Consumption of CH3Cl, CH3Br, and CH3I and emission of CHCl3, CHBr3, and CH2Br2 from the forefield of a retreating Arctic glacier

The Arctic is one of the most rapidly warming regions of the Earth, with predicted temperature increases of 5–7 ∘C and the accompanying extensive retreat of Arctic glacial systems by 2100. Retreating glaciers will reveal new land surfaces for microbial colonisation, ultimately succeeding to tundra over decades to centuries. An unexplored dimension to these changes is the impact upon the emission and consumption of halogenated organic compounds (halocarbons). Halocarbons are involved in several important atmospheric processes, including ozone destruction, and despite considerable research, uncertainties remain in the natural cycles of some of these compounds. Using flux chambers, we measured halocarbon fluxes across the glacier forefield (the area between the present-day position of a glacier's ice-front and that at the last glacial maximum) of a high-Arctic glacier in Svalbard, spanning recently exposed sediments (<10 years) to approximately 1950-year-old tundra. Forefield land surfaces were found to consume methyl chloride (CH3Cl) and methyl bromide (CH3Br), with both consumption and emission of methyl iodide (CH3I) observed. Bromoform (CHBr3) and dibromomethane (CH2Br2) have rarely been measured from terrestrial sources but were here found to be emitted across the forefield. Novel measurements conducted on terrestrial cyanobacterial mats covering relatively young surfaces showed similar measured fluxes to the oldest, vegetated tundra sites for CH3Cl, CH3Br, and CH3I (which were consumed) and for CHCl3 and CHBr3 (which were emitted). Consumption rates of CH3Cl and CH3Br and emission rates of CHCl3 from tundra and cyanobacterial mat sites were within the ranges reported from older and more established Arctic tundra elsewhere. Rough calculations showed total emissions and consumptions of these gases across the Arctic were small relative to other sources and sinks due to the small surface area represented by glacier forefields. We have demonstrated that glacier forefields can consume and emit halocarbons despite their young age and low soil development, particularly when cyanobacterial mats are present

An analytical inversion method for determining regional and global emissions of greenhouse gases: Sensitivity studies and application to halocarbons

A new analytical inversion method has been developed to determine the regional and global emissions of long-lived atmospheric trace gases. It exploits in situ measurement data from three global networks and builds on backward simulations with a Lagrangian particle dispersion model. The emission information is extracted from the observed concentration increases over a baseline that is itself objectively determined by the inversion algorithm. The method was applied to two hydrofluorocarbons (HFC-134a, HFC-152a) and a hydrochlorofluorocarbon (HCFC-22) for the period January 2005 until March 2007. Detailed sensitivity studies with synthetic as well as with real measurement data were done to quantify the influence on the results of the a priori emissions and their uncertainties as well as of the observation and model errors. It was found that the global a posteriori emissions of HFC-134a, HFC-152a and HCFC-22 all increased from 2005 to 2006. Large increases (21%, 16%, 18%, respectively) from 2005 to 2006 were found for China, whereas the emission changes in North America (−9%, 23%, 17%, respectively) and Europe (11%, 11%, −4%, respectively) were mostly smaller and less systematic. For Europe, the a posteriori emissions of HFC-134a and HFC-152a were slightly higher than the a priori emissions reported to the United Nations Framework Convention on Climate Change (UNFCCC). For HCFC-22, the a posteriori emissions for Europe were substantially (by almost a factor 2) higher than the a priori emissions used, which were based on HCFC consumption data reported to the United Nations Environment Programme (UNEP). Combined with the reported strongly decreasing HCFC consumption in Europe, this suggests a substantial time lag between the reported time of the HCFC-22 consumption and the actual time of the HCFC-22 emission. Conversely, in China where HCFC consumption is increasing rapidly according to the UNEP data, the a posteriori emissions are only about 40% of the a priori emissions. This reveals a substantial storage of HCFC-22 and potential for future emissions in China. Deficiencies in the geographical distribution of stations measuring halocarbons in relation to estimating regional emissions are also discussed in the paper. Applications of the inversion algorithm to other greenhouse gases such as methane, nitrous oxide or carbon dioxide are foreseen for the future

Optimal estimation of the surface fluxes of methyl chloride using a 3-D global chemical transport model

Methyl chloride (CH3Cl) [CH subscript 3 Cl] is a chlorine-containing trace gas in the atmosphere contributing significantly to stratospheric ozone depletion. Large uncertainties in estimates of its source and sink magnitudes and temporal and spatial variations currently exist. GEIA inventories and other bottom-up emission estimates are used to construct a priori maps of the surface fluxes of CH3Cl [CH subscript 3 Cl]. The Model of Atmospheric Transport and Chemistry (MATCH), driven by NCEP interannually varying meteorological data, is then used to simulate CH3Cl [CH subscript 3 Cl] mole fractions and quantify the time series of sensitivities of the mole fractions at each measurement site to the surface fluxes of various regional and global sources and sinks. We then implement the Kalman filter (with the unit pulse response method) to estimate the surface fluxes on regional/global scales with monthly resolution from January 2000 to December 2004. High frequency observations from the AGAGE, SOGE, NIES, and NOAA/ESRL HATS in situ networks and low frequency observations from the NOAA/ESRL HATS flask network are used to constrain the source and sink magnitudes. The inversion results indicate global total emissions around 4100 ± 470 Gg yr−1 [yr superscript -1] with very large emissions of 2200 ± 390 Gg yr−1 [yr superscript -1] from tropical plants, which turn out to be the largest single source in the CH3Cl [CH subscript 3 Cl] budget. Relative to their a priori annual estimates, the inversion increases global annual fungal and tropical emissions, and reduces the global oceanic source. The inversion implies greater seasonal and interannual oscillations of the natural sources and sink of CH3Cl [CH subscript 3 Cl] compared to the a priori. The inversion also reflects the strong effects of the 2002/2003 globally widespread heat waves and droughts on global emissions from tropical plants, biomass burning and salt marshes, and on the soil sink.United States. National Aeronautics and Space Administration (Grant NNX07AE89G)United States. National Aeronautics and Space Administration (Grant NAG5-12669)United States. National Aeronautics and Space Administration (Grant NNX07AF09G)United States. National Aeronautics and Space Administration (Grant NNX07AE87G)National Science Foundation (U.S.) (Grant ATM-0120468)United States. National Aeronautics and Space Administration (Grant NAG5-12099

European aerosol phenomenology - 8 : Harmonised source apportionment of organic aerosol using 22 Year-long ACSM/AMS datasets

Organic aerosol (OA) is a key component of total submicron particulate matter (PM1), and comprehensive knowledge of OA sources across Europe is crucial to mitigate PM1 levels. Europe has a well-established air quality research infrastructure from which yearlong datasets using 21 aerosol chemical speciation monitors (ACSMs) and 1 aerosol mass spectrometer (AMS) were gathered during 2013-2019. It includes 9 non-urban and 13 urban sites. This study developed a state-of-the-art source apportionment protocol to analyse long-term OA mass spectrum data by applying the most advanced source apportionment strategies (i.e., rolling PMF, ME-2, and bootstrap). This harmonised protocol was followed strictly for all 22 datasets, making the source apportionment results more comparable. In addition, it enables quantification of the most common OA components such as hydrocarbon-like OA (HOA), biomass burning OA (BBOA), cooking-like OA (COA), more oxidised-oxygenated OA (MO-OOA), and less oxidised-oxygenated OA (LO-OOA). Other components such as coal combustion OA (CCOA), solid fuel OA (SFOA: mainly mixture of coal and peat combustion), cigarette smoke OA (CSOA), sea salt (mostly inorganic but part of the OA mass spectrum), coffee OA, and ship industry OA could also be separated at a few specific sites. Oxygenated OA (OOA) components make up most of the submicron OA mass (average = 71.1%, range from 43.7 to 100%). Solid fuel combustion-related OA components (i.e., BBOA, CCOA, and SFOA) are still considerable with in total 16.0% yearly contribution to the OA, yet mainly during winter months (21.4%). Overall, this comprehensive protocol works effectively across all sites governed by different sources and generates robust and consistent source apportionment results. Our work presents a comprehensive overview of OA sources in Europe with a unique combination of high time resolution (30-240 min) and long-term data coverage (9-36 months), providing essential information to improve/validate air quality, health impact, and climate models.Peer reviewe

Atmospheric histories and emissions of chlorofluorocarbons CFC-13 (CClF3), ΣCFC-114 (C2Cl2F4), and CFC-115 (C2ClF5)

Based on observations of the chlorofluorocarbons CFC-13 (chlorotrifluoromethane), ΣCFC-114 (combined measurement of both isomers of dichlorotetrafluoroethane), and CFC-115 (chloropentafluoroethane) in atmospheric and firn samples, we reconstruct records of their tropospheric histories spanning nearly 8 decades. These compounds were measured in polar firn air samples, in ambient air archived in canisters, and in situ at the AGAGE (Advanced Global Atmospheric Gases Experiment) network and affiliated sites. Global emissions to the atmosphere are derived from these observations using an inversion based on a 12-box atmospheric transport model. For CFC-13, we provide the first comprehensive global analysis. This compound increased monotonically from its first appearance in the atmosphere in the late 1950s to a mean global abundance of 3.18 ppt (dry-air mole fraction in parts per trillion, pmol mol1) in 2016. Its growth rate has decreased since the mid-1980s but has remained at a surprisingly high mean level of 0.02 ppt yr⁻¹ since 2000, resulting in a continuing growth of CFC-13 in the atmosphere. ΣCFC-114 increased from its appearance in the 1950s to a maximum of 16.6 ppt in the early 2000s and has since slightly declined to 16.3 ppt in 2016. CFC-115 increased monotonically from its first appearance in the 1960s and reached a global mean mole fraction of 8.49 ppt in 2016. Growth rates of all three compounds over the past years are significantly larger than would be expected from zero emissions. Under the assumption of unchanging lifetimes and atmospheric transport patterns, we derive global emissions from our measurements, which have remained unexpectedly high in recent years: mean yearly emissions for the last decade (2007–2016) of CFC-13 are at 0.48 ± 0.15 kt yr⁻¹ (> 15 % of past peak emissions), of ΣCFC-114 at 1.90 ± 0.84 kt yr⁻¹ (∼ 10 % of peak emissions), and of CFC-115 at 0.80 ± 0.50 kt yr⁻¹(> 5 % of peak emissions). Mean yearly emissions of CFC-115 for 2015–2016 are 1.14 ± 0.50 kt yr⁻¹ and have doubled compared to the 2007–2010 minimum. We find CFC-13 emissions from aluminum smelters but if extrapolated to global emissions, they cannot account for the lingering global emissions determined from the atmospheric observations. We find impurities of CFC-115 in the refrigerant HFC-125 (CHF₂CF₃) but if extrapolated to global emissions, they can neither account for the lingering global CFC-115 emissions determined from the atmospheric observations nor for their recent increases. We also conduct regional inversions for the years 2012–2016 for the northeastern Asian area using observations from the Korean AGAGE site at Gosan and find significant emissions for ΣCFC-114 and CFC-115, suggesting that a large fraction of their global emissions currently occur in northeastern Asia and more specifically on the Chinese mainland

Corrigendum to &quot;Global and regional emission estimates for HCFC-22&quot;, Atmos. Chem. Phys., 12, 10033–10050, 2012

No abstract available

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)&nbsp;ppt Cl in 2017, with &gt;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)&nbsp;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

Global and regional emissions of HFC-125 (CHF[subscript 2]CF[subscript 3]) from in situ and air archive atmospheric observations at AGAGE and SOGE observatories

High-frequency, in situ observations from the Advanced Global Atmospheric Gases Experiment (AGAGE) and System for Observation of halogenated Greenhouse gases in Europe (SOGE) networks for the period 1998 to 2008, combined with archive flask measurements dating back to 1978, have been used to capture the rapid growth of HFC-125 (CHF[subscript 2]CF[subscript 3]) in the atmosphere. HFC-125 is the fifth most abundant HFC, and it currently makes the third largest contribution of the HFCs to atmospheric radiative forcing. At the beginning of 2008 the global average was 5.6 ppt in the lower troposphere and the growth rate was 16% yr[superscript −1]. The extensive observations have been combined with a range of modeling techniques to derive global emission estimates in a top-down approach. It is estimated that 21 kt were emitted globally in 2007, and the emissions are estimated to have increased 15% yr[superscript −1] since 2000. These estimates agree within approximately 20% with values reported to the United Nations Framework Convention on Climate Change (UNFCCC) provided that estimated emissions from East Asia are included. Observations of regionally polluted air masses at individual AGAGE sites have been used to produce emission estimates for Europe (the EU-15 countries), the United States, and Australia. Comparisons between these top-down estimates and bottom-up estimates based on reports by individual countries to the UNFCCC show a range of approximately four in the differences. This process of independent verification of emissions, and an understanding of the differences, is vital for assessing the effectiveness of international treaties, such as the Kyoto Protocol