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In this paper, we present the first data from an alternative extraction method for atmospheric 14CO2 analysis, based on the direct trapping of whole air samples onto a molecular sieve zeolite (13X) trap, incorporated into a commercially available automated graphitization system. Results are presented for both inter-laboratory comparison samples and an in-house reference standard. The in-house reference was used to calculate the standard deviation of measurements (2.0‰). This newly developed method will facilitate faster sample processing and therefore lower cost per analysis, critical for scaling up such studies.

Hydrofluorocarbons (HFCs) are used in a range of industrial applications and have largely replaced previously used gases (CFCs and HCFCs). HFCs are not ozone-depleting but have large global warming potentials and are, therefore, reported to the United Nations Framework Convention on Climate Change (UNFCCC). Here, we use four independent inverse models to estimate European emissions of the two HFCs contributing the most to global warming (HFC-134a and HFC-125) and of SF6 for the year 2011. Using an ensemble of inverse models offers the possibility to better understand systematic uncertainties in inversions. All systems relied on the same measurement time series from Jungfraujoch (Switzerland), Mace Head (Ireland), and Monte Cimone (Italy) and the same a priori estimates of the emissions, but differed in terms of the Lagrangian transport model (FLEXPART, NAME), inversion method (Bayesian, extended Kalman filter), treatment of baseline mole fractions, spatial gridding, and a priori uncertainties. The model systems were compared with respect to the ability to reproduce the measurement time series, the spatial distribution of the posterior emissions, uncertainty reductions, and total emissions estimated for selected countries. All systems were able to reproduce the measurement time series very well, with prior correlations between 0.5 and 0.9 and posterior correlations being higher by 0.05 to 0.1. For HFC-125, all models estimated higher emissions from Spain + Portugal than reported to UNFCCC (median higher by 390 %) though with a large scatter between individual estimates. Estimates for Germany (+140 %) and Ireland (+850 %) were also considerably higher than UNFCCC, whereas the estimates for France and the UK were consistent with the national reports. In contrast to HFC-125, HFC-134a emissions from Spain + Portugal were broadly consistent with UNFCCC, and emissions from Germany were only 30 % higher. The data suggest that the UK over-reports its HFC-134a emissions to UNFCCC, as the model median emission was significantly lower, by 50 %. An overestimation of both HFC-125 and HFC-134a emissions by about a factor of 2 was also found for a group of eastern European countries (Czech Republic + Poland + Slovakia), though with less confidence since the measurement network has a low sensitivity to these countries. Consistent with UNFCCC, the models identified Germany as the highest national emitter of SF6 in Europe, and the model median emission was only 1 % lower than the UNFCCC numbers. In contrast, the model median emissions were 2–3 times higher than UNFCCC numbers for Italy, France, and Spain + Portugal. The country-aggregated emissions from the different models often did not overlap within the range of the analytical uncertainties formally given by the inversion systems, suggesting that parametric and structural uncertainties are often dominant in the overall a posteriori uncertainty. The current European network of three routine monitoring sites for synthetic greenhouse gases has the potential to identify significant shortcomings in nationally reported emissions, but a denser network would be needed for more reliable monitoring of country-wide emissions of these important greenhouse gases across Europe.

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We present inverse modelling (top down) estimates of European methane (CH4) emissions for 2006–2012 based on a new quality-controlled and harmonised in situ data set from 18 European atmospheric monitoring stations. We applied an ensemble of seven inverse models and performed four inversion experiments, investigating the impact of different sets of stations and the use of a priori information on emissions. The inverse models infer total CH4 emissions of 26.8 (20.2–29.7) Tg CH4 yr−1 (mean, 10th and 90th percentiles from all inversions) for the EU-28 for 2006–2012 from the four inversion experiments. For comparison, total anthropogenic CH4 emissions reported to UNFCCC (bottom up, based on statistical data and emissions factors) amount to only 21.3 Tg CH4 yr−1 (2006) to 18.8 Tg CH4 yr−1 (2012). A potential explanation for the higher range of top-down estimates compared to bottom-up inventories could be the contribution from natural sources, such as peatlands, wetlands, and wet soils. Based on seven different wetland inventories from the Wetland and Wetland CH4 Inter-comparison of Models Project (WETCHIMP), total wetland emissions of 4.3 (2.3–8.2) Tg CH4 yr−1 from the EU-28 are estimated. The hypothesis of significant natural emissions is supported by the finding that several inverse models yield significant seasonal cycles of derived CH4 emissions with maxima in summer, while anthropogenic CH4 emissions are assumed to have much lower seasonal variability. Taking into account the wetland emissions from the WETCHIMP ensemble, the top-down estimates are broadly consistent with the sum of anthropogenic and natural bottom-up inventories. However, the contribution of natural sources and their regional distribution remain rather uncertain. Furthermore, we investigate potential biases in the inverse models by comparison with regular aircraft profiles at four European sites and with vertical profiles obtained during the Infrastructure for Measurement of the European Carbon Cycle (IMECC) aircraft campaign. We present a novel approach to estimate the biases in the derived emissions, based on the comparison of simulated and measured enhancements of CH4 compared to the background, integrated over the entire boundary layer and over the lower troposphere. The estimated average regional biases range between −40 and 20 % at the aircraft profile sites in France, Hungary and Poland.

We present a comprehensive estimate of nitrous oxide (N2O) emissions using observations and models from 1995 to 2008. High-frequency records of tropospheric N2O are available from measurements at Cape Grim, Tasmania; Cape Matatula, American Samoa; Ragged Point, Barbados; Mace Head, Ireland; and at Trinidad Head, California using the Advanced Global Atmospheric Gases Experiment (AGAGE) instrumentation and calibrations. The Global Monitoring Division of the National Oceanic and Atmospheric Administration/Earth System Research Laboratory (NOAA/ESRL) has also collected discrete air samples in flasks and in situ measurements from remote sites across the globe and analyzed them for a suite of species including N2O. In addition to these major networks, we include in situ and aircraft measurements from the National Institute of Environmental Studies (NIES) and flask measurements from the Tohoku University and Commonwealth Scientific and Industrial Research Organization (CSIRO) networks. All measurements show increasing atmospheric mole fractions of N2O, with a varying growth rate of 0.1–0.7% per year, resulting in a 7.4% increase in the background atmospheric mole fraction between 1979 and 2011. Using existing emission inventories as well as bottom-up process modeling results, we first create globally gridded a priori N2O emissions over the 37 years since 1975. We then use the three-dimensional chemical transport model, Model for Ozone and Related Chemical Tracers version 4 (MOZART v4), and a Bayesian inverse method to estimate global as well as regional annual emissions for five source sectors from 13 regions in the world. This is the first time that all of these measurements from multiple networks have been combined to determine emissions. Our inversion indicates that global and regional N2O emissions have an increasing trend between 1995 and 2008. Despite large uncertainties, a significant increase is seen from the Asian agricultural sector in recent years, most likely due to an increase in the use of nitrogenous fertilizers, as has been suggested by previous studies.

This study examines N2O emission estimates from five different atmospheric inversion frameworks based on chemistry transport models (CTMs). The five frameworks differ in the choice of CTM meteorological data prior uncertainties and inversion method but use the same prior emissions and observation data set. The posterior modelled atmospheric N2O mole fractions are compared to observations to assess the performance of the inversions and to help diagnose problems in the modelled transport. Additionally the mean emissions for 2006 to 2008 are compared in terms of the spatial distribution and seasonality. Overall there is a good agreement among the inversions for the mean global total emission which ranges from 16.1 to 18.7 TgN yrg'1 and is consistent with previous estimates. Ocean emissions represent between 31 and 38 of the global total compared to widely varying previous estimates of 24 to 38. Emissions from the northern mid to high latitudes are likely to be more important with a consistent shift in emissions from the tropics and subtropics to the mid to high latitudes in the Northern Hemisphere; the emission ratio for 0 30° N to 30 90° N ranges from 1.5 to 1.9 compared with 2.9 to 3.0 in previous estimates. The largest discrepancies across inversions are seen for the regions of South and East Asia and for tropical and South America owing to the poor observational constraint for these areas and to considerable differences in the modelled transport especially inter hemispheric exchange rates and tropical convective mixing. Estimates of the seasonal cycle in N2O emissions are also sensitive to errors in modelled stratosphere to troposphere transport in the tropics and southern extratropics. Overall the results show a convergence in the global and regional emissions compared to previous independent studies.

The growth in atmospheric methane (CH4) concentrations over the past 2 decades has shown large variability on a timescale of several years. Prior to 1999 the globally averaged CH4 concentration was increasing at a rate of 6.0 ppb yr−1, but during a stagnation period from 1999 to 2006 this growth rate slowed to 0.6 ppb yr−1. From 2007 to 2009 the growth rate again increased to 4.9 ppb yr−1. These changes in growth rate are usually ascribed to variations in CH4 emissions. We have used a 3-D global chemical transport model, driven by meteorological reanalyses and variations in global mean hydroxyl (OH) concentrations derived from CH3CCl3 observations from two independent networks, to investigate these CH4 growth variations. The model shows that between 1999 and 2006 changes in the CH4 atmospheric loss contributed significantly to the suppression in global CH4 concentrations relative to the pre-1999 trend. The largest factor in this is relatively small variations in global mean OH on a timescale of a few years, with minor contributions of atmospheric transport of CH4 to its sink region and of atmospheric temperature. Although changes in emissions may be important during the stagnation period, these results imply a smaller variation is required to explain the observed CH4 trends. The contribution of OH variations to the renewed CH4 growth after 2007 cannot be determined with data currently available.

High frequency, in situ observations from 11 globally distributed sites for the period 1994–2014 and archived air measurements dating from 1978 onward have been used to determine the global growth rate of 1,1-difluoroethane (HFC-152a, CH3CHF2). These observations have been combined with a range of atmospheric transport models to derive global emission estimates in a top-down approach. HFC-152a is a greenhouse gas with a short atmospheric lifetime of about 1.5 years. Since it does not contain chlorine or bromine, HFC-152a makes no direct contribution to the destruction of stratospheric ozone and is therefore used as a substitute for the ozone depleting chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs). The concentration of HFC-152a has grown substantially since the first direct measurements in 1994, reaching a maximum annual global growth rate of 0.84 ± 0.05 ppt yr−1 in 2006, implying a substantial increase in emissions up to 2006. However, since 2007, the annual rate of growth has slowed to 0.38 ± 0.04 ppt yr−1 in 2010 with a further decline to an annual average rate of growth in 2013–2014 of −0.06 ± 0.05 ppt yr−1. The annual average Northern Hemisphere (NH) mole fraction in 1994 was 1.2 ppt rising to an annual average mole fraction of 10.1 ppt in 2014. Average annual mole fractions in the Southern Hemisphere (SH) in 1998 and 2014 were 0.84 and 4.5 ppt, respectively. We estimate global emissions of HFC-152a have risen from 7.3 ± 5.6 Gg yr−1 in 1994 to a maximum of 54.4 ± 17.1 Gg yr−1 in 2011, declining to 52.5 ± 20.1 Gg yr−1 in 2014 or 7.2 ± 2.8 Tg-CO2 eq yr−1. Analysis of mole fraction enhancements above regional background atmospheric levels suggests substantial emissions from North America, Asia, and Europe. Global HFC emissions (so called “bottom up” emissions) reported by the United Nations Framework Convention on Climate Change (UNFCCC) are based on cumulative national emission data reported to the UNFCCC, which in turn are based on national consumption data. There appears to be a significant underestimate ( > 20 Gg) of “bottom-up” reported emissions of HFC-152a, possibly arising from largely underestimated USA emissions and undeclared Asian emissions.

HFC-23 (also known as CHF3 [CHF subscript 3], fluoroform or trifluoromethane) is a potent greenhouse gas (GHG), with a global warming potential (GWP) of 14 800 for a 100-year time horizon. It is an unavoidable by-product of HCFC-22 (CHClF2 [CHCIF subscript 2], chlorodifluoromethane) production. HCFC-22, an ozone depleting substance (ODS), is used extensively in commercial refrigeration and air conditioning, in the extruded polystyrene (XPS) foam industries (dispersive applications) and also as a feedstock in fluoropolymer manufacture (a non-dispersive use). Aside from small markets in specialty uses, HFC-23 has historically been considered a waste gas that was, and often still is, simply vented to the atmosphere. Efforts have been made in the past two decades to reduce HFC-23 emissions, including destruction (incineration) in facilities in developing countries under the United Nations Framework Convention on Climate Change's (UNFCCC) Clean Development Mechanism (CDM), and by process optimization and/or voluntary incineration by most producers in developed countries. We present observations of lower-tropospheric mole fractions of HFC-23 measured by "Medusa" GC/MSD instruments from ambient air sampled in situ at the Advanced Global Atmospheric Gases Experiment (AGAGE) network of five remote sites (2007–2009) and in Cape Grim air archive (CGAA) samples (1978–2009) from Tasmania, Australia. These observations are used with the AGAGE 2-D atmospheric 12-box model and an inverse method to produce model mole fractions and a "top-down" HFC-23 emission history. The model 2009 annual mean global lower-tropospheric background abundance is 22.6 (±0.2) pmol mol−1 [mol superscript -1]. The derived HFC-23 emissions show a "plateau" during 1997–2003, followed by a rapid ~50% increase to a peak of 15.0 (+1.3/−1.2) Gg/yr in 2006. Following this peak, emissions of HFC-23 declined rapidly to 8.6 (+0.9/−1.0) Gg/yr in 2009, the lowest annual emission of the past 15 years. We derive a 1990–2008 "bottom-up" HFC-23 emission history using data from the United Nations Environment Programme and the UNFCCC. Comparison with the top-down HFC-23 emission history shows agreement within the stated uncertainties. In the 1990s, HFC-23 emissions from developed countries dominated all other sources, then began to decline and eventually became fairly constant during 2003–2008. By this point, with developed countries' emissions essentially at a plateau, the major factor controlling the annual dynamics of global HFC-23 emissions became the historical rise of developing countries' HCFC-22 dispersive use production, which peaked in 2007. Thereafter in 2007–2009, incineration through CDM projects became a larger factor, reducing global HFC-23 emissions despite rapidly rising HCFC-22 feedstock production in developing countries., NASA Upper Atmospheric Research Program (Grant NNX07AE89G), NASA Upper Atmospheric Research Program (Grant NNX07AF09G), NASA Upper Atmospheric Research Program (Grant NNX07AE87G)

European CH4 and N2O emissions are estimated for 2006 and 2007 using four inverse modelling systems, based on different global and regional Eulerian and Lagrangian transport models. This ensemble approach is designed to provide more realistic estimates of the overall uncertainties in the derived emissions, which is particularly important for verifying bottom-up emission inventories. We use continuous observations from 10 European stations (including 5 tall towers) for CH4 and 9 continuous stations for N2O, complemented by additional European and global discrete air sampling sites. The available observations mainly constrain CH4 and N2O emissions from north-western and eastern Europe. The inversions are strongly driven by the observations and the derived total emissions of larger countries show little dependence on the emission inventories used a priori. Three inverse models yield 26–56% higher total CH4 emissions from north-western and eastern Europe compared to bottom-up emissions reported to the UNFCCC, while one model is close to the UNFCCC values. In contrast, the inverse modelling estimates of European N2O emissions are in general close to the UNFCCC values, with the overall range from all models being much smaller than the UNFCCC uncertainty range for most countries. Our analysis suggests that the reported uncertainties for CH4 emissions might be underestimated, while those for N2O emissions are likely overestimated.

We report on HCFC-22 data acquired by the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS) in reduced spectral resolution nominal mode in the period from January 2005 to April 2012 from version 5.02 level-1b spectral data and covering an altitude range from the upper troposphere (above cloud top altitude) to about 50 km. The profile retrieval was performed by constrained nonlinear least squares fitting of measured limb spectral radiances to modelled spectra. The spectral v4-band at 816.5 ± 13 cm-1 was used for the retrieval. A Tikhonov-type smoothing constraint was applied to stabilise the retrieval. In the lower stratosphere, we find a global volume mixing ratio of HCFC-22 of about 185 pptv in January 2005. The linear growth rate in the lower latitudes lower stratosphere was about 6 to 7 pptv yr-1 in the period 2005-2012. The obtained profiles were compared with ACE-FTS satellite data v3.5, as well as with MkIV balloon profiles and in situ cryosampler balloon measurements. Between 13 and 22 km, average agreement within -3 to +5 pptv (MIPAS–ACE) with ACE-FTS v3.5 profiles is demonstrated. Agreement with MkIV solar occultation balloon-borne measurements is within 10-20 pptv below 30 km and worse above, while in situ cryosampler balloon measurements are systematically lower over their full altitude range by 15-50 pptv below 24 km and less than 10 pptv above 28 km. Obtained MIPAS HCFC-22 time series below 10 km altitude are shown to agree mostly well to corresponding time series of near-surface abundances from NOAA/ESRL and AGAGE networks, although a more pronounced seasonal cycle is obvious in the satellite data, probably due to tropopause altitude fluctuations and subsidence of polar winter stratospheric air into the troposphere. A parametric model consisting of constant, linear, quasi-biennial oscillation (QBO) and several sine and cosine terms with different periods has been fitted to the temporal variation of stratospheric HCFC-22 for all 10° latitude/1 to 2 km altitude bins. The relative linear variation was always positive, with relative increases of 40-70% decade-1 in the tropics and global lower stratosphere, and up to 120% decade-1 in the upper stratosphere of the northern polar region and the southern extratropical hemisphere. In the middle stratosphere between 20 and 30 km, the observed trend is not consistent with the age of stratospheric air-corrected trend at ground, but stronger positive at the Southern Hemisphere and less strong increasing in the Northern Hemisphere, hinting towards changes in the stratospheric circulation over the observation period.

International audience; The 1,1,1,2-tetrafluoroethane (HFC-134a), an important alternative to CFC-12 in accordance with the Montreal Protocol on Substances that Deplete the Ozone Layer, is a high global warming potential greenhouse gas. Here we evaluate variations in global and regional HFC-134a emissions and emission trends, from 1995 to 2010, at a relatively high spatial and temporal (3.75°in longitude × 2.5°in latitude and 8 day) resolution, using surface HFC-134a measurements. Our results show a progressive increase of global HFC-134a emissions from 19 ± 2 Gg/yr in 1995 to 167 ± 5 Gg/yr in 2010, with both a slowdown in developed countries and a 20%/yr increase in China since 2005. A seasonal cycle is also seen since 2002, which becomes enhanced over time, with larger values during the boreal summer.

This study examines N2O emission estimates from five different atmospheric inversion frameworks based on chemistry transport models (CTMs). The five frameworks differ in the choice of CTM, meteorological data, prior uncertainties and inversion method but use the same prior emissions and observation data set. The posterior modelled atmospheric N2O mole fractions are compared to observations to assess the performance of the inversions and to help diagnose problems in the modelled transport. Additionally, the mean emissions for 2006 to 2008 are compared in terms of the spatial distribution and seasonality. Overall, there is a good agreement among the inversions for the mean global total emission, which ranges from 16.1 to 18.7 TgN yrĝ̂'1 and is consistent with previous estimates. Ocean emissions represent between 31 and 38% of the global total compared to widely varying previous estimates of 24 to 38%. Emissions from the northern mid- to high latitudes are likely to be more important, with a consistent shift in emissions from the tropics and subtropics to the mid- to high latitudes in the Northern Hemisphere; the emission ratio for 0-30° N to 30-90° N ranges from 1.5 to 1.9 compared with 2.9 to 3.0 in previous estimates. The largest discrepancies across inversions are seen for the regions of South and East Asia and for tropical and South America owing to the poor observational constraint for these areas and to considerable differences in the modelled transport, especially inter-hemispheric exchange rates and tropical convective mixing. Estimates of the seasonal cycle in N2O emissions are also sensitive to errors in modelled stratosphere-to-troposphere transport in the tropics and southern extratropics. Overall, the results show a convergence in the global and regional emissions compared to previous independent studies.

Atmospheric measurements show that emissions of hydrofluorocarbons (HFCs) and hydrochlorofluorocarbons are now the primary drivers of the positive growth in synthetic greenhouse gas (SGHG) radiative forcing. We infer recent SGHG emissions and examine the impact of future emissions scenarios, with a particular focus on proposals to reduce HFC use under the Montreal Protocol. If these proposals are implemented, overall SGHG radiative forcing could peak at around 355mWm(-2) in 2020, before declining by approximately 26% by 2050, despite continued growth of fully fluorinated greenhouse gas emissions. Compared to no HFC policy projections, this amounts to a reduction in radiative forcing of between 50 and 240mWm(-2) by 2050 or a cumulative emissions saving equivalent to 0.5 to 2.8years of CO2 emissions at current levels. However, more complete reporting of global HFC emissions is required, as less than half of global emissions are currently accounted for.Key PointsMeasurements of all the major synthetic greenhouse gases have been compiled These measurements have been used to infer recent global emissions trends Based on these trends, future emissions scenarios have been investigated