Global modelling of H2 mixing ratios and isotopic compositions with the TM5 model

The isotopic composition of molecular hydrogen (H2) contains independent information for constraining the global H2 budget. To explore this, we have implemented hydrogen sources and sinks, including their isotopic composition, into the global chemistry transport model TM5. For the first time, a global model now includes a simplified but explicit isotope reaction scheme for the photochemical production of H2. We present a comparison of modelled results for the H2 mixing ratio and isotope composition with available measurements on the seasonal to inter annual time scales for the years 2001–2007. The base model results agree well with observations for H2 mixing ratios. For dD[H2], modelled values are slightly lower than measurements. A detailed sensitivity study is performed to identify the most important parameters for modelling the isotopic composition of H2. The results show that on the global scale, the discrepancy between model and measurements can be closed by adjusting the default values of the isotope effects in deposition, photochemistry and the stratosphere-troposphere exchange within the known range of uncertainty. However, the available isotope data do not provide sufficient information to uniquely constrain the global isotope budget. Therefore, additional studies focussing on the isotopic composition near the tropopause and on the isotope effects in the photochemistry and deposition are recommended

Sulfur hexafluoride - A powerful new atmospheric tracer

Long-term observations of the atmospheric trace gas sulfur hexafluoride (SF6) at four background monitoring stations, Neumayer, Antarctica (1986-1994), Cape Grim, Tasmania (1978-1994), Izana, Canary Islands (1991-1994) and Alert, Canada (1993-1994) are presented. These data sets are supplemented by two meridional profiles collected over the Atlantic Ocean (1990 and 1993) and occasional observations at the regional site Fraserdale, Canada (1994). The analytical system and the method of SF6 calibration are described. Compared with data from Neumayer and Izana reported earlier, measurements are updated for all sites until the end of 1994 and the precision has improved by more than a factor of 2. With the Cape Grim archived air samples, the atmospheric SF6 chronology is extended by 8 more years back to 1978. For the period from January 1978 to December 1994 the data confirm a stable and unbroken quadratic rise in tropospheric SF6 from 0.50 to 3.11 ppt in the southern hemisphere and for July 1991 to December 1994 from 2.69 to 3.44 ppt in the northern hemisphere. The global mean tropospheric increase rate in late 1994 was 0.225 ppt/yr (6.9%/yr). The long term trend and interhemispheric gradients are due to industrial production and emission, rising approximately linearly with time and located predominantly (94%) in the northern hemisphere. The interhemispheric exchange time (1.7+/-0.2 yr) derived from SF6 ground level observations when using a two-box model of the atmosphere is considerably larger if compared to the exchange time derived from two- and three-dimensional models (1.1 yr). The chemical and biological inertness of SF6 up to stratospheric conditions results in an atmospheric lifetime of more than 800 years and makes SF6 a powerful tool for modelling transport processes in the atmosphere. Moreover, the tropospheric SF6 chronology is a very valuable input function for mixing studies in linked compartments like the stratosphere, the hydrosphere and the cryosphere

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

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

Chlorine isotope composition in chlorofluorocarbons CFC-11, CFC-12 and CFC-113 in firn, stratospheric and tropospheric air

The stratospheric degradation of chlorofluorocarbons (CFCs) releases chlorine, which is a major contributor to the destruction of stratospheric ozone (O3). A recent study reported strong chlorine isotope fractionation during the breakdown of the most abundant CFC (CFC-12, CCl2F2, Laube et al., 2010a), similar to effects seen in nitrous oxide (N2O). Using air archives to obtain a long-term record of chlorine isotope ratios in CFCs could help to identify and quantify their sources and sinks. We analyse the three most abundant CFCs and show that CFC-11 (CCl3F) and CFC-113 (CClF2CCl2F) exhibit significant stratospheric chlorine isotope fractionation, in common with CFC-12. The apparent isotope fractionation (εapp) for mid- and high-latitude stratospheric samples are (-2.4±0.5) ‰ and (-2.3±0.4) ‰ for CFC-11, (-12.2±1.6) ‰ and (-6.8±0.8) ‰ for CFC-12 and (-3.5±1.5) ‰ and (-3.3±1.2) ‰ for CFC-113, respectively. Assuming a constant isotope composition of emissions, we calculate the expected trends in the tropospheric isotope signature of these gases based on their stratospheric 37Cl enrichment and stratosphere-troposphere exchange. We compare these projections to the long-term δ(37Cl) trends of all three CFCs, measured on background tropospheric samples from the Cape Grim air archive (Tasmania, 1978 – 2010) and tropospheric firn air samples from Greenland (NEEM site) and Antarctica (Fletcher Promontory site). From 1970 to the present-day, projected trends agree with tropospheric measurements, suggesting that within analytical uncertainties a constant average emission isotope delta is a compatible scenario. The measurement uncertainty is too high to determine whether the average emission isotope delta has been affected by changes in CFC manufacturing processes, or not. Our study increases the suite of trace gases amenable to direct isotope ratio measurements in small air volumes (approximately 200 ml), using a single-detector gas chromatography-mass spectrometry system

Partitioning of the global fossil CO2 sink using a 19-year trend in atmospheric O2

O2/N2 is measured in the Cape Grim Air Archive (CGAA), a suite of tanks filled with background air at Cape Grim, Tasmania (40.7°S, 144.8°E) between April 1978 and January 1997. Derived trends are compared with published O2/N2 records and assessed against limits on interannual variability of net terrestrial exchanges imposed by trends of δ13C in CO2. Two old samples from 1978 and 1987 and eight from 1996/97 survive critical selection criteria and give a mean 19-year trend in δ(O2/N2) of -16.7 ± 0.5 per meg yr-1, implying net storage of +2.3 ± 0.7 GtC (1015 g carbon) yr-1 of fossil fuel CO2 in the oceans and +0.2 ± 0.9 GtC yr-1 in the terrestrial biosphere. The uptake terms are consistent for both O2/N2 and δ13C tracers if the mean 13C isotopic disequilibrium flux, combining terrestrial and oceanic contributions, is 93 ± 15 GtC ‰ yr-1. Copyright 1999 by the American Geophysical Union

Trace gases and CO2 isotope records from cabo de rama, India

Concentrations of carbon dioxide (CO2), methane (CH4), carbon monoxide (CO), nitrous oxide (N2O) and hydrogen (H2), and the stable carbon (δ 13C-CO2) and oxygen (δ 18O-CO2) isotopic composition of CO2 have been measured in air samples collected from Cabo de Rama (CRI), India, for the period 1993-2002. The observations show clear signatures of Northern and Southern Hemispheric (NH and SH) air masses, mixed with their regional fluxes and chemical loss mechanisms, resulting in complex seasonal variation of these gases. The CRI measurements are compared with remote marine sites at Seychelles and Mauna Loa. Simulations of two major anthropogenic greenhouse gases (CO2 and CH4) concentrations using a chemistry-transport model for the CRI site suggest that globally optimized fluxes can produce results comparable to the observations. We discuss that CRI observations have provided critical guidance in optimizing the fluxes to constrain the regional source/sinks balance

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