Atmospheric observation-based global SF6 emissions - comparison of top-down and bottom-up estimates

Emissions of sulphur hexafluoride (SF6), one of the strongest greenhouse gases on a per molecule basis, are targeted to be collectively reduced under the Kyoto Protocol. Because of its long atmospheric lifetime (≈3000 years), the accumulation of SF6 in the atmosphere is a direct measure of its global emissions. Examination of our extended data set of globally distributed high-precision SF6 observations shows an increase in SF6 abundance from near zero in the 1970s to a global mean of 6.7 ppt by the end of 2008. In-depth evaluation of our long-term data records shows that the global source of SF6 decreased after 1995, most likely due to SF6 emission reductions in industrialised countries, but increased again after 1998. By subtracting those emissions reported by Annex I countries to the United Nations Framework Convention of Climatic Change (UNFCCC) from our observation-inferred SF6 source leaves a surprisingly large gap of more than 70–80% of non-reported SF6 emissions in the last decade

Abrupt reversal in emissions and atmospheric abundance of HCFC-133a (CF3CH2Cl)

Hydrochlorofluorocarbon HCFC-133a (CF3CH2Cl) is an anthropogenic compound whose consumption for emissive use is restricted under the Montreal Protocol. A recent study showed rapidly increasing atmospheric abundances and emissions. We report that, following this rise, the at- mospheric abundance and emissions have declined sharply in the past three years. We find a Northern Hemisphere HCFC-133a increase from 0.13 ppt (dry air mole fraction in parts-per-trillion) in 2000 to 0.50 ppt in 2012–mid-2013 followed by an abrupt reversal to 0.44 ppt by early 2015. Global emissions derived from these observations peaked at 3.1 kt in 2011, followed by a rapid decline of 0.5 kt yr−2 to 1.5 kt yr−1 in 2014. Sporadic HCFC-133a pollution events are detected in Europe from our high-resolution HCFC-133a records at three European stations, and in Asia from sam- ples collected in Taiwan. European emissions are estimated to be <0.1 kt yr−1 although emission hotspots were identi- fied in France

Isotopic ordering in atmospheric O2 as a tracer of ozone photochemistry and the tropical atmosphere

The distribution of isotopes within O2 molecules can be rapidly altered when they react with atomic oxygen. This mechanism is globally important: while other contributions to the global budget of O2 impart isotopic signatures, the O(3P) + O2 reaction resets all such signatures in the atmosphere on subdecadal timescales. Consequently, the isotopic distribution within O2 is determined by O3 photochemistry and the circulation patterns that control where that photochemistry occurs. The variability of isotopic ordering in O2 has not been established, however. We present new measurements of 18O18O in air (reported as Δ36 values) from the surface to 33 km altitude. They confirm the basic features of the clumped-isotope budget of O2: Stratospheric air has higher Δ36 values than tropospheric air (i.e., more 18O18O), reflecting colder temperatures and fast photochemical cycling of O3. Lower Δ36 values in the troposphere arise from photochemistry at warmer temperatures balanced by the influx of high-Δ36 air from the stratosphere. These observations agree with predictions derived from the GEOS-Chem chemical transport model, which provides additional insight. We find a link between tropical circulation patterns and regions where Δ36 values are reset in the troposphere. The dynamics of these regions influences lapse rates, vertical and horizontal patterns of O2 reordering, and thus the isotopic distribution toward which O2 is driven in the troposphere. Temporal variations in Δ36 values at the surface should therefore reflect changes in tropospheric temperatures, photochemistry, and circulation. Our results suggest that the tropospheric O3 burden has remained within a ±10% range since 1978

Trends and emissions of six perfluorocarbons in the Northern Hemisphere and Southern Hemisphere

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

Country-Scale Analysis of Methane Emissions with a High-Resolution Inverse Model Using GOSAT and Surface Observations

We employed a global high-resolution inverse model to optimize the CH4 emission using Greenhouse gas Observing Satellite (GOSAT) and surface observation data for a period from 2011–2017 for the two main source categories of anthropogenic and natural emissions. We used the Emission Database for Global Atmospheric Research (EDGAR v4.3.2) for anthropogenic methane emission and scaled them by country to match the national inventories reported to the United Nations Framework Convention on Climate Change (UNFCCC). Wetland and soil sink prior fluxes were simulated using the Vegetation Integrative Simulator of Trace gases (VISIT) model. Biomass burning prior fluxes were provided by the Global Fire Assimilation System (GFAS). We estimated a global total anthropogenic and natural methane emissions of 340.9 Tg CH4 yr−1 and 232.5 Tg CH4 yr−1, respectively. Country-scale analysis of the estimated anthropogenic emissions showed that all the top-emitting countries showed differences with their respective inventories to be within the uncertainty range of the inventories, confirming that the posterior anthropogenic emissions did not deviate from nationally reported values. Large countries, such as China, Russia, and the United States, had the mean estimated emission of 45.7 ± 8.6, 31.9 ± 7.8, and 29.8 ± 7.8 Tg CH4 yr−1, respectively. For natural wetland emissions, we estimated large emissions for Brazil (39.8 ± 12.4 Tg CH4 yr−1), the United States (25.9 ± 8.3 Tg CH4 yr−1), Russia (13.2 ± 9.3 Tg CH4 yr−1), India (12.3 ± 6.4 Tg CH4 yr−1), and Canada (12.2 ± 5.1 Tg CH4 yr−1). In both emission categories, the major emitting countries all had the model corrections to emissions within the uncertainty range of inventories. The advantages of the approach used in this study were: (1) use of high-resolution transport, useful for simulations near emission hotspots, (2) prior anthropogenic emissions adjusted to the UNFCCC reports, (3) combining surface and satellite observations, which improves the estimation of both natural and anthropogenic methane emissions over spatial scale of countries

CO2 surface fluxes at grid point scale estimated from a global 21 year reanalysis of atmospheric measurements

This paper documents a global Bayesian variational inversion of CO2 surface fluxes during the period 1988–2008. Weekly fluxes are estimated on a 3.75° × 2.5° (longitude-latitude) grid throughout the 21 years. The assimilated observations include 128 station records from three large data sets of surface CO2 mixing ratio measurements. A Monte Carlo approach rigorously quantifies the theoretical uncertainty of the inverted fluxes at various space and time scales, which is particularly important for proper interpretation of the inverted fluxes. Fluxes are evaluated indirectly against two independent CO2 vertical profile data sets constructed from aircraft measurements in the boundary layer and in the free troposphere. The skill of the inversion is evaluated by the improvement brought over a simple benchmark flux estimation based on the observed atmospheric growth rate. Our error analysis indicates that the carbon budget from the inversion should be more accurate than the a priori carbon budget by 20% to 60% for terrestrial fluxes aggregated at the scale of subcontinental regions in the Northern Hemisphere and over a year, but the inversion cannot clearly distinguish between the regional carbon budgets within a continent. On the basis of the independent observations, the inversion is seen to improve the fluxes compared to the benchmark: the atmospheric simulation of CO2 with the Bayesian inversion method is better by about 1 ppm than the benchmark in the free troposphere, despite possible systematic transport errors. The inversion achieves this improvement by changing the regional fluxes over land at the seasonal and at the interannual time scales.This work was performed using HPC resources from GENCI‐ (CCRT/CINES/IDRIS; grant 2009‐ t2009012201). It was cofunded by the European Commission under the EU Seventh Research Framework Programme (grant agreements 212196, COCOS, and 218793, MACC)

Global CO2 fluxes inferred from surface air-sample measurements and from TCCON retrievals of the CO2 total column

We present the first estimate of the global distribution of CO2surface fluxes from 14 stations of the Total Carbon Column Observing Network (TCCON). The evaluation of this inversion is based on 1) comparison with the fluxes from a classical inversion of surface air-sample-measurements, and 2) comparison of CO2mixing ratios calculated from the inverted fluxes with independent aircraft measurements made during the two years analyzed here, 2009 and 2010. The former test shows similar seasonal cycles in the northern hemisphere and consistent regional carbon budgets between inversions from the two datasets, even though the TCCON inversion appears to be less precise than the classical inversion. The latter test confirms that the TCCON inversion has improved the quality (i.e., reduced the uncertainty) of the surface fluxes compared to the assumed or prior fluxes. The consistency between the surface-air-sample-based and the TCCON-based inversions despite remaining flaws in transport models opens the possibility of increased accuracy and robustness of flux inversions based on the combination of both data sources and confirms the usefulness of space-borne monitoring of the CO2 column.It was co-funded by the European Commission under the EU Seventh Research Framework Programme (grants agreements 218793, MACC, and 212196, COCOS

Aircraft‐Based Observations of Ozone‐Depleting Substances in the Upper Troposphere and Lower Stratosphere in and Above the Asian Summer Monsoon

Recent studies show that the Asian summer monsoon anticyclone (ASMA) transports emissions from the rapidly industrializing nations in Asia into the tropical upper troposphere. Here, we present a unique set of measurements on over 100 air samples collected on multiple flights of the M55 Geophysica high altitude research aircraft over the Mediterranean, Nepal, and Northern India during the summers of 2016 and 2017 as part of the European Union project StratoClim. These air samples were measured for 27 ozone‐depleting substances (ODSs), many of which were enhanced above expected levels, including the chlorinated very short‐lived substances, dichloromethane (CH2Cl2), 1,2‐dichloroethane (CH2ClCH2Cl), and chloroform (CHCl3). CH2Cl2 mixing ratios in the tropopause region were 65–136 parts per trillion (ppt) in comparison to previous estimates of mixing ratios in the tropical tropopause layer of 30–44 ppt in 2013–2014. Backward trajectories, calculated with the trajectory module of the chemistry‐transport model CLaMS and driven by the ERA5 reanalysis, indicate possible source regions of CH2Cl2 in South Asia. We derived total equivalent chlorine (ECl), and equivalent effective stratospheric chlorine (EESC) and found that these quantities were substantially higher than previous estimates in the literature. EESC at mean age‐of‐air of 3 years based on the 2016 measurements was 1,861–1,872 ppt in comparison to a previously estimated EESC of 1,646 ppt. Our findings show that the ASMA transports larger than expected mixing ratios of long‐lived and very short‐lived ODSs into the upper troposphere and lower stratosphere, likely leading to an impact on the stratospheric ozone layer