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High-frequency atmospheric measurements of methane (CH[subscript 4]), nitrous oxide (N[subscript 2]O) and sulfur hexafluoride (SF[subscript 6]) from Darjeeling, India are presented from December 2011 (CH[subscript 4])/March 2012 (N[subscript 2]O and SF[subscript 6]) through February 2013. These measurements were made on a gas chromatograph equipped with a flame ionization detector and electron capture detector, and were calibrated on the Tohoku University, the Scripps Institution of Oceanography (SIO)-98 and SIO-2005 scales for CH[subscript 4], N[subscript 2]O and SF[subscript 6], respectively. The observations show large variability and frequent pollution events in CH[subscript 4] and N[subscript 2]O mole fractions, suggesting significant sources in the regions sampled by Darjeeling throughout the year. By contrast, SF[subscript 6] mole fractions show little variability and only occasional pollution episodes, likely due to weak sources in the region. Simulations using the Numerical Atmospheric dispersion Modelling Environment (NAME) particle dispersion model suggest that many of the enhancements in the three gases result from the transport of pollutants from the densely populated Indo-Gangetic Plains of India to Darjeeling. The meteorology of the region varies considerably throughout the year from Himalayan flows in the winter to the strong south Asian summer monsoon. The model is consistent in simulating a diurnal cycle in CH[subscript 4] and N[subscript 2]O mole fractions that is present during the winter but absent in the summer and suggests that the signals measured at Darjeeling are dominated by large-scale (~100 km) flows rather than local (, Massachusetts Institute of Technology. Center for Global Change Science (Director's Fund), Massachusetts Institute of Technology. Joint Program on the Science & Policy of Global Change, Martin Family Society of Fellows for Sustainability, MIT Energy Initiative, MIT International Science and Technology Initiative, United States. National Aeronautics and Space Administration (Grant NNX11AF17G), United States. National Oceanic and Atmospheric Administration (Contract RA133R09CN0062)

[1] Observations of tropospheric N2O mixing ratio show significant variability on interannual timescales (0.2 ppb, 1 standard deviation). We found that interannual variability in N2O is weakly correlated with that in CFC-12 and SF6 for the northern extratropics and more strongly correlated for the southern extratropics, suggesting that interannual variability in all these species is influenced by large-scale atmospheric circulation changes and, for SF6 in particular, interhemispheric transport. N2O interannual variability was not, however, correlated with polar lower stratospheric temperature, which is used as a proxy for stratosphere-to-troposphere transport in the extratropics. This suggests that stratosphere-to-troposphere transport is not a dominant factor in year-to-year variations in N2O growth rate. Instead, we found strong correlations of N2O interannual variability with the Multivariate ENSO Index. The climate variables, precipitation, soil moisture, and temperature were also found to be significantly correlated with N2O interannual variability, suggesting that climate-driven changes in soil N2O flux may be important for variations in N2O growth rate.

This work reassesses the global atmospheric budget of H2 with the TM5 model. The recent adjustment of the calibration scale for H2 translates into a change in the tropospheric burden. Furthermore, the ECMWF Reanalysis-Interim (ERA-Interim) data from the European Centre for Medium-Range Weather Forecasts (ECMWF) used in this study show slower vertical transport than the operational data used before. Consequently, more H2 is removed by deposition. The deposition parametrization is updated because significant deposition fluxes for snow, water, and vegetation surfaces were calculated in our previous study. Timescales of 1-2h are asserted for the transport of H2 through the canopies of densely vegetated regions. The global scale variability of H2 and [DH2] is well represented by the updated model. H2 is slightly overestimated in the Southern Hemisphere because too little H2 is removed by dry deposition to rainforests and savannahs. The variability in H2 over Europe is further investigated using a high-resolution model subdomain. It is shown that discrepancies between the model and the observations are mainly caused by the finite model resolution. The tropospheric burden is estimated at 165 +/- 8TgH2. The removal rates of H2 by deposition and photochemical oxidation are estimated at 53 +/- 4 and 23 +/- 2TgH2/yr, resulting in a tropospheric lifetime of 2.2 +/- 0.2year.

The global methane (CH4) budget is becoming an increasingly important component for managing realistic pathways to mitigate climate change. This relevance, due to a shorter atmospheric lifetime and a stronger warming potential than carbon dioxide, is challenged by the still unexplained changes of atmospheric CH4 over the past decade. Emissions and concentrations of CH4 are continuing to increase, making CH4 the second most important human-induced greenhouse gas after carbon dioxide. Two major difficulties in reducing uncertainties come from the large variety of diffusive CH4 sources that overlap geographically, and from the destruction of CH4 by the very short-lived hydroxyl radical (OH). To address these difficulties, we have established a consortium of multi-disciplinary scientists under the umbrella of the Global Carbon Project to synthesize and stimulate research on the methane cycle, and producing regular (similar to biennial) updates of the global methane budget. This consortium includes atmospheric physicists and chemists, biogeochemists of surface and marine emissions, and socio-economists who study anthropogenic emissions. Following Kirschke et al. (2013), we propose here the first version of a living review paper that integrates results of top-down studies (exploiting atmospheric observations within an atmospheric inverse-modelling framework) and bottom-up models, inventories and data-driven approaches (including process-based models for estimating land surface emissions and atmospheric chemistry, and inventories for anthropogenic emissions, data-driven extrapolations). For the 2003-2012 decade, global methane emissions are estimated by top-down inversions at 558 TgCH(4) yr(-1), range 540-568. About 60% of global emissions are anthropogenic (range 50-65 %). Since 2010, the bottom-up global emission inventories have been closer to methane emissions in the most carbon-intensive Representative Concentrations Pathway (RCP8.5) and higher than all other RCP scenarios. Bottom-up approaches suggest larger global emissions (736 TgCH(4) yr(-1), range 596-884) mostly because of larger natural emissions from individual sources such as inland waters, natural wetlands and geological sources. Considering the atmospheric constraints on the top-down budget, it is likely that some of the individual emissions reported by the bottom-up approaches are overestimated, leading to too large global emissions. Latitudinal data from top-down emissions indicate a predominance of tropical emissions (similar to 64% of the global budget, amp;lt;30 degrees N) as compared to mid (similar to 32 %, 30-60 degrees N) and high northern latitudes (similar to 4 %, 60-90 degrees N). Top-down inversions consistently infer lower emissions in China (similar to 58 TgCH(4) yr(-1), range 51-72, -14 %) and higher emissions in Africa (86 TgCH(4) yr(-1), range 73-108, + 19 %) than bottom-up values used as prior estimates. Overall, uncertainties for anthropogenic emissions appear smaller than those from natural sources, and the uncertainties on source categories appear larger for top-down inversions than for bottom-up inventories and models. The most important source of uncertainty on the methane budget is attributable to emissions from wetland and other inland waters. We show that the wetland extent could contribute 30-40% on the estimated range for wetland emissions. Other priorities for improving the methane budget include the following: (i) the development of process-based models for inland-water emissions, (ii) the intensification of methane observations at local scale (flux measurements) to constrain bottom-up land surface models, and at regional scale (surface networks and satellites) to constrain top-down inversions, (iii) improvements in the estimation of atmospheric loss by OH, and (iv) improvements of the transport models integrated in top-down inversions. The data presented here can be downloaded from the Carbon Dioxide Information Analysis Center (http://doi.org/10.3334/CDIAC/GLOBAL_METHANE_BUDGET_2016_V1.1) and the Global Carbon Project. Funding Agencies|Swiss National Science Foundation; NASA [NNX14AF93G, NNX14AO73G]; National Environmental Science Program - Earth Systems and Climate Change Hub; European Commission [283576, 633080]; ESA Climate Change Initiative Greenhouse Gases Phase 2 project; US Department of Energy, BER [DE-AC02-05CH11231]; FAO member countries; Environment Research and Technology Development Fund of the Ministry of the Environment, Japan [2-1502]; ERC [322998]; NERC [NE/J00748X/1]; Swedish Research Council VR; Research Council of Norway [244074]; NSF [1243232, 1243220]; National Science and Engineering Research Council of Canada (NSERC); Chinas QianRen Program; CSIRO Australia; Australian Bureau of Meteorology; Australian Institute of Marine Science; Australian Antarctic Division; NOAA USA; Meteorological Service of Canada; National Aeronautic and Space Administration (NASA) [NAG5-12669, NNX07AE89G, NNX11AF17G, NNX07AE87G, NNX07AF09G, NNX11AF15G, NNX11AF16G]; Department of Energy and Climate Change (DECC, UK) [GA01081]; Commonwealth Scientific and Industrial Research Organization (CSIRO Australia); Bureau of Meteorology (Australia); Joint DECC/Defra Met Office Hadley Centre Climate Programme [GA01101]

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 3.90 (3.20−4.30) Tg CO2e. We evaluate the RAC (Refrigeration and Air-Conditioning) model, a bottom up model used to quantify UK emissions from refrigeration and air-conditioning sectors. Within mobile air-conditioning (MAC), the largest RAC sector and most significant UK source (59%), we find a number of assumptions that may be considered oversimplistic and conservative; most notably the unit refill rate. Finally, a Bayesian approach is used to estimate probable inventory inputs required for minimization of the emissions discrepancy. Our top-down estimates provide only a weak constraint on inventory model parameters and consequently, we are unable to suggest discrete values. However, a significant revision of the MAC servicing rate, coupled with a reassessment of non-RAC aerosol emissions, are required if the discrepancy between methods is to be reduced.

Carbon tetrachloride (CCl4) is an ozone-depleting substance, which is controlled by the Montreal Protocol and for which the atmospheric abundance is decreasing. However, the current observed rate of this decrease is known to be slower than expected based on reported CCl4 emissions and its estimated overall atmospheric lifetime. Here we use a three-dimensional (3-D) chemical transport model to investigate the impact on its predicted decay of uncertainties in the rates at which CCl4 is removed from the atmosphere by photolysis, by ocean uptake and by degradation in soils. The largest sink is atmospheric photolysis (74 % of total), but a reported 10 % uncertainty in its combined photolysis cross section and quantum yield has only a modest impact on the modelled rate of CCl4 decay. This is partly due to the limiting effect of the rate of transport of CCl4 from the main tropospheric reservoir to the stratosphere, where photolytic loss occurs. The model suggests large interannual variability in the magnitude of this stratospheric photolysis sink caused by variations in transport. The impact of uncertainty in the minor soil sink (9 % of total) is also relatively small. In contrast, the model shows that uncertainty in ocean loss (17 % of total) has the largest impact on modelled CCl4 decay due to its sizeable contribution to CCl4 loss and large lifetime uncertainty range (147 to 241 years). With an assumed CCl4 emission rate of 39 Gg year−1, the reference simulation with the best estimate of loss processes still underestimates the observed CCl4 (overestimates the decay) over the past 2 decades but to a smaller extent than previous studies. Changes to the rate of CCl4 loss processes, in line with known uncertainties, could bring the model into agreement with in situ surface and remote-sensing measurements, as could an increase in emissions to around 47 Gg year−1. Further progress in constraining the CCl4 budget is partly limited by systematic biases between observational datasets. For example, surface observations from the National Oceanic and Atmospheric Administration (NOAA) network are larger than from the Advanced Global Atmospheric Gases Experiment (AGAGE) network but have shown a steeper decreasing trend over the past 2 decades. These differences imply a difference in emissions which is significant relative to uncertainties in the magnitudes of the CCl4 sinks.

Changes of atmospheric methane (CH4) since 2005 have been evaluated using Fourier Transform Infrared (FTIR) solar observations performed at ten ground-based sites, all members of the Network for Detection of Atmospheric Composition Change (NDACC). From this, we find an increase of atmospheric methane total columns that amounts to 0.31 ± 0.03 % year−1 (2-sigma level of uncertainty) for the 2005–2014 period. Comparisons with in situ methane measurements at both local and global scales show good agreement. We used the GEOS-Chem Chemical Transport Model tagged simulation that accounts for the contribution of each emission source and one sink in the total methane, simulated over the 2005–2012 time period and based on emissions inventories and transport. After regridding according to NDACC vertical layering using a conservative regridding scheme and smoothing by convolving with respective FTIR seasonal averaging kernels, the GEOS-Chem simulation shows an increase of atmospheric methane of 0.35 ± 0.03 % year−1 between 2005 and 2012, which is in agreement with NDACC measurements over the same time period (0.30 ± 0.04 % year−1, averaged over ten stations). Analysis of the GEOS-Chem tagged simulation allows us to quantify the contribution of each tracer to the global methane change since 2005. We find that natural sources such as wetlands and biomass burning contribute to the inter-annual variability of methane. However, anthropogenic emissions such as coal mining, and gas and oil transport and exploration, which are mainly emitted in the Northern Hemisphere and act as secondary contributors to the global budget of methane, have played a major role in the increase of atmospheric methane observed since 2005. Based on the GEOS-Chem tagged simulation, we discuss possible cause(s) for the increase of methane since 2005, which is still unexplained.

We present a compact and versatile cryofocusing–thermodesorption unit, which we developed for quantitative analysis of halogenated trace gases in ambient air. Possible applications include aircraft-based in situ measurements, in situ monitoring and laboratory operation for the analysis of flask samples. Analytes are trapped on adsorptive material cooled by a Stirling cooler to low temperatures (e.g. −80 °C) and subsequently desorbed by rapid heating of the adsorptive material (e.g. +200 °C). The set-up involves neither the exchange of adsorption tubes nor any further condensation or refocusing steps. No moving parts are used that would require vacuum insulation. This allows for a simple and robust design. Reliable operation is ensured by the Stirling cooler, which neither contains a liquid refrigerant nor requires refilling a cryogen. At the same time, it allows for significantly lower adsorption temperatures compared to commonly used Peltier elements. We use gas chromatography – mass spectrometry (GC–MS) for separation and detection of the preconcentrated analytes after splitless injection. A substance boiling point range of approximately −80 to +150 °C and a substance mixing ratio range of less than 1 ppt (pmol mol−1) to more than 500 ppt in preconcentrated sample volumes of 0.1 to 10 L of ambient air is covered, depending on the application and its analytical demands. We present the instrumental design of the preconcentration unit and demonstrate capabilities and performance through the examination of analyte breakthrough during adsorption, repeatability of desorption and analyte residues in blank tests. Examples of application are taken from the analysis of flask samples collected at Mace Head Atmospheric Research Station in Ireland using our laboratory GC–MS instruments and by data obtained during a research flight with our in situ aircraft instrument GhOST-MS (Gas chromatograph for the Observation of Tracers – coupled with a Mass Spectrometer).

Perfluorocarbons (PFCs) are very potent and long-lived greenhouse gases in the atmosphere, released predominantly during aluminium production and semiconductor manufacture. They have been targeted for emission controls under the United Nations Framework Convention on Climate Change. Here we present the first continuous records of the atmospheric abundance of CF4 (PFC-14), C2F6 (PFC-116) and C3F8 (PFC-218) from 1800 to 2014. The records are derived from high-precision measurements of PFCs in air extracted from polar firn or ice at six sites (DE08, DE08-2, DSSW20K, EDML, NEEM and South Pole) and air archive tanks and atmospheric air sampled from both hemispheres. We take account of the age characteristics of the firn and ice core air samples and demonstrate excellent consistency between the ice core, firn and atmospheric measurements. We present an inversion for global emissions from 1900 to 2014. We also formulate the inversion to directly infer emission factors for PFC emissions due to aluminium production prior to the 1980s. We show that 19th century atmospheric levels, before significant anthropogenic influence, were stable at 34.1 ± 0.3 ppt for CF4 and below detection limits of 0.002 and 0.01 ppt for C2F6 and C3F8, respectively. We find a significant peak in CF4 and C2F6 emissions around 1940, most likely due to the high demand for aluminium during World War II, for example for construction of aircraft, but these emissions were nevertheless much lower than in recent years. The PFC emission factors for aluminium production in the early 20th century were significantly higher than today but have decreased since then due to improvements and better control of the smelting process. Mitigation efforts have led to decreases in emissions from peaks in 1980 (CF4) or early-to-mid-2000s (C2F6 and C3F8) despite the continued increase in global aluminium production; however, these decreases in emissions appear to have recently halted. We see a temporary reduction of around 15 % in CF4 emissions in 2009, presumably associated with the impact of the global financial crisis on aluminium and semiconductor production.

Carbon tetrachloride (CCl4) is a long-lived radiatively-active compound able to destroy stratospheric ozone. Due to its inclusion in the Montreal Protocol on Substances that Deplete the Ozone Layer, the last two decades have seen a sharp decrease in its large scale emissive use with a consequent decline of its atmospheric mole fractions. However, the Montreal Protocol restrictions do not apply to the use of carbon tetrachloride as feedstock for the production of other chemicals, implying the risk of fugitive emissions from the industry sector. The occurrence of such unintended emissions is suggested by a significant discrepancy between global emissions as derived by reported production and feedstock usage (bottom-up emissions), and those based on atmospheric observations (top-down emissions). In order to better constrain the atmospheric budget of carbon tetrachloride, several studies based on a combination of atmospheric observations and inverse modelling have been conducted in recent years in various regions of the world. This study is focused on the European scale and based on long-term high-frequency observations at three European sites, combined with a Bayesian inversion methodology. We estimated that average European emissions for 2006–2014 were 2.3 (± 0.8) Gg yr−1, with an average decreasing trend of 7.3 % per year. Our analysis identified France as the main source of emissions over the whole study period, with an average contribution to total European emissions of 25 %. The inversion was also able to allow the localisation of emission "hot-spots" in the domain, with major source areas in Southern France, Central England (UK) and Benelux (Belgium, The Netherlands, Luxembourg), where most of industrial scale production of basic organic chemicals are located. According to our results, European emissions correspond to 4.0 % of global emissions for 2006–2012. Together with other regional studies, our results allow a better constraint of the global budget of carbon tetrachloride and a better quantification of the gap between top-down and bottom-up estimates.

We report on HCFC-22 data acquired by the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS) in the reduced spectral resolution nominal observation mode. The data cover the period from January 2005 to April 2012 and the 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 modelled spectra to the measured limb spectral radiances. The spectral ν[subscript 4]-band at 816.5 ± 13 cm[superscript −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 rate of linear growth in the lower latitudes lower stratosphere was about 6 to 7 pptv year[superscript −1] in the period 2005–2012. The profiles obtained were compared with ACE-FTS satellite data v3.5, as well as with MkIV balloon profiles and 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. MIPAS HCFC-22 time series below 10 km altitude are shown to agree mostly well to corresponding time series of near-surface abundances from the NOAA/ESRL and AGAGE networks, although a more pronounced seasonal cycle is obvious in the satellite data. This is attributed 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[superscript −1] in the tropics and global lower stratosphere, and up to 120 % decade[superscript −1] in the upper stratosphere of the northern polar region and the southern extratropical hemisphere. Asian HCFC-22 emissions have become the major source of global upper tropospheric HCFC-22. In the upper troposphere, monsoon air, rich in HCFC-22, is instantaneously mixed into the tropics. In the middle stratosphere, between 20 and 30 km, the observed trend is inconsistent with the trend at the surface (corrected for the age of stratospheric air), hinting at circulation changes. There exists a stronger positive trend in HCFC-22 in the Southern Hemisphere and a more muted positive trend in the Northern Hemisphere, implying a potential change in the stratospheric circulation over the observation period.

The El Nino-Southern Oscillation (ENSO) affects the tropospheric concentrations of many trace gases. Here we investigate the ENSO influence on mercury concentrations measured in the upper troposphere during Civil Aircraft for the Regular Investigation of the atmosphere Based on an Instrumented Container flights and at ground at Cape Point, South Africa, and Mace Head, Ireland. Mercury concentrations cross-correlate with Southern Oscillation Index (SOI) with a lag of 8 +/- 2 months. Highest mercury concentrations are always found at the most negative SOI values, i.e., 8 months after El Nino, and the amplitude of the interannual variations fluctuates between similar to 5 and 18%. The time lag is similar to that of CO whose interannual variations are driven largely by emissions from biomass burning (BB). The amplitude of the interannual variability of tropospheric mercury concentrations is consistent with the estimated variations in mercury emissions from BB. We thus conclude that BB is a major factor driving the interannual variation of tropospheric mercury concentrations.

The observed seasonal cycles of a selection of reactive hydrocarbons in baseline air masses at Mace Head, Ireland are consistent with a simple picture of largely man-made sources and oxidation by hydroxyl (OH) radicals. As a result, the observed seasonal cycles become more pronounced the more reactive the species are with OH. For the pentanes, the assumption of little wintertime removal breaks down, leading to an apparent dampening of the seasonal cycles relative to ethane, propane and the butanes. A global chemistry-transport model is used to describe the seasonal cycles of the hydrocarbons at Mace Head and provided an accurate description of their observed amplitudes and phases. The model derived local OH concentrations in baseline air masses required to support the observed seasonal cycles of the hydrocarbons averaged 1.38 ± 1.1 × 106 molecule cm−3. Peak daytime levels during summertime reached 1.2 × 107 molecule cm−3.

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. The aggregated halocarbon emissions over the study area are estimated at 125 (106-150) Tg of CO(2) equiv/y, of which the hydrofluorocarbons (HFCs) make up the most important fraction with 41% (31-52%). We find that chlorofluorocarbon (CFC) emissions from banks are still significant and account for 35% (27-43%) of total halocarbon emissions in Europe. The regional differences in per capita emissions are only small for the HFCs, while emissions of CFCs and hydrochlorofluorocarbons (HCFCs) tend to be higher in Western Europe compared to Eastern Europe. In total, the inferred per capita emissions are similar to estimates for China, but 3.5 (2.3-4.5) times lower than for the United States. Our study demonstrates the large benefits of adding a strategically well placed measurement site to the existing European observation network of halocarbons, as it extends the coverage of the inversion domain toward Eastern Europe and helps to better constrain the emissions over Central Europe.

We present atmospheric sulfur hexafluoride (SF6) mole fractions and emissions estimates from the 1970s to 2008. Measurements were made of archived air samples starting from 1973 in the Northern Hemisphere and from 1978 in the Southern Hemisphere, using the Advanced Global Atmospheric Gases Experiment (AGAGE) gas chromatographic-mass spectrometric (GC-MS) systems. These measurements were combined with modern high-frequency GC-MS and GC-electron capture detection (ECD) data from AGAGE monitoring sites, to produce a unique 35-year atmospheric record of this potent greenhouse gas. Atmospheric mole fractions were found to have increased by more than an order of magnitude between 1973 and 2008. The 2008 growth rate was the highest recorded, at 0.29 ± 0.02 pmolmol−1 yr−1. A three-dimensional chemical transport model and a minimum variance Bayesian inverse method was used to estimate annual emission rates using the measurements, with a priori estimates from the Emissions Database for Global Atmospheric Research (EDGAR, version 4). Consistent with the mole fraction growth rate maximum, global emissions during 2008 were also the highest in the 1973–2008 period, reaching 7.4 ± 0.6 Gg yr−1 (1-σ uncertainties) and surpassing the previous maximum in 1995. The 2008 values follow an increase in emissions of 48 ± 20% since 2001. A second global inversion which also incorporated National Oceanic and Atmospheric Administration (NOAA) flask measurements and in situ monitoring site data agreed well with the emissions derived using AGAGE measurements alone. By estimating continent-scale emissions using all available AGAGE and NOAA surface measurements covering the period 2004–2008, with no pollution filtering, we find that it is likely that much of the global emissions rise during this five-year period originated primarily from Asian developing countries that do not report detailed, annual emissions to the United Nations Framework Convention on Climate Change (UNFCCC). We also find it likely that SF6 emissions reported to the UNFCCC were underestimated between at least 2004 and 2005.

Carbon tetrachloride (CCl4) has substantial stratospheric ozone depletion potential and its consumption is controlled under the Montreal Protocol and its amendments. We implement a Kalman filter using atmospheric CCl4 measurements and a 3-dimensional chemical transport model to estimate the interannual regional industrial emissions and seasonal global oceanic uptake of CCl4 for the period of 1996–2004. The Model of Atmospheric Transport and Chemistry (MATCH), driven by offline National Center for Environmental Prediction (NCEP) reanalysis meteorological fields, is used to simulate CCl4 mole fractions and calculate their sensitivities to regional sources and sinks using a finite difference approach. High frequency observations from the Advanced Global Atmospheric Gases Experiment (AGAGE) and the Earth System Research Laboratory (ESRL) of the National Oceanic and Atmospheric Administration (NOAA) and low frequency flask observations are together used to constrain the source and sink magnitudes, estimated as factors that multiply the a priori fluxes. Although industry data imply that the global industrial emissions were substantially declining with large interannual variations, the optimized results show only small interannual variations and a small decreasing trend. The global surface CCl4 mole fractions were declining in this period because the CCl4 oceanic and stratospheric sinks exceeded the industrial emissions. Compared to the a priori values, the inversion results indicate substantial increases in industrial emissions originating from the South Asian/Indian and Southeast Asian regions, and significant decreases in emissions from the European and North American regions., 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 NAG5-12099), National Science Foundation (U.S.) (grant ATM-0120468), United States. National Aeronautics and Space Administration (Grant NNX07AF09G), United States. National Aeronautics and Space Administration (Grant NNX07AE87G), Great Britain. Department for Environment, Food and Rural Affairs (grants EPG 1/1/159), Great Britain. Department for Environment, Food and Rural Affairs (grant CPEG 24), Great Britain. Department for Environment, Food and Rural Affairs (grants GA01081), Australia. Bureau of Meteorology, CSIRO Marine and Atmospheric Research

HFC-23 (also known as CHF3, 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, 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. 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.

Continuous in-situ measurements of NMHCs at Mace Head, Ireland during two full annual cycles from January 2005 to January 2007 were used to investigate NMHC emission sources and transport including dilution and photochemical oxidation. The Mace Head research station is ideally located to sample a wide range of air masses including polluted European transport, clean North Atlantic and Arctic air masses and the ultra-clean, Southern Atlantic air masses. The variety in air mass sampling is used to investigate interaction of emissions, transport, dilution and photochemistry. Variability of long-lived hydrocarbon ratios is used to assess and estimate typical transport times from emission source to the Mace Head receptor. Seasonality in the ratios of isomeric alkane pairs (for butane and pentanes) are used to assess the effects of atmospheric transport and photochemical ageing. Finally, the natural logarithms of NMHC ratios are used to assess photochemical oxidation.

Simultaneous chloroform (CHCl3) emission and ozone (O3) deposition are regularly observed under nocturnal inversions during the summer months from and to the peat bogs in the vicinity of the Mace Head Atmospheric Research Station, Connemara, Co Galway, Ireland. Emissions were estimated using the nocturnal box model applied to routine atmospheric observations collected over a 14-year period from 1995 to 2008. Strict criteria were applied in the selection of events of low wind speed, under a stable night-time inversion layer in baseline air conditions, with no transport from Europe. The mean peatland CHCl3 flux was 2.91 μg m−2 h−1 with highly variable fluxes ranging from 0.44 to 12.94 μg m−2 h−1. These fluxes are generally larger than those reported previously for similar biomes and if representative would make a significant contribution to the global estimated source of CHCl3. Fluxes were not strongly correlated with either atmospheric temperature or the level of precipitation. Over the 14-year period there appears to have been a small increase in overall CHCl3 emissions, although we stress that the nocturnal box model has a number of limitations and assumptions which should be taken into account.

Methane emissions from the peat bogs in Connemara, Ireland have been inferred from the trace gas observations at the Mace Head Atmospheric Research Station using the nocturnal box method. A total of 237 local events, during April to September, over a 12-year period have been studied. Simultaneous emissions of methane, carbon dioxide and chloroform are routinely observed under nocturnal inversions with low wind speeds from the peat bogs proximal to Mace Head. Night-time deposition of ozone and hydrogen occurs concurrently with these emissions. Using the temporally correlated methane and ozone data we estimate methane emissions from each event. Simultaneous methane and chloroform emissions, together with ozone and hydrogen deposition have been characterised, leading to the estimation of methane emission rates for each event. The mean methane emission flux was found to be 400 ± 90 ng m−2 s−1. A strong seasonal cycle was found in the methane emission fluxes but there was little evidence of a long-term trend in the emissions from the peat bogs in the vicinity of the Mace Head station.

This document is a supplement to “Physical Exchanges at the Air–Sea Interface: UK–SOLAS Field Measurements,” by Ian M. Brooks, Margaret J. Yelland, Robert C. Upstill-Goddard, Philip D. Nightingale, Steve Archer, Eric d’Asaro, Rachael Beale, Cory Beatty, Byron Blomquist, A. Anthony Bloom, Barbara J. Brooks, John Cluderay, David Coles, John Dacey, Michael DeGrandpre, Jo Dixon, William M. Drennan, Joseph Gabriele, Laura Goldson, Nick Hardman-Mountford, Martin K. Hill, Matt Horn, Ping-Chang Hsueh, Barry Huebert, Gerrit de Leeuw, Timothy G. Leighton, Malcolm Liddicoat, Justin J. N. Lingard, Craig McNeil, James B. McQuaid, Ben I. Moat, Gerald Moore, Craig Neill, Sarah J. Norris, Simon O’Doherty, Robin W. Pascal, John Prytherch, Mike Rebozo, Erik Sahlee, Matt Salter, Ute Schuster, Ingunn Skjelvan, Hans Slagter, Michael H. Smith, Paul D. Smith, Meric Srokosz, John A. Stephens, Peter K. Taylor, Maciej Telszewski, Roisin Walsh, Brian Ward, David K. Woolf, Dickon Young, and Henk Zemmelink (Bull. Amer. Meteor. Soc., 90, 629–644) • ©2009 American Meteorological Society • Corresponding author: Ian M. Brooks, Institute for Climate and Atmospheric Science, School of Earth and Environment, University of Leeds, Leeds LS2 9JT, United Kingdom • E-mail: i.brooks@see.leeds.ac.uk • DOI:10.1175/2008BAMS2578.2

We have used an AGCM (atmospheric general circulation model)-based Chemistry Transport Model (ACTM) for the simulation of methane (CH4) in the height range of earth’s surface to about 90 km. The model simulations are compared with measurements at hourly, daily, monthly and interannual time scales by filtering or averaging all the timeseries appropriately. From this model-observation comparison, we conclude that the recent (1990-2006) trends in growth rate and seasonal cycle at most measurement sites can be fairly successfully modeled by using existing knowledge of CH4 flux trends and seasonality. A large part of the interannual variability (IAV) in CH4 growth rate is apparently controlled by IAV in atmospheric dynamics at the tropical sites and forest fires in the high latitude sites. The flux amplitudes are optimized with respect to the available hydroxyl radical (OH) distribution and model transport for successful reproduction of latitudinal and longitudinal distribution of observed CH4 mixing ratio at the earth’s surface. Estimated atmospheric CH4 lifetime in this setup is 8.6 years. We found a small impact (less than 0.5 ppb integrated over 1 year) of OH diurnal variation, due to temperature dependence of reaction rate coefficient, on CH4 simulation compared to the transport related variability (order of ±15 ppb at interannual timescales). Model-observation comparisons of seasonal cycles, synoptic variations and diurnal cycles are shown to be useful for validating regional flux distribution patterns and strengths. Our results, based on two emission scenarios, suggest reduced emissions from temperate and tropical Asia region (by 13, 5, 3 Tg-CH4 for India, China and Indonesia, respectively), and compensating increase (by 9, 9, 3 Tg-CH4 for Russia, United States and Canada, respectively) in the boreal Northern Hemisphere (NH) are required for improved model-observation agreement.

The mixing ratios of HCFC-141b (1,1-dichlorofluoroethane) and HCFC-142b (1-chloro-1,1-difluoroethane) have been rising steadily in baseline air at Mace Head, Ireland over the 10-year period from 1994 to 2004. These HCFCs are widely used replacements for the chlorofluorocarbons phased out under the Montreal Protocol and its subsequent amendments. Analysis of the HCFC content of regionally-polluted air arriving at Mace Head from the European continent shows that European emissions reached a peak during 2000–2001 and have declined subsequently, following the phase-out in their usage. European emissions of HCFC-141b have been further constrained by observations at the High-Alpine Jungfraujoch site. The reductions are consistent with the phase-out of HCFC production and use from the year 2001 onwards mandated by European regulations designed to exceed the requirements of the Montreal Protocol.

HFC-365mfc (1,1,1,3,3-pentafluorobutane) is an industrial chemical used for polyurethane foam blowing. From early 2003, HFC-365mfc has been commercially produced as a substitute for HCFC-141b, whose use in Europe has been banned since January 2004. We describe the first detection of HFC-365mfc in the atmosphere and report on a 2 year long record at the high Alpine station of Jungfraujoch (Switzerland) and the Atlantic coast station of Mace Head (Ireland). The measurements at Jungfraujoch are used to estimate the central European emissions of HFC-365mfc, HCFC-141b, and CFC-11. For HFC-365mfc, we estimate the central European emissions (Germany, France, Italy, Switzerland, The Netherlands, Belgium, and Luxembourg) in 2003 and 2004 as 400-500 tonnes year(-1). These emissions are about one-third lower on a per capita basis than what we estimate from the Mace Head measurements for the total of Europe. The estimated emissions of HCFC-141b for central Europe are higher (i.e., 7.2-3.5 ktonnes year(-1)) with a decreasing trend in the period from 2000 to 2004. Residual emissions of CFC-11 are estimated at 2.4-4.7 ktonnes year(-1) in the same time period. The Po Valley (northern Italy) appears to be a main source region for HFC-365mfc and for the former blowing agents HCFC-141b and CFC-11. In 2004, the emissions of HFC-365mfc arose from a wider region of Europe, which we attribute to an increased penetration of HFC-365mfc into the European market.

Atmospheric trace-gas inversion refers to any technique used to predict spatial and temporal fluxes using mole-fraction measurements and atmospheric simulations obtained from computer models. Studies to date are most often of a data-assimilation flavour, which implicitly consider univariate statistical models with the flux as the variate of interest. This univariate approach typically assumes that the flux field is either a spatially correlated Gaussian process or a spatially uncorrelated non-Gaussian process with prior expectation fixed using flux inventories (e.g., NAEI or EDGAR in Europe). Here, we extend this approach in three ways. First, we develop a bivariate model for the mole-fraction field and the flux field. The bivariate approach allows optimal prediction of both the flux field and the mole-fraction field, and it leads to significant computational savings over the univariate approach. Second, we employ a lognormal spatial process for the flux field that captures both the lognormal characteristics of the flux field (when appropriate) and its spatial dependence. Third, we propose a new, geostatistical approach to incorporate the flux inventories in our updates, such that the posterior spatial distribution of the flux field is predominantly data-driven. The approach is illustrated on a case study of methane (CH$_4$) emissions in the United Kingdom and Ireland., 39 pages, 8 figures

The UK is one of several countries around the world that has enacted legislation to reduce its greenhouse gas emissions. In this study, we present top-down emissions of methane (CH4) and nitrous oxide (N2O) for the UK and Ireland over the period August~2012 to August~2014. These emissions were inferred using measurements from a network of four sites around the two countries. We used a hierarchical Bayesian inverse framework to infer fluxes as well as a set of covariance parameters that describe uncertainties in the system. We inferred average UK total emissions of 2.09 (1.65–2.67) Tg yr−1 CH4 and 0.101 (0.068–0.150) Tg yr−1 N2O and found our derived UK estimates to be generally lower than the a priori emissions, which consisted primarily of anthropogenic sources and with a smaller contribution from natural sources. We used sectoral distributions from the UK National Atmospheric Emissions Inventory (NAEI) to determine whether these discrepancies can be attributed to specific source sectors. Because of the distinct distributions of the two dominant CH4 emissions sectors in the UK, agriculture and waste, we found that the inventory may be overestimated in agricultural CH4 emissions. We found that annual mean N2O emissions were consistent with both the prior and the anthropogenic inventory but we derived a significant seasonal cycle in emissions. This seasonality is likely due to seasonality in fertilizer application and in environmental drivers such as temperature and rainfall, which are not reflected in the annual resolution inventory. Through the hierarchical Bayesian inverse framework, we quantified uncertainty covariance parameters and emphasized their importance for high-resolution emissions estimation. We inferred average model errors of approximately 20 and 0.4 ppb and correlation timescales of 1.0 (0.72–1.43) and 2.6 (1.9–3.9) days for CH4 and N2O, respectively. These errors are a combination of transport model errors as well as errors due to unresolved emissions processes in the inventory. We found the largest CH4 errors at the Tacolneston station in eastern England, which may be due to sporadic emissions from landfills and offshore gas in the North Sea.

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. However, our measurement-based estimates of individual HFC species suggest that emissions, from reporting countries, of the most abundant HFC, HFC-134a, were only 79% (63-95%) of the UNFCCC inventory total, while other HFC emissions were significantly greater than the reported values. These results suggest that there are inaccuracies in the reporting methods for individual HFCs, which appear to cancel when aggregated together.

The UK is one of several countries around the world that has enacted legislation to reduce its greenhouse gas emissions. Monitoring of emissions has been done through a detailed sectoral level bottom-up inventory (UK National Atmospheric Emissions Inventory, NAEI) from which national totals are submitted yearly to the United Framework Convention on Climate Change. In parallel, the UK government has funded four atmospheric monitoring stations to infer emissions through top-down methods that assimilate atmospheric observations. In this study, we present top-down emissions of methane (CH4) and nitrous oxide (N2O) for the UK and Ireland over the period August 2012 to August 2014. We used a hierarchical Bayesian inverse framework to infer fluxes as well as a set of covariance parameters that describe uncertainties in the system. We inferred average UK emissions of 2.08 (1.72–2.47) Tg yr−1 CH4 and 0.105 (0.087–0.127) Tg yr−1 N2O and found our derived estimates to be generally lower than the inventory. We used sectoral distributions from the NAEI to determine whether these discrepancies can be attributed to specific source sectors. Because of the distinct distributions of the two dominant CH4 emissions sectors in the UK, agriculture and waste, we found that the inventory may be overestimated in agricultural CH4 emissions. We also found that N2O fertilizer emissions from the NAEI may be overestimated and we derived a significant seasonal cycle in emissions. This seasonality is likely due to seasonality in fertilizer application and in environmental drivers such as temperature and rainfall, which are not reflected in the annual resolution inventory. Through the hierarchical Bayesian inverse framework, we quantified uncertainty covariance parameters and emphasized their importance for high-resolution emissions estimation. We inferred average model errors of approximately 20 and 0.4 ppb and correlation timescales of 1.0 (0.72–1.43) and 2.6 (1.9–3.9) days for CH4 and N2O, respectively. These errors are a combination of transport model errors as well as errors due to unresolved emissions processes in the inventory. We found the largest CH4 errors at the Tacolneston station in eastern England, which is possibly to do with sporadic emissions from landfills and offshore gas in the North Sea.

Here we present high frequency long-term observations of ethane, benzene and methyl chloride from the AGAGE Ragged Point, Barbados, monitoring station made using a custom built GC-MS system. Our analysis focuses on the first three years of data (2005–2007) and on the interpretation of periodic episodes of high concentrations of these compounds. We focus specifically on an exemplar episode during September 2007 to assess if these measurements are impacted by long-range transport of biomass burning and biogenic emissions. We use the Lagrangian Particle Dispersion model, NAME, run forwards and backwards in time to identify transport of air masses from the North East of Brazil during these events. To assess whether biomass burning was the cause we used hot spots detected using the MODIS instrument to act as point sources for simulating the release of biomass burning plumes. Excellent agreement for the arrival time of the simulated biomass burning plumes and the observations of enhancements in the trace gases indicates that biomass burning strongly influenced these measurements. These modelling data were then used to determine the emissions required to match the observations and compared with bottom up estimates based on burnt area and literature emission factors. Good agreement was found between the two techniques highlight the important role of biomass burning. The modelling constrained by in situ observations suggests that the emission factors were representative of their known upper limits, with the in situ data suggesting slightly greater emissions of ethane than the literature emission factors account for. Further analysis was performed concluding only a small role for biogenic emissions of methyl chloride from South America impacting measurements at Ragged Point. These results highlight the importance of long-term high frequency measurements of NMHC and ODS and highlight how these data can be used to determine sources of emissions 1000’s km away.

A global 3-D chemistry-transport model STOCHEM has been employed to study trends in the mole fractions of methane, carbon monoxide and ozone in baseline air masses entering Europe from the Atlantic Ocean over the period from 1990 to 2030. With a range of emission scenarios for man-made ozone precursor emission sources available, a wide range of model trends were predicted for the period up to 2030. In the scenario based on current planned air pollution controls, IIASA CLE, methane shows a strong upward trend, ozone shows a weaker upward trend, and carbon monoxide is approximately flat in baseline air masses. In one of the more pessimistic IPCC SRES scenarios, A2, all three gases show future increases. However, in the scenario based on maximum feasible emission reductions, IIASA MFR all three trace gases decline. By 2030, projected climate change reduces the growth in CH4, but has insignificant effects on baseline CO and O3 in these simulations. Global or hemispheric ozone precursor emissions and their controls exert a potentially large external influence on Europe’s air quality. This influence is currently not taken into account in future European air quality policy formulation. r 2005 Elsevier Ltd. All rights reserved.

In situ atmospheric observations of bromoform (CHBr3) made over a 2.5 year period at Mace Head, Ireland from May 2001- Dec 2003, including during the NAMBLEX (North Atlantic Marine Boundary Layer Experiment) campaign, show broad maxima from spring until autumn and winter minima, with mixing ratios of 5.3+1.0 pptv (mid March - mid October) and 1.8+0.8 pptv (December-February). This indicates that, unlike CHCl3, which has a summer minimum and winter maximum at Mace Head, local biological sources of CHBr3 have a greater influence on the atmospheric data than photochemical decay during long-range transport. The emission sources are predominantly macroalgal, but we find evidence for a small terrestrial flux from peatland ecosystems, which so far has not been accounted for in the CHBr3 budget. Sharp increases in CHCl3 and CHBr3 concentrations and decreases in O3 concentrations occurred at night when the wind direction switched from an ocean- to a land-based sector (land breeze) and the wind speed dropped to below 5 ms-1. These observations infer a shallow atmospheric boundary layer with increased O3 deposition and concentration of local emissions of both CHCl3 and CHBr3. The ratio of ΔCHCl3/ΔCHBr3 varied strongly according to the prevailing wind direction; from 0.60+0.15 in south-easterly (100-170° and northerly (340-20°) air to 2.5+0.4 in north-easterly (40-70°) air. Of these land-sectors, the south-easterly air masses are likely to be strongly influenced by macroalgal beds along the coast and the emission ratios probably reflect those from seaweeds in addition to land sources. The north-easterly airmasses however had an immediate fetch inland, which locally is comprised of coastal peatland ecosystems (peat bogs and coastal conifer plantations), previously identified as being strong sources of atmospheric CHCl3 under these conditions. Although we cannot entirely rule out other local land or coastal sources, our observations also suggest peatland ecosystem emissions of CHBr3. We use correlations between CHCl3 and CHBr3 during the north-easterly land breeze events in conjunction with previous estimates of local wetland CHCl3 release to tentatively deduce a global wetland CHBr3 source of 20.4(0.4-948) Gg yr-1, which is approximately 7% of the total global source.

Improved monitoring of non-CO2 greenhouse gases in air samples is presented, achieved using a new analytical system based on preconcentration, gas-chromatography and mass spectrometry. In addition to the major HFCs, HCFCs and CFCs, the new observations include the first in situ time series of the C1–C3 PFCs (CF4, C2F6 and C3F8) and the more volatile of the HFCs (CHF3, CH2F2, CH3CF3) alongside SF6, all of which are now monitored routinely as part of the Advanced Global Atmospheric Gases Experiment (AGAGE). Observed trends in newly monitored species are shown, obtained from 1–2 years continuous in situ air analyses at remote monitoring sites at Mace Head (Ireland) and Cape Grim (Australia). Observed deviations in the air background for these gas species are linked to modelled trajectories of air masses arriving at the monitoring stations to indicate potential source regions for emissions in Europe and Australia. In addition, preliminary estimates of 2004 mixing ratio growth rates of compounds are deduced from the observations, which highlight the importance of continuous atmospheric monitoring for verification of consumption-based emission estimates of non-CO2 greenhouse gases.

In situ AGAGE GC-MS measurements of methyl bromide (CH3Br) and methyl chloride (CH3Cl) at Mace Head, Ireland and Cape Grim, Tasmania (1998–2001) reveal a complex pattern of sources. At Mace Head both gases have well-defined seasonal cycles with similar average annual decreases of 3.0% yr−1 (CH3Br) and 2.6% yr−1 (CH3Cl), and mean northern hemisphere baseline mole fractions of 10.37 ± 0.05 ppt and 535.7 ± 2.2 ppt, respectively. We have used a Lagrangian dispersion model and local meteorological data to segregate the Mace Head observations into different source regions, and interpret the results in terms of the known sources and sinks of these two key halocarbons. At Cape Grim CH3Br and CH3Cl also show annual decreases in their baseline mixing ratios of 2.5% yr−1 and 1.5% yr−1, respectively. Mean baseline mole fractions were 7.94 ± 0.03 ppt (CH3Br) and 541.3 ± 1.1 ppt (CH3Cl). Although CH3Cl has astrong seasonal cycle there is no well-defined seasonal cycle in the Cape Grim CH3Br record. The fact that both gases are steadily decreasing in the atmosphere at both locations implies that a change has occurred which is affecting a common, major source of both gases (possibly biomass burning) and/or their major sink process (destruction by hydroxyl radical).

This study presents the quantification of the emissions of the refrigerants CFC-12 (CCl2F2), HCFC-22 (CHClF2), and HFC-134a (CF3CH2F) from road traffic in Switzerland. These gases are used as refrigerants in car air conditioning systems (A/C-systems) and in cool aggregates for refrigeration transport. All three substances act as greenhouse gases, and CFC-12 and HCFC-22 are in addition stratospheric ozone depleting chemicals. The measurements have been performed in a highway tunnel in the area of Zürich and cover a large number of individual vehicles, which are thought to be representative of a typical European car fleet. The average emission rates per vehicle were found to be 1.0 +/- 0.2 mg h(-1) for CFC-12, 0.6 +/- 0.4 mg h(-1) for HCFC-22, and 6.2 +/- 0.8 mg h(-1) for HFC-134a. These emission factors have been measured for driving vehicles and represent an average emission rate for all types of vehicles regardless of whether they are equipped with an A/C-unit or not. For an average vehicle equipped with an A/C-unit, these results translate into losses of about 14 mg h(-1) for HFC-134a and 20-30 mg h(-1) for CFC-12, when the estimated distribution of HFC-134a-A/C-units (45%) and CFC-12-A/C-units (3-5%) in the car fleet were taken into account. The emissions of CFC-12 and HFC-134a were mainly attributed to the losses from A/C-systems of passenger cars, whereas the emissions of HCFC-22 originate from losses of refrigeration systems of transport trucks. The observed emissions are discussed in respect to their environmental impact and compared to the overall greenhouse gas emissions of road traffic.

The results of a field campaign carried out from early spring through to the late summer of 2000, in Bristol, England, are presented. Continuous measurements of over 40 hydrocarbons have been made at an urban background site, located at Bristol University, for approximately nine months using a Gas Chromatography - Flame Ionisation Detection (GC-FID) system and for a selection of halocarbons for approximately one month using a Gas Chromatography - Electron Capture Detection (GC-ECD) system. In this paper we present the time-series of the nine halocarbons and selected hydrocarbons. Daytime and night-time hydroxyl radical concentrations have been estimated based on the diurnal variations of a selection of the measured hydrocarbons. The average summer daytime concentration of OH was found to be 2.5x106 molecules cm-3 and the night-time concentration to be in the range 104 to 105 molecules cm-3. In addition, the role played by certain VOCs in the formation of ozone is assessed using the POCP (Photochemical Ozone Creation Potential) concept.

A GC-ECD system has been used to make continuous measurements of nine halocarbons in the urban environment of Bristol, England over the course of about one month. A GC-FID system was deployed in the same location which simultaneously monitored over 30 C2–C8 hydrocarbons. In this paper, the halocarbon time series is presented and compared with the hydrocarbon data set. The influence of local sources is investigated by comparing the fluctuations in halocarbon concentrations with local weather conditions. A complex time series is seen, with no species displaying any clear diurnal cycle. Additionally, large deviations from baseline levels are observed for many of the compounds at different times. Local small-scale industry and landfill sites are postulated as the source of many of these excursions. The geography of Bristol has been found to influence levels of pollution in the city as the surrounding hills trap emissions and prevent their quick dispersion.

There are large uncertainties in identifying and quantifying the natural and anthropogenic sources of chloromethanes – methyl chloride (CH3Cl), chloroform (CHCl3) and dichloromethane (CH2Cl2), which are responsible for about 15% of the total chlorine in the stratosphere. We report two years of in situ observations of these species from the AGAGE (Advanced Global Atmospheric Gas Experiment) program at Cape Grim, Tasmania (41° S, 145° E). The average background levels of CH3Cl, CHCl3 and CH2Cl2 during 1998–2000 were 551± 8, 6.3± 0.2 and 8.9± 0.2 ppt (dry air mole fractions expressed in parts per 1012) respectively, with a two-year average amplitude of the seasonal cycles in background air of 25, 1.1 and 1.5 ppt respectively. The CH3Cl and CHCl3 records at Cape Grim show clear episodes of elevated mixing ratios up to 1300 ppt and 55 ppt respectively, which are highly correlated, suggesting common source(s). Trajectory analyses show that the sources of CH3Cl and CHCl3 that are responsible for these elevated observations are located in coastal-terrestrial and/or coastal-seawater regions in Tasmania and the south-eastern Australian mainland. Elevated levels of CH2Cl2 (up to 70 ppt above background) are associated mainly with emissions from the Melbourne/Port Phillip region, a large urban/industrial complex (population 3.5 million) 300 km north of Cape Grim.

An episode of exceptionally high PM10 and PM2.5 levels was observed during the night of the 2–3 March 2000 throughout England and Wales. The weather was characterised by strong westerly winds and widespread rainfall associated with a low pressure system to the north of Scotland, conditions usually associated with relatively clean, unpolluted air. Possible sources included volcanic ash from an eruption on 26 February 2000 in Iceland, or dust from large sandstorms over the Sahara. A combination of atmospheric transport modelling using the Lagrangian dispersion model NAME, an analyses of satellite imagery and observational data from Mace Head has shown that the most likely origin of the episode was long range transport of dust from the Sahara region of North Africa. Further modelling studies have revealed a number of previously unidentified dust episodes, and indicate that transport of dust from the Sahara can occur several times a year. Dust episodes are of interest for a number of reasons, particulate levels can be elevated over a wide area and in some instances can significantly exceeded current air quality standards. If a natural source is identified over which there can be no control, there are implications for the setting of air quality standards.

Methyl chloroform (MCF) is a man-made chlorinated solvent contributing to the destruction of stratospheric ozone and is controlled under the "Montreal Protocol on Substances that Deplete the Ozone Layer" and its amendments, which called for its phase-out in 1996 in developed countries and 2015 in developing countries. Long-term, high-frequency observations of MCF carried out at three European sites show a constant decline in the background mixing ratios of MCF. However, we observe persistent non-negligible mixing ratio enhancements of MCF in pollution episodes, suggesting unexpectedly high ongoing emissions in Europe. In order to identify the source regions and to give an estimate of the magnitude of such emissions, we have used a Bayesian inversion method and a point source analysis, based on high-frequency long-term observations at the three European sites. The inversion identified southeastern France (SEF) as a region with enhanced MCF emissions. This estimate was confirmed by the point source analysis. We performed this analysis using an 11-year data set, from January 2002 to December 2012. Overall, emissions estimated for the European study domain decreased nearly exponentially from 1.1 Gg yr−1 in 2002 to 0.32 Gg yr−1 in 2012, of which the estimated emissions from the SEF region accounted for 0.49 Gg yr−1 in 2002 and 0.20 Gg yr−1 in 2012. The European estimates are a significant fraction of the total semi-hemisphere (30–90° N) emissions, contributing a minimum of 9.8% in 2004 and a maximum of 33.7% in 2011, of which on average 50% are from the SEF region. On the global scale, the SEF region is thus responsible for a minimum of 2.6% (in 2003) and a maximum of 10.3% (in 2009) of the global MCF emissions.

N[subscript 2]O surface fluxes were estimated for 1999 to 2009 using a time-dependent Bayesian inversion technique. Observations were drawn from 5 different networks, incorporating 59 surface sites and a number of ship-based measurement series. To avoid biases in the inverted fluxes, the data were adjusted to a common scale and scale offsets were included in the optimization problem. The fluxes were calculated at the same resolution as the transport model (3.75° longitude × 2.5° latitude) and at monthly time resolution. Over the 11-year period, the global total N[subscript 2]O source varied from 17.5 to 20.1 Tg a[superscript −1] N. Tropical and subtropical land regions were found to consistently have the highest N[subscript 2]O emissions, in particular in South Asia (20 ± 3% of global total), South America (13 ± 4%) and Africa (19 ± 3%), while emissions from temperate regions were smaller: Europe (6 ± 1%) and North America (7 ± 2%). A significant multi-annual trend in N[subscript 2]O emissions (0.045 Tg a[superscript −2] N) from South Asia was found and confirms inventory estimates of this trend. Considerable interannual variability in the global N[subscript 2]O source was observed (0.8 Tg a[superscript −1] N, 1 standard deviation, SD) and was largely driven by variability in tropical and subtropical soil fluxes, in particular in South America (0.3 Tg a[superscript −1] N, 1 SD) and Africa (0.3 Tg a[superscript −1] N, 1 SD). Notable variability was also found for N[subscript 2]O fluxes in the tropical and southern oceans (0.15 and 0.2 Tg a[superscript −1] N, 1 SD, respectively). Interannual variability in the N[subscript 2]O source shows some correlation with the El Niño–Southern Oscillation (ENSO), where El Niño conditions are associated with lower N[subscript 2]O fluxes from soils and from the ocean and vice versa for La Niña conditions.

The hydroxyl radical (OH) is the dominant oxidizing chemical in the atmosphere. It destroys most air pollutants and many gases involved in ozone depletion and the greenhouse effect. Global measurements of 1,1,1-trichloroethane (CH 3 CCl 3 , methyl chloroform) provide an accurate method for determining the global and hemispheric behavior of OH. Measurements show that CH 3 CCl 3 levels rose steadily from 1978 to reach a maximum in 1992 and then decreased rapidly to levels in 2000 that were lower than the levels when measurements began in 1978. Analysis of these observations shows that global OH levels were growing between 1978 and 1988, but the growth rate was decreasing at a rate of 0.23 ± 0.18% year −2 , so that OH levels began declining after 1988. Overall, the global average OH trend between 1978 and 2000 was −0.64 ± 0.60% year −1 . These variations imply important and unexpected gaps in current understanding of the capability of the atmosphere to cleanse itself.

A technique is described for identifying probable source locations for a range of greenhouse and ozone-depleting trace gases from the long-term measurements made at Mace Head, Ireland. The Met. Office's dispersion model NAME is used to predict concentrations at Mace Head from all possible sources in Europe, then source regions identified as those which consistently lead to elevated concentrations at Mace Head. Estimates of European emissions and their distribution are presented for a number of trace gases for the period 1995–1998. Estimated emission patterns are realistic, given the nature and varied applications of the species considered. The results indicate that whilst there are limitations, useful information about source distribution can be extracted from continuous measurements at a remote site. It is probable that much improved estimates could be derived if observations were available from a number of sites. The ability to assess emissions has obvious implications in monitoring compliance with internationally agreed quota and protocols.

We describe in detail the instrumentation and calibrations used in the Atmospheric Lifetime Experiment (ALE), the Global Atmospheric Gases Experiment (GAGE), and the Advanced Global Atmospheric Gases Experiment (AGAGE) and present a history of the majority of the anthropogenic ozone-depleting and climate-forcing gases in air based on these experiments. Beginning in 1978, these three successive automated high-frequency in situ experiments have documented the long-term behavior of the measured concentrations of these gases over the past 20 years, and show both the evolution of latitudinal gradients and the high-frequency variability due to sources and circulation. We provide estimates of the long-term trends in total chlorine contained in long-lived halocarbons involved in ozone depletion. We summarize interpretations of these measurements using inverse methods to determine trace gas lifetimes and emissions. Finally, we provide a combined observational and modeled reconstruction of the evolution of chlorocarbons by latitude in the atmosphere over the past 60 years which can be used as boundary conditions for interpreting trapped air in glaciers and oceanic measurements of chlorocarbon tracers of the deep oceanic circulation. Some specific conclusions are as follows: (1) International compliance with the Montreal Protocol is so far resulting in chlorofluorocarbon and chlorocarbon mole fractions comparable to target levels; (2) mole fractions of total chlorine contained in long-lived halocarbons (CCl 2 F 2 , CCl 3 F, CH 3 CCl 3 , CCl 4 , CHClF 2 , CCl 2 FCClF 2 , CH 3 Cl, CH 2 Cl 2 , CHCl 3 , CCl 2 =CCl 2 ) in the lower troposphere reached maximum values of about 3.6 ppb in 1993 and are beginning to slowly decrease in the global lower atmosphere; (3) the chlorofluorocarbons have atmospheric lifetimes consistent with destruction in the stratosphere being their principal removal mechanism; (4) multiannual variations in chlorofluorocarbon and chlorocarbon emissions deduced from ALE/GAGE/AGAGE data are consistent approximately with variations estimated independently from industrial production and sales data where available (CCl 2 F 2 (CFC-12) and CCl 2 FCClF 2 (CFC-113) show the greatest discrepancies); (5) the mole fractions of the hydrochlorofluorocarbons and hydrofluorocarbons, which are replacing the regulated halocarbons, are rising very rapidly in the atmosphere, but with the exception of the much longer manufactured CHClF 2 (HCFC-22), they are not yet at levels sufficient to contribute significantly to atmospheric chlorine loading. These replacement species could in the future provide independent estimates of the global weighted-average OH concentration provided their industrial emissions are accurately documented; (6) in the future, analysis of pollution events measured using high-frequency in situ measurements of chlorofluorocarbons and their replacements may enable emission estimates at the regional level, which, together with industrial end-use data, are of sufficient accuracy to be capable of identifying regional noncompliance with the Montreal Protocol.

Continuous high-frequency (every 40-min) automatic measurements of hydrogen have been made at the Mace Head atmospheric research station on the Atlantic Ocean coast of Ireland throughout 1994–1998. These observations represent one the most comprehensive in situ records of a trace gas that has received comparatively little attention. Individual measurements have been sorted by four independent methods to separate clean, maritime air masses from regionally polluted European air masses. Hydrogen concentrations in midlatitude Northern Hemisphere baseline air show a distinct seasonal cycle with highest concentrations during spring and lowest concentrations during late autumn, with a peak-to-trough amplitude of 38±6 ppb, averaged over the observed seasonal cycles from 1994 to 1998. The mean hydrogen concentration in midlatitude Northern Hemisphere baseline air on January 1, 1995, was estimated as 496.5 ppb with an upward trend of 1.2±0.8 ppb yr−1. Evidence has also been obtained for European pollution sources with source strength of about 0.8 Tg yr−1 and for deposition of hydrogen to soils. The observation of slightly elevated hydrogen concentrations relative to baseline levels in tropical maritime air masses points to a latitudinal gradient in hydrogen with higher concentrations in lower latitudes of the Northern Hemisphere and in the Southern Hemisphere. This is confirmed by comparable hydrogen observations at Cape Grim, Tasmania, which are consistently higher than measurements recorded at Mace Head. Mean hemispheric concentrations of 504 and 520 ppb have been estimated for the Northern and Southern Hemispheres, respectively, for January 1, 1996, corresponding to a total atmospheric hydrogen burden of 182 Tg.

Chromatographic analysis of very volatile hydrohalocarbons and chlorofluorocarbons has proved to be a difficult task due to the generally poor retention of these compounds on commercially available wall coated open tubular capillary columns. Although porous layer open tubular (PLOT) capillary columns coated with alumina/KCl, or alumina/Na 2 SO 4 provide adequate resolution for this class of compound they induce dehydrochlorination of certain hydrohalocarbons. More recently PLOT columns coated with Porapak porous polymer materials Q, S and U have been shown to provide inadequate resolution and high column bleed at the high column temperatures required for separation. We present results from the analysis of mixtures of hydrohalocarbons, chlorofluorocarbons, halocarbons, and halons, using a commercially available cyclodextrin PLOT column.

During the EASE/OXICOA campaign of the NERC ACSOE programme, trichloroethylene and a wide range of man-made halocarbons and radiatively-active trace gases were monitored with high precision and high frequency throughout July 1996 at Mace Head on the Atlantic Ocean coast of Ireland. Trichloroethylene concentrations in concert with many other trace gases became elevated as regionally-polluted and photochemically-aged air masses reached Mace Head. However, as the anticyclonic air masses retreated during 19 and 20 July, trace gas concentrations remained elevated for a significant period. During this 2–4 day period, trichloroethylene concentrations decayed significantly, though the concentrations of the other more chemically-inert trace gases did not. A detailed interpretation of this behaviour using a Lagrangian dispersion model has allowed the estimation of average and peak OH radical concentrations of 3 and 9×106 molecule cm-3, respectively, during the travel from the source areas in the U.K. and the low countries out to Mace Head. Using a simple box model, the available Mace Head measurements, when combined into a detailed chemical mechanism, generated OH radical concentrations which peaked at 7×106 molecule cm-3, in close agreement with the estimates based on trichloroethylene decay.