, South Africa's contribution to global emissions is small (<2.5%), but future monitoring is needed to ensure South Africa's compliance with regulation set out by the Montreal Protocol and its Amendments.

Recent Trends in Stratospheric Chlorine From Very Short-Lived Substances.

Very short-lived substances (VSLS), including dichloromethane (CH2Cl2), chloroform (CHCl3), perchloroethylene (C2Cl4), and 1,2-dichloroethane (C2H4Cl2), are a stratospheric chlorine source and therefore contribute to ozone depletion. We quantify stratospheric chlorine trends from these VSLS (VSLCltot) using a chemical transport model and atmospheric measurements, including novel high-altitude aircraft data from the NASA VIRGAS (2015) and POSIDON (2016) missions. We estimate VSLCltot increased from 69 (±14) parts per trillion (ppt) Cl in 2000 to 111 (±22) ppt Cl in 2017, with >80% delivered to the stratosphere through source gas injection, and the remainder from product gases. The modeled evolution of chlorine source gas injection agrees well with historical aircraft data, which corroborate reported surface CH2Cl2 increases since the mid-2000s. The relative contribution of VSLS to total stratospheric chlorine increased from ~2% in 2000 to ~3.4% in 2017, reflecting both VSLS growth and decreases in long-lived halocarbons. We derive a mean VSLCltot growth rate of 3.8 (±0.3) ppt Cl/year between 2004 and 2017, though year-to-year growth rates are variable and were small or negative in the period 2015-2017. Whether this is a transient effect, or longer-term stabilization, requires monitoring. In the upper stratosphere, the modeled rate of HCl decline (2004-2017) is -5.2% per decade with VSLS included, in good agreement to ACE satellite data (-4.8% per decade), and 15% slower than a model simulation without VSLS. Thus, VSLS have offset a portion of stratospheric chlorine reductions since the mid-2000s.

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.

Re-Evaluation of the UK's HFC-134a Emissions Inventory Based on Atmospheric Observations.

Independent verification of national greenhouse gas inventories is a vital measure for cross-checking the accuracy of emissions data submitted to the United Nations Framework Convention on Climate Change (UNFCCC). We infer annual UK emissions of HFC-134a from 1995 to 2012 using atmospheric observations and an inverse modeling technique, and compare with the UK's annual UNFCCC submission. By 2010, the inventory is almost twice as large as our estimates, with an "emissions gap" equating to 3.90 (3.20-4.30) Tg CO2e. We evaluate the RAC (Refrigeration and Air-Conditioning) model, a bottom up model used to quantify UK emissions from refrigeration and air-conditioning sectors. Within mobile air-conditioning (MAC), the largest RAC sector and most significant UK source (59%), we find a number of assumptions that may be considered oversimplistic and conservative; most notably the unit refill rate. Finally, a Bayesian approach is used to estimate probable inventory inputs required for minimization of the emissions discrepancy. Our top-down estimates provide only a weak constraint on inventory model parameters and consequently, we are unable to suggest discrete values. However, a significant revision of the MAC servicing rate, coupled with a reassessment of non-RAC aerosol emissions, are required if the discrepancy between methods is to be reduced.

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.

Measurements of OVOCs and NMHCs in a Swiss highway tunnel for estimation of road transport emissions.

Eighteen oxygenated volatile organic compounds (OVOCs) and eight nonmethane hydrocarbons (NMHCs) were measured continuously during a two-week campaign in 2004 in the Gubrist highway tunnel (Switzerland). The study aimed to estimate selected OVOC and NMHC emissions of the current vehicle fleet under highway conditions. For the measured OVOCs the highest EFs were found for ethanol (9.7 mg/km), isopropanol (3.2 mg/km), and acetaldehyde (2.5 mg/km), followed by acetone, benzaldehyde, and acrolein. Formaldehyde, the most abundant OVOC measured in other studies, was not measured by the method applied. Relative emissions of the measured OVOCs were estimated to contribute approximately 6 and 4% to the total road traffic VOC emissions from Switzerland and Europe, respectively. Results are compared with those from previous studies from the same tunnel performed in 1993 and 2002, and from campaigns in other tunnels. A continuous reduction in the emission factors (EFs) was determined for all measured compounds from 1993 until 2004. The relative contributions of light-duty vehicles (LDV) and heavy-duty vehicles (HDV) to the total emissions indicated that OVOCs were mainly produced by the HDVs, whereas LDVs dominated the production of the NMHCs.