Unexplained high and persistent methyl bromide emissions in China.

Methyl bromide (CHBr) is an important ozone-depleting substance whose use is regulated under the Montreal Protocol. Quantifying emissions on the national scale is required to assess compliance with the Montreal Protocol and thereby ensure the timely recovery of the ozone layer. However, the spatial-temporal patterns of China's national CHBr emissions remain unclear.

Atmospheric observation and emission estimation of HFC-125 and HFC-32 in China from four representative cities.

HFC-125 and HFC-32 are fluorinated greenhouse gases of great concern due to their high GWPs and increasing background atmospheric concentrations. Long-term atmospheric observations of HFC-125 and HFC-32 were carried out in four representative cities of China (Beijing, Guangzhou, Hangzhou, and Lanzhou) from January 2012 to October 2019. Overall, the annual mean atmospheric concentrations of HFC-125 and HFC-32 both showed increasing trends, with average rates of 4.

Increases in Global and East Asian Nitrogen Trifluoride (NF) Emissions Inferred from Atmospheric Observations.

Nitrogen trifluoride (NF) is a potent and long-lived greenhouse gas that is widely used in the manufacture of semiconductors, photovoltaic cells, and flat panel displays. Using atmospheric observations from eight monitoring stations from the Advanced Global Atmospheric Gases Experiment (AGAGE) and inverse modeling with a global 3-D atmospheric chemical transport model (GEOS-Chem), we quantify global and regional NF emission from 2015 to 2021. We find that global emissions have grown from 1.

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

Sulfur hexafluoride (SF) is a potent greenhouse gas. Here we use long-term atmospheric observations to determine SF emissions from China between 2011 and 2021, which are used to evaluate the Chinese national SF emission inventory and to better understand the global SF budget. SF emissions in China substantially increased from 2.

Ozonolysis can produce long-lived greenhouse gases from commercial refrigerants.

Hydrofluoroolefins are being adopted as sustainable alternatives to long-lived fluorine- and chlorine-containing gases and are finding current or potential mass-market applications as refrigerants, among a myriad of other uses. Their olefinic bond affords relatively rapid reaction with hydroxyl radicals present in the atmosphere, leading to short lifetimes and proportionally small global warming potentials. However, this type of functionality also allows reaction with ozone, and whilst these reactions are slow, we show that the products of these reactions can be extremely long-lived.

Anthropogenic Chloroform Emissions from China Drive Changes in Global Emissions.

Emissions of chloroform (CHCl), 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 CHCl from China were derived by atmospheric measurement-based "top-down" inverse modeling and a sector-based "bottom-up" inventory method. Top-down CHCl emissions grew from 78 (72-83) Gg yr in 2011 to a maximum of 193 (178-204) Gg yr in 2017, followed by a decrease to 147 (138-154) Gg yr in 2018, after which emissions remained relatively constant through 2020.

Step Change in Improving the Accuracy of Nitrous Oxide Reference Materials for Underpinning Atmospheric Composition Measurements.

We have employed a new approach to quantify the amount fraction of nitrous oxide in a synthetic air matrix gas used to prepare high-accuracy reference materials of the same component. Until now, this was the largest contributor to the measurement uncertainty of nitrous oxide in air reference materials at atmospheric amount fractions (∼330 nmol mol), as identified in a recent international comparison. A novel preconcentration method has resulted in a measurement of 363 pmol mol of nitrous oxide in a synthetic air matrix gas with an expanded uncertainty of 27 pmol mol.

In Situ Observations of Halogenated Gases at the Shangdianzi Background Station and Emission Estimates for Northern China.

Halogenated gases include ozone-depleting substances and greenhouse gases, such as chlorofluorocarbons, halons, hydrochlorofluorocarbons, hydrofluorocarbons, and perfluorinated gases. In situ atmospheric observations of major halogenated gases were conducted at the Shangdianzi (SDZ) background station, China, from October 2020 to September 2021 using ODS5-pro, a newly developed measurement system. The measurement time series of 36 halogenated gases showed occasional pollution events, where background conditions represented 25% (CHCl) to 81% (CFCl, CFC-13) of the measurements.

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 (CFCl), CFC-12 (CFCl), CCl, HCFC-22 (CHClF), HCFC-141b (CHClF), HCFC-142b (CHClF), HFC-23 (CHF), HFC-134a (CHF), and CHCl.

A renewed rise in global HCFC-141b emissions between 2017-2021.

Global emissions of the ozone-depleting gas HCFC-141b (1,1-dichloro-1-fluoroethane, CHCClF) 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.

Estimate of hydrochlorofluorocarbon emissions during 2011-2018 in the Yangtze River Delta, China.

Hydrochlorofluorocarbons (HCFCs) are used as temporary substitutes for chlorofluorocarbons and other ozone-depleting substances because they have reduced ozone depletion and global warming potentials. The consumption and production of HCFCs are regulated via the Montreal Protocol and its amendments till 2013, with a complete phase-out being scheduled by 2030 for Article 5 parties (developing countries). To better understand the characteristics and emissions of HCFCs in the Yangtze River Delta (YRD), which is the largest metropolitan area in China, weekly flask samples were collected at the Lin'an regional background station located in the YRD from 2011 to 2018 and measured for four HCFCs (HCFC-22, HCFC-141b, HCFC-142b, and HCFC-124).

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 (CHCl).

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).

Direct field evidence of autocatalytic iodine release from atmospheric aerosol.

Reactive iodine plays a key role in determining the oxidation capacity, or cleansing capacity, of the atmosphere in addition to being implicated in the formation of new particles in the marine boundary layer. The postulation that heterogeneous cycling of reactive iodine on aerosols may significantly influence the lifetime of ozone in the troposphere not only remains poorly understood but also heretofore has never been observed or quantified in the field. Here, we report direct ambient observations of hypoiodous acid (HOI) and heterogeneous recycling of interhalogen product species (i.

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

Unregulated chlorocarbons, here defined as dichloromethane (CHCl), perchloroethene (CCl), chloroform (CHCl), and methyl chloride (CHCl), are gases not regulated by the Montreal Protocol. While CHCl 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.

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.

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

Very short-lived substances (VSLS), including dichloromethane (CHCl), chloroform (CHCl), perchloroethylene (CCl), and 1,2-dichloroethane (CHCl), are a stratospheric chlorine source and therefore contribute to ozone depletion. We quantify stratospheric chlorine trends from these VSLS (VSLCl) 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 VSLCl 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.

Role of atmospheric oxidation in recent methane growth.

The growth in global methane (CH) 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 CH sink, in the recent CH growth. We also examine the influence of systematic uncertainties in OH concentrations on CH emissions inferred from atmospheric observations.

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.

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.

Determination of gas-phase ozonolysis rate coefficients of a number of sesquiterpenes at elevated temperatures using the relative rate method.

The rates of ozonolysis of four sesquiterpenes, β-caryophyllene, α-humulene, isolongifolene and α-cedrene, are determined in the gas phase at an elevated temperature of 366 ± 3 K and a pressure of ~780 Torr using the EXTreme RAnge chamber (EXTRA). The experimentally obtained rate coefficients agree with extrapolated room temperature rate coefficients for isolongifolene and α-cedrene but not for β-caryophyllene and α-humulene, which were found to be three orders of magnitude slower than this in the literature. These new measurements support the hypothesis that operating under ambient conditions, kinetic measurements of condensable species can be influenced adversely by heterogeneous processes and should therefore be treated with caution.

Future emissions and atmospheric fate of HFC-1234yf from mobile air conditioners in Europe.

HFC-1234yf (2,3,3,3-tetrafluoropropene) is under discussion for replacing HFC-134a (1,1,1,2-tetrafluoroethane) as a cooling agent in mobile air conditioners (MACs) in the European vehicle fleet. Some HFC-1234yf will be released into the atmosphere, where it is almost completely transformed to the persistent trifluoroacetic acid (TFA). Future emissions of HFC-1234yf after a complete conversion of the European vehicle fleet were assessed.

European emissions of halogenated greenhouse gases inferred from atmospheric measurements.

European emissions of nine representative halocarbons (CFC-11, CFC-12, Halon 1211, HCFC-141b, HCFC-142b, HCFC-22, HFC-125, HFC-134a, HFC-152a) are derived for the year 2009 by combining long-term observations in Switzerland, Italy, and Ireland with campaign measurements from Hungary. For the first time, halocarbon emissions over Eastern Europe are assessed by top-down methods, and these results are compared to Western European emissions. The employed inversion method builds on least-squares optimization linking atmospheric observations with calculations from the Lagrangian particle dispersion model FLEXPART.