# AGAGE Accomplishments: 2010-2015

As a record of the accomplishments in AGAGE, we provide below the abstracts of all AGAGE papers published in the last 6 years supported in whole or part by the current 5-year AGAGE grant from NASA (including papers led by non-AGAGE scientists but with AGAGE co-authors supported in whole or part by NASA).

Displaying 1 − 161 of 161 accomplishments.

### 2010

#### Inverse modeling of European CH4 emissions 2001–2006 (2010) [link]

Authors: Bergamaschi, Krol, Meirink, Dentener, Segers, van Aardenne, Monni, Vermeulen, Schmidt, Ramonet, Yver, Meinhardt, Nisbet, Fisher, O’Doherty, Dlugokencky

European CH4 emissions are estimated for the period 2001–2006 using a four-dimensional variational (4DVAR) inverse modeling system, based on the atmospheric zoom model TM5. Continuous observations are used from various European monitoring stations, complemented by European and global flask samples from the NOAA/ESRL network. The available observations mainly provide information on the emissions from northwest Europe (NWE), including the UK, Ireland, the BENELUX countries, France and Germany. The inverse modeling estimates for the total anthropogenic emissions from NWE are 21% higher compared to the EDGARv4.0 emission inventory and 40% higher than values reported to U.N. Framework Convention on Climate Change. Assuming overall uncertainties on the order of 30% for both bottom-up and top-down estimates, all three estimates can be still considered to be consistent with each other. However, the uncertainties in the uncertainty estimates prevent us from verifying (or falsifying) the bottom-up inventories in a strict sense. Sensitivity studies show some dependence of the derived spatial emission patterns on the set of atmospheric monitoring stations used, but the total emissions for the NWE countries appear to be relatively robust. While the standard inversions include a priori information on the spatial and temporal emission patterns from bottom-up inventories, a further sensitivity inversion without this a priori information results in very similar NWE country totals, demonstrating that the available observations provide significant constraints on the emissions from the NWE countries independent from bottom-up inventories.

#### On the effect of a global adoption of various fractions of biodiesel on key species in the troposphere (2010) [link]

Authors: Cooke, Marven, Utembe, Archibald, Ensor, Jenkin, Derwent, O’Doherty, Shallcross

Biodiesel use is being promoted worldwide as a green alternative to conventional diesel. A global three-dimensional chemistry transport model is employed to investigate the impact on air quality and global tropospheric composition of adopting biodiesel as a fractional component of diesel use. Five global simulations are conducted where emission changes of hydrocarbons and nitrogen oxides were applied within the model to investigate changes in tropospheric pollutants. Hydrocarbon emission reductions lead to an overall improvement in air quality with reductions in ozone, organic aerosol, aromatic species and PAN. However when the increase in NOx, caused by increased exhaust temperature, is included there is negligible difference in ozone production between mineral diesel and biodiesel blends. The cause of these effects is discussed.

#### A 15 year record of high-frequency, in situ measurements of hydrogen at Mace Head, Ireland (2010) [link]

Authors: Grant, Witham, Simmonds, Manning, O’Doherty

Continuous high-frequency measurements of atmospheric molecular hydrogen have been made at Mace Head atmospheric research station on the west coast of Ireland from March 1994 to December 2008. The presented data provides information on long term trends and seasonal cycles of hydrogen in background northern hemispheric air. Individual measurements have been sorted using a Lagrangian dispersion model to separate clean background air from regionally polluted European air masses and those transported from southerly latitudes. No significant trend was observed in background northern hemispheric air over the 15 year record, elevations in yearly means were accounted for from large scale biomass burning events. Seasonal cycles show the expected pattern with maxima in spring and minima in late autumn. The mean hydrogen mole fraction in baseline northern hemispheric air was found to be 500.1 ppb. Air transported from southerly latitudes showed an elevation from baseline mean of 11.0 ppb, reflecting both the latitudinal gradient of hydrogen, with higher concentrations in the Southern Hemisphere, and the photochemical source of hydrogen from low northern latitudes. European polluted air masses arriving at Mace Head showed mean elevation of 5.3 ppb from baseline air masses, reflecting hydrogen's source from primary emissions like fossil fuel combustion. Forward modelling of transport of hydrogen to Mace Head suggests that the ratio of hydrogen to carbon monoxide in primary emissions is considerably less in non-traffic sources than traffic sources.

#### High-frequency urban measurements of molecular hydrogen and carbon monoxide in the United Kingdom (2010) [link]

Authors: Grant, Stanley, Henshaw, Shallcross, O’Doherty

High-frequency measurements of atmospheric molecular hydrogen (H2) and carbon monoxide (CO) were made at an urban site in the United Kingdom (UK) from mid-December, 2008 until early March, 2009. Very few measurements of H2 exist in the urban environment, particularly within the UK, but are an essential component in the assessment of anthropogenic emissions of H2 and to a certain extent CO. These data provide detailed information on urban time-series, diurnal cycles as well as sources and sinks of both H2 and CO at urban locations. High-frequency data were found to be strongly influenced by local meteorological conditions of wind speed and temperature. Diurnal cycles were found to follow transport frequency very closely due to the sites proximity to major carriageways, consequently a strong correlation was found between H2 and CO mole fractions. Background subtracted mean and rush hour molar H2/CO emission ratios of 0.53±0.08 and 0.57±0.06 respectively, were calculated from linear fitting of data. The scatter plot of all H2 and CO data displayed an unusual two population pattern, thought to be associated with a large industrial area 85 km to the west of the site. However, the definitive source of this two branch pattern could not be fully elucidated. H2 emissions from transport in the UK were estimated to be 188±39 Gg H2/yr, with 8.1±2.3 Tg/yr of H2 produced from vehicle emissions globally. H2 and CO deposition velocities were calculated during stable night-time inversion events when a clear decay of both species was observed. CO was found to have a much higher deposition velocity than H2, 1.3±0.8×10−3 and 2.2±1.5×10−4 m s−1 (1σ) respectively, going against the law of molecular diffusivity. The source of this unusual result was investigated, however no conclusive explanation was found for increased loss of CO over H2 during stable night time inversion events.

#### The municipal solid waste landfill as a source of ozone-depleting substances in the United States and United Kingdom (2010) [link]

Authors: Hodson, Martin, Prinn

This study provides observation-based national estimates of CFC-11, CFC-12, CFC-113, and 1,1,1-trichloroethane emissions for the United States (US) and United Kingdom (UK) from municipal solid waste (MSW) landfills. The scarcity of national estimates has lead to the assumption that a significant fraction of the lingering ozone-depleting substance (ODS) emissions, which have been detected in industrialized countries, could be emitted from landfills. Spatial coverage was achieved through sampling at seven landfills in Massachusetts and through data provided by nine UK landfills. Linear least square regressions of recovered ODS vs. CH4 were used in combination with national estimates of landfill CH4 emissions to estimate 2006 national US and UK ODS landfill emissions. The ODS landfill emission estimates were then compared to recent estimates of total US and UK ODS emissions. US ODS landfill emissions are 0.4%–1% (0.006–0.09 Gg/year) of total US emissions. UK ODS landfill emission estimates are 1% (0.008 Gg/year) and 6% (0.03 Gg/year) of total UK CFC-11 and CFC-12 emissions, respectively. This indicates that landfills are only a minor source of lingering ODS emissions in the US, but may be more significant for CFC-12 emissions in the UK. The implication is that the majority of current ODS emissions in industrialized countries is likely coming from equipment still in use.

#### Regional atmospheric emissions determined from measurements at Jeju Island, Korea: Halogenated compounds from China (2010) [link]

Authors: Kim, Kim, Stohl, Mühle, Kim, Park, Kang, Lee, Harth, Salameh, Weiss

High-frequency in-situ measurements of a wide range of halogenated compounds including chlorofluorocarbons (CFCs), halons, hydrochlorofluorocarbons (HCFCs), hydrofluorocarbons (HFCs), perfluorinated compounds (PFCs), sulfur hexafluoride (SF6), and other chlorinated and brominated compounds have been made at Gosan (Jeju Island, Korea). Regional emissions of HCFC-22 (CHClF2) calculated from inverse modeling were combined with interspecies correlation methods to estimate national emissions for China, a major emitter of industrial halogenated gases. Our results confirm the signs of successful phase-out of primary ozone-depleting species such as CFCs, halons and many chlorinated or brominated compounds, along with substantial emissions of replacement HCFCs. Emissions derived for HFCs, PFCs, and SF6 were compared to published estimates and found to be a significant fraction of global totals. Overall, Chinese emissions of the halogenated compounds discussed here represent 19(14–17)% and 20(15–26)% of global emissions when evaluated in terms of their Ozone Depletion Potentials and 100-year Global Warming Potentials, respectively.

#### Reactive Halogens in the Marine Boundary Layer (RHaMBLe): the tropical North Atlantic experiments (2010) [link]

Authors: Lee, McFiggans, Allan, Baker, Ball, Benton, Carpenter, Commane, Finley, Evans, Fuentes, Furneaux, Goddard, Good, Hamilton, Heard, Herrmann, Hollingsworth, Hopkins, Ingham, Irwin, Jones, Jones, Keene, Lawler, Lehmann, Lewis, Long, Mahajan, Methven, Moller, Müller, Müller, Niedermeier, O’Doherty, Oetjen, Plane, Pszenny, Read, Saiz-Lopez, Saltzman, Sander, von Glasow, Whalley, Wiedensohler, Young

The NERC UK SOLAS-funded Reactive Halogens in the Marine Boundary Layer (RHaMBLe) programme comprised three field experiments. This manuscript presents an overview of the measurements made within the two simultaneous remote experiments conducted in the tropical North Atlantic in May and June 2007. Measurements were made from two mobile and one ground-based platforms. The heavily instrumented cruise D319 on the RRS Discovery from Lisbon, Portugal to São Vicente, Cape Verde and back to Falmouth, UK was used to characterise the spatial distribution of boundary layer components likely to play a role in reactive halogen chemistry. Measurements onboard the ARSF Dornier aircraft were used to allow the observations to be interpreted in the context of their vertical distribution and to confirm the interpretation of atmospheric structure in the vicinity of the Cape Verde islands. Long-term ground-based measurements at the Cape Verde Atmospheric Observatory (CVAO) on São Vicente were supplemented by long-term measurements of reactive halogen species and characterisation of additional trace gas and aerosol species during the intensive experimental period. This paper presents a summary of the measurements made within the RHaMBLe remote experiments and discusses them in their meteorological and chemical context as determined from these three platforms and from additional meteorological analyses. Air always arrived at the CVAO from the North East with a range of air mass origins (European, Atlantic and North American continental). Trace gases were present at stable and fairly low concentrations with the exception of a slight increase in some anthropogenic components in air of North American origin, though NOx mixing ratios during this period remained below 20 pptv (note the non-IUPAC adoption in this manuscript of pptv and ppbv, equivalent to pmol mol−1 and nmol mol−1 to reflect common practice). Consistency with these air mass classifications is observed in the time series of soluble gas and aerosol composition measurements, with additional identification of periods of slightly elevated dust concentrations consistent with the trajectories passing over the African continent. The CVAO is shown to be broadly representative of the wider North Atlantic marine boundary layer; measurements of NO, O3 and black carbon from the ship are consistent with a clean Northern Hemisphere marine background. Aerosol composition measurements do not indicate elevated organic material associated with clean marine air. Closer to the African coast, black carbon and NO levels start to increase, indicating greater anthropogenic influence. Lower ozone in this region is possibly associated with the increased levels of measured halocarbons, associated with the nutrient rich waters of the Mauritanian upwelling. Bromide and chloride deficits in coarse mode aerosol at both the CVAO and on D319 and the continuous abundance of inorganic gaseous halogen species at CVAO indicate significant reactive cycling of halogens.
Aircraft measurements of O3 and CO show that surface measurements are representative of the entire boundary layer in the vicinity both in diurnal variability and absolute levels. Above the inversion layer similar diurnal behaviour in O3 and CO is observed at lower mixing ratios in the air that had originated from south of Cape Verde, possibly from within the ITCZ. ECMWF calculations on two days indicate very different boundary layer depths and aircraft flights over the ship replicate this, giving confidence in the calculated boundary layer depth.

#### The global SF6 source inferred from long-term high precision atmospheric measurements and its comparison with emission inventories (2010) [link]

Authors: Levin, Naegler, Heinz, Osusko, Cuevas, Engel, Ilmberger, Langenfelds, Neininger, Rohden, Steele, Weller, Worthy, Zimov

Emissions of sulphur hexafluoride (SF6), one of the strongest greenhouse gases on a per molecule basis, are targeted to be collectively reduced under the Kyoto Protocol. Because of its long atmospheric lifetime (estimated as 800 to 3200 years), the accumulation of SF6 in the atmosphere is a direct measure of its global emissions. Examination of our extended data set of globally distributed high-precision SF6 observations shows an increase in SF6 abundance from near zero in the 1970s to a global mean of 6.7 ppt by the end of 2008. In-depth evaluation of our long-term data records shows that the global source of SF6 decreased after 1995, most likely due to SF6 emission reductions in industrialised countries, but increased again after 1998. By subtracting those emissions reported by Annex I countries to the United Nations Framework Convention of Climatic Change (UNFCCC) from our observation-inferred SF6 source leaves a surprisingly large gap of more than 70–80% of non-reported SF6 emissions in the last decade. This suggests a strong under-estimation of emissions in Annex I countries and underlines the urgent need for independent atmospheric verification of greenhouse gases emissions accounting.

#### HFC-23 (CHF3) emission trend response to HCFC-22 (CHClF2) production and recent HFC-23 emission abatement measures (2010) [link]

Authors: Miller, Rigby, Kuijpers, Krummel, Steele, Leist, Fraser, McCulloch, Harth, Salameh, Mühle, Weiss, Prinn, Wang, O’Doherty, Greally, Simmonds

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.

#### Perfluorocarbons in the global atmosphere: tetrafluoromethane, hexafluoroethane, and octafluoropropane (2010) [link]

Authors: Mühle, Ganesan, Miller, Salameh, Harth, Greally, Rigby, Porter, Steele, Trudinger, Krummel, O’Doherty, Fraser, Simmonds, Prinn, Weiss

We present atmospheric baseline growth rates from the 1970s to the present for the long-lived, strongly infrared-absorbing perfluorocarbons (PFCs) tetrafluoromethane (CF4), hexafluoroethane (C2F6), and octafluoropropane (C3F8) in both hemispheres, measured with improved accuracies (~1–2%) and precisions (<0.3%, or <0.2 ppt (parts per trillion dry air mole fraction), for CF4; <1.5%, or <0.06 ppt, for C2F6; <4.5%, or <0.02 ppt, for C3F8 within the Advanced Global Atmospheric Gases Experiment (AGAGE). Pre-industrial background values of 34.7±0.2 ppt CF4 and 0.1±0.02 ppt C2F6 were measured in air extracted from Greenland ice and Antarctic firn. Anthropogenic sources are thought to be primary aluminum production (CF4, C2F6, C3F8), semiconductor production (C2F6, CF4, C3F8) and refrigeration use (C3F8). Global emissions calculated with the AGAGE 2-D 12-box model are significantly higher than most previous emission estimates. The sum of CF4 and C2F6 emissions estimated from aluminum production and non-metal production are lower than observed global top-down emissions, with gaps of ~6 Gg/yr CF4 in recent years. The significant discrepancies between previous CF4, C2F6, and C3F8 emission estimates and observed global top-down emissions estimated from AGAGE measurements emphasize the need for more accurate, transparent, and complete emission reporting, and for verification with atmospheric measurements to assess the emission sources of these long-lived and potent greenhouse gases, which alter the radiative budget of the atmosphere, essentially permanently, once emitted.

#### Methane from the East Siberian Arctic Shelf (2010) [link]

Authors: Petrenko, Etheridge, Weiss, Brook, Schaefer, Severinghaus, Smith, Lowe, Hua, Riedel

In their Report “Extensive methane venting to the atmosphere from sediments of the East Siberian Arctic Shelf” (5 March, p. 1246), N. Shakhova et al. write that methane (CH4) release resulting from thawing Arctic permafrost “is a likely positive feedback to climate warming.” They add that the release of Arctic CH4 was implied in previous climate shifts as well as in the recently renewed rise in atmospheric CH4. These claims are not supported by all the literature they cite. Their reference 5 (1) presents measurements of emissions only of carbon dioxide, not CH4. Their reference 8 (2), a study we conducted, suggests that a very large (~50%) increase in atmospheric CH4 concentration associated with an abrupt warming event ~11,600 years ago was driven mainly by wetlands, without distinguishing between high and low latitudes. Their reference 9 (3) was published in 1993 and is not relevant to the renewed growth of atmospheric CH4 that started in 2007. Their reference 10 (4) does not imply Arctic CH4 releases in this renewed growth, and other recent work (5) also does not support sustained new emissions from the Arctic as the cause. These findings of CH4 emissions from the Arctic sea floor [in the Report and in (6)] add to our understanding of the atmospheric CH4 budget, but they do not show that Arctic warming has produced a positive feedback in radiative forcing by causing these emissions to increase recently. A newly discovered CH4 source is not necessarily a changing source, much less a source that is changing in response to Arctic warming. Shakhova et al. do acknowledge these distinctions, but in these times of enhanced scrutiny of climate change science, it is important to communicate all evidence to the scientific community and the public clearly and accurately.

#### Progress in the global phase-out of methyl bromide and the relative effectiveness of soil disinfestations strategies (2010) [link]

Authors: Porter, Pizano, Besri, Fraser

The Montreal Protocol which regulates ozone depleting gases is the most effective environmental protocol and now has a commitment from all Parties in the world. It has dramatically reduced consumption of the major ozone depleting chemical, methyl bromide (MB), and represents an excellent model for future phaseout of other environmentally damaging products, such as those involved with climate change. Over a fifteen year period, 85% of MB (c. 45,000 t) used for preplant soil fumigation has been phased out and a wide range of chemical and non chemical technologies adopted for disease and weed control in agriculture. In addition to use of alternative fumigants there has been an increased use of substrate systems, grafting and plant resistance for disease control which, in most cases, avoid the need for soil disinfestation. An international metaanalysis has shown that other fumigants, such as 1,3-dichloropropene (1,3 D)/chloropicrin (Pic), metham sodium, iodomethane (MI)/Pic, with or without barrier films are effective and these also have been adopted by growers as alternatives strategies for soil disinfestation with generally equivalent yields to MB. The implementation of these alternatives has led to a 45% fall in bromine in the atmosphere and this is very important to ozone layer recovery. Internationally, pressure is mounting to restrict use of all fumigants worldwide (EC Reg 2037/US Cluster Analysis) and this will further stimulate new technologies for plant disease control. There are also moves to restrict MB, approx. 10,300 tonnes a year, used for quarantine and pre-shipment (QPS). The pressure on fumigant use globally will continue to stimulate development of more sustainable integrated pest management (IPM) strategies that are beneficial to soil health and crop yields.

#### History of atmospheric SF6 from 1973 to 2008 (2010) [link]

Authors: Rigby, Mühle, Miller, Prinn, Krummel, Steele, Fraser, Salameh, Harth, Weiss, Greally, O’Doherty, Simmonds, Vollmer, Reimann, Kim, Kim, Wang, Olivier, Dlugokencky, Dutton, Hall, Elkins

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.

#### Deep air convection in the firn at a zero-accumulation site, central Antarctica (2010) [link]

Authors: Severinghaus, Albert, Courville, Fahnestock, Kawamura, Montzka, Mühle, Scambos, Shields, Shuman, Suwa, Tans, Weiss

Ice cores provide unique archives of past atmospheres and climate, but interpretation of trapped-gas records and their climatic significance has been hampered by a poor knowledge of the prevalence of air convection in the firn layer on top of polar ice sheets. In particular, the phasing of greenhouse gases and climate from ice cores has been obscured by a discrepancy between empirical and model-based estimates of the age difference between trapped gases and enclosing ice, which may be due to air convection. Here we show that deep air convection (> 23 m) occurs at a windy, near-zero-accumulation rate site in central Antarctica known informally as the Megadunes site (80.77914 °S, 124.48796 °E). Deep convection is evident in depth profiles of air withdrawn from the firn layer, in the observed pattern of the nitrogen isotope ratio 15N/14N, the argon isotope ratio 40Ar/36Ar, and in the mixing ratios of the anthropogenic halocarbons methyl chloroform (CH3CCl3) and HFC-134a (CH2FCF3). Transport parameters (diffusivities) were inferred and air was dated using measured carbon dioxide (CO2) and methane (CH4) mixing ratios, by comparing with the Law Dome atmospheric record, which shows that these are the oldest firn air samples ever recovered (CO2 mean age = 1863 AD). The low accumulation rate and the consequent intense metamorphism of the firn (due to prolonged exposure to seasonal temperature cycling) likely contribute to deep air convection via large grain size and vertical cracks that act as conduits for vigorous air motion. The Megadunes site provides a possible modern analog for the glacial conditions in the Vostok, Dome Fuji, and Dome C ice core records and a possible explanation for lower-than-expected 15N/14N ratios in trapped air bubbles at these times. A general conclusion is that very low accumulation rate causes deep air convection via its effect on firn structural characteristics.

#### Natural chloroform emissions from the blanket peat bogs in the vicinity of Mace Head, Ireland over a 14-year period (2010) [link]

Authors: Simmonds, Derwent, Manning, O’Doherty, Spain

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.

#### Hydrochlorofluorocarbon and hydrofluorocarbon emissions in East Asia determined by inverse modeling (2010) [link]

Authors: Stohl, Kim, Li, O’Doherty, Mühle, Salameh, Saito, Vollmer, Wan, Weiss, Yao, Yokouchi, Zhou

The emissions of three hydrochlorofluorocarbons, HCFC-22 (CHClF2), HCFC-141b (CH3CCl2F) and HCFC-142b (CH3CClF2) and three hydrofluorocarbons, HFC-23 (CHF3), HFC-134a (CH2FCF3) and HFC-152a (CH3CHF2) from four East Asian countries and the Taiwan region for the year 2008 are determined by inverse modeling. The inverse modeling is based on in-situ measurements of these halocarbons at the Japanese stations Cape Ochi-ishi and Hateruma, the Chinese station Shangdianzi and the South Korean station Gosan. For every station and every 3 h, 20-day backward calculations were made with the Lagrangian particle dispersion model FLEXPART. The model output, the measurement data, bottom-up emission information and corresponding uncertainties were fed into an inversion algorithm to determine the regional emission fluxes. The model captures the observed variation of halocarbon mixing ratios very well for the two Japanese stations but has difficulties explaining the large observed variability at Shangdianzi, which is partly caused by small-scale transport from Beijing that is not adequately captured by the model. Based on HFC-23 measurements, the inversion algorithm could successfully identify the locations of factories known to produce HCFC-22 and emit HFC-23 as an unintentional byproduct. This lends substantial credibility to the inversion method. We report national emissions for China, North Korea, South Korea and Japan, as well as emissions for the Taiwan region. Halocarbon emissions in China are much larger than the emissions in the other countries together and contribute a substantial fraction to the global emissions. Our estimates of Chinese emissions for the year 2008 are 65.3±6.6 kt/yr for HCFC-22 (17% of global emissions extrapolated from Montzka et al., 2009), 12.1±1.6 kt/yr for HCFC-141b (22%), 7.3±0.7 kt/yr for HCFC-142b (17%), 6.2±0.7 kt/yr for HFC-23 (>50%), 12.9±1.7 kt/yr for HFC-134a (9% of global emissions estimated from Velders et al., 2009) and 3.4±0.5 kt/yr for HFC-152a (7%).

#### Statistical analysis of eight surface ozone measurement series for various sites in Ireland (2010) [link]

Authors: Tripathi, Jennings, O'Dowd, Coleman, Leinert, O'Leary, Moran, O’Doherty, Spain

Data from various stations having different measurement record periods between 1988 and 2007 are analyzed to investigate the surface ozone concentration, long-term trends, and seasonal changes in and around Ireland. Time series statistical analysis is performed on the monthly mean data using seasonal and trend decomposition procedures and the Box-Jenkins approach (autoregressive integrated moving average). In general, ozone concentrations in the Irish region are found to have a negative trend at all sites except at the coastal sites of Mace Head and Valentia. Data from the most polluted Dublin city site have shown a very strong negative trend of −0.33 ppb/yr with a 95% confidence limit of 0.17 ppb/yr (i.e., −0.33 ± 0.17) for the period 2002−2007, and for the site near the city of Cork, the trend is found to be −0.20 ± 0.11 ppb/yr over the same period. The negative trend for other sites is more pronounced when the data span is considered from around the year 2000 to 2007. Rural sites of Wexford and Monaghan have also shown a very strong negative trend of −0.99 ± 0.13 and −0.58 ± 0.12, respectively, for the period 2000−2007. Mace Head, a site that is representative of ozone changes in the air advected from the Atlantic to Europe in the marine planetary boundary layer, has shown a positive trend of about +0.16 ± 0.04 ppb per annum over the entire period 1988−2007, but this positive trend has reduced during recent years (e.g., in the period 2001−2007). Cluster analysis for back trajectories are performed for the stations having a long record of data, Mace Head and Lough Navar. For Mace Head, the northern and western clean air sectors have shown a similar positive trend (+0.17 ± 0.02 ppb/yr for the northern sector and +0.18 ± 0.02 ppb/yr for the western sector) for the whole period, but partial analysis for the clean western sector at Mace Head shows different trends during different time periods with a decrease in the positive trend since 1988 indicating a deceleration in the ozone trend for Atlantic air masses entering Europe.

#### Optimal estimation of the surface fluxes of methyl chloride using a 3-D global chemical transport model (2010) [link]

Authors: Xiao, Prinn, Fraser, Simmonds, Weiss, O’Doherty, Miller, Salameh, Harth, Krummel, Porter, Mühle, Greally, Cunnold, Wang, Montzka, Elkins, Dutton, Thompson, Butler, Hall, Reimann, Vollmer, Stordal, Lunder, Maione, Arduini, Yokouchi

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

#### Atmospheric three-dimensional inverse modeling of regional industrial emissions and global oceanic uptake of carbon tetrachloride (2010) [link]

Authors: Xiao, Prinn, Fraser, Weiss, Simmonds, O’Doherty, Miller, Salameh, Harth, Krummel, Golombek, Porter, Butler, Elkins, Dutton, Hall, Steele, Wang, Cunnold

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.

#### The seasonal cycles and photochemistry of C2–C5 alkanes at Mace Head (2010) [link]

Authors: Yates, Derwent, Simmonds, Greally, O’Doherty, Shallcross

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.

#### Analysis of 3-year observations of CFC-11, CFC-12 and CFC-113 from a semi-rural site in China (2010) [link]

Authors: Zhang, Zhou, Yao, Vollmer, Greally, Simmonds, Reimann, Stordal, Maione, Xu, Zhang

In-situ measurements of atmospheric chlorofluorocarbons (CFCs) can be used to the assess their global and regional emissions and to check for compliance with phase-out schedules under Montreal protocol and its amendments. The atmospheric mixing ratios of CFC-11 (CCl3F), CFC-12 (CCl2F2) and CFC-113 (CCl2F–CClF2) have been measured by an automated in-situ GC-ECDs system at the regional Chinese Global Atmosphere Watch (GAW) station Shangdianzi (SDZ), from November 2006 to October 2009. The time series for these three principal CFCs showed large episodic events and background conditions occurred for approximately 30% (CFC-11), 52% (CFC-12) and 56% (CFC-113) of the measurements. The mean background mixing ratios for CFC-11, CFC-12 and CFC-113 were 244.8 ppt (parts per trillion, 10−12, molar) 539.6 ppt and 76.8 ppt, respectively, for 2006–2009. The enhanced CFC mixing ratios compared to AGAGE sites such as Trinidad Head (THD), US and Mace Head (MHD), Ireland suggest regional influences even during background conditions at SDZ, which is much closer to highly-populated areas. Between 2006 and 2009 background CFCs exhibited downward trends at rates of −2.0 ppt yr−1 for CFC-11, −2.5 ppt yr−1 for CFC-12 and −0.7 ppt yr−1 for CFC-113. De-trended 3-year average background seasonal cycles displayed small fluctuations with peak-to-trough amplitudes of 1.0 ± 0.02 ppt (0.4%) for background CFC-11, 1.3 ± 2.1 ppt (0.3%) for CFC-12 and 0.2 ± 0.4 ppt (0.3%) for CFC-113. On the other hand, during pollution periods these CFCs showed much larger seasonal cycles of 11.2 ± 10.7 ppt (5%) for CFC-11, 7.5 ± 6.5 ppt (2%) for CFC-12 and 1.0 ± 1.2 ppt (1.2%) for CFC-113, with apparent winter minima and early summer maxima. This enhancement was attributed to prevailing wind directions from urban regions in summer and to enhanced anthropogenic sources during the warm season. In general, horizontal winds from northeast showed negative contribution to atmospheric CFCs loading, whereas South Western advection (urban sector: Beijing) had positive contributions.

### 2011

#### Emissions of Halogenated Compounds in East Asia Determined from Measurements at Jeju Island, Korea (2011) [link]

Authors: Kim, Kim, Mühle, Kim, Park, Stohl, Kang, Arnold, Harth, Salameh, Weiss

High-frequency in situ measurements at Gosan (Jeju Island, Korea) during November 2007 to December 2008 have been combined with interspecies correlation analysis to estimate national emissions of halogenated compounds (HCs) in East Asia, including the chlorofluorocarbons (CFCs), halons, hydrochlorofluorocarbons (HCFCs), hydrofluorocarbons (HFCs), perfluorocarbons (PFCs), sulfur hexafluoride (SF6), and other chlorinated and brominated compounds. Our results suggest that overall China is the dominant emitter of HCs in East Asia, however significant emissions are also found in South Korea, Japan and Taiwan for HFC-134a, HFC-143a, C2F6, SF6, CH3CCl3, and HFC-365mfc. The combined emissions of CFCs, halon-1211, HCFCs, HFCs, PFCs, and SF6 from all four countries in 2008 are 25.3, 1.6, 135, 42.6, 3.6, and 2.0 kt/a, respectively. They account for approximately 15%, 26%, 29%, 16%, 32%, and 26.5% of global emissions, respectively. Our results show signs that Japan has successfully phased out CFCs and HCFCs in compliance with the Montreal Protocol (MP), Korea has started transitioning from HCFCs to HFCs, while China still significantly consumes HCFCs. Taiwan, while not directly regulated under the MP, is shown to have adapted the use of HFCs. Combined analysis of emission rates and the interspecies correlation matrix presented in this study proves to be a powerful tool for monitoring and diagnosing changes in consumption of HCs in East Asia.

#### Source attribution of the changes in atmospheric methane for 2006–2008 (2011) [link]

Authors: Bousquet, Ringeval, Pison, Dlugokencky, Brunke, Carouge, Chevallier, Fortems-Cheiney, Frankenberg, Hauglustaine, Krummel, Langenfelds, Ramonet, Schmidt, Steele, Szopa, Yver, Viovy, Ciais

The recent increase of atmospheric methane is investigated by using two atmospheric inversions to quantify the distribution of sources and sinks for the 2006–2008 period, and a process-based model of methane emissions by natural wetland ecosystems. Methane emissions derived from the two inversions are consistent at a global scale: emissions are decreased in 2006 (−7 Tg) and increased in 2007 (+21 Tg) and 2008 (+18 Tg), as compared to the 1999–2006 period. The agreement on the latitudinal partition of the flux anomalies for the two inversions is fair in 2006, good in 2007, and not good in 2008. In 2007, a positive anomaly of tropical emissions is found to be the main contributor to the global emission anomalies (~60–80%) for both inversions, with a dominant share attributed to natural wetlands (~2/3), and a significant contribution from high latitudes (~25%). The wetland ecosystem model produces smaller and more balanced positive emission anomalies between the tropics and the high latitudes for 2006, 2007 and 2008, mainly due to precipitation changes during these years. At a global scale, the agreement between the ecosystem model and the inversions is good in 2008 but not satisfying in 2006 and 2007. Tropical South America and Boreal Eurasia appear to be major contributors to variations in methane emissions consistently in the inversions and the ecosystem model. Finally, changes in OH radicals during 2006–2008 are found to be less than 1% in inversions, with only a small impact on the inferred methane emissions.

#### A three-dimensional synthesis inversion of the molecular hydrogen cycle: Sources and sinks budget and implications for the soil uptake (2011) [link]

Authors: Bousquet, Yver, Pison, Li, Fortems, Hauglustaine, Szopa, Rayner, Novelli, Langenfelds, Steele, Ramonet, Schmidt, Foster, Morfopoulos, Ciais

Our understanding of the global budget of atmospheric hydrogen (H2) contains large uncertainties. An atmospheric Bayesian inversion of H2 sources and sinks is presented for the period 1991–2004, based on a two networks of flask measurement stations. The types of fluxes and the spatial scales potentially resolvable by the inversion are first estimated from an analysis of the correlations of errors between the different processes and regions emitting or absorbing H2. Then, the estimated budget of H2 and its uncertainties is presented and discussed, for five groups of fluxes and three groups of large regions, in terms of mean fluxes, seasonal and interannual variations, and long-term trends. One main focus of the study is the improvement of the estimate of H2 soil uptake, which is the largest sink of H2. Various sensitivity tests are performed defining an ensemble of more than 20 inversions. We show that inferring a robust estimate of the H2 soil uptake requires to prescribe the prior magnitude of some other sources and sinks with a small uncertainty. Doing so an estimate of the H2 soil uptake of −62 ± 3 Tg y−1 is inferred for the period 1991–2004 (the uncertainty is the residual error after inversion). The inferred soil H2 sink presents a negative long-term trend that is qualitatively consistent with a bottom-up process-based model.

#### Inverse modelling of European N2O emissions: assimilating observations from different networks (2011) [link]

Authors: Corazza, Bergamaschi, Vermeulen, Aalto, Haszpra, Meinhardt, O’Doherty, Thompson, Moncrieff, Popa, Steinbacher, Jordan, Dlugokencky, Brühl, Krol, Dentener

We describe the setup and first results of an inverse modelling system for atmospheric N2O, based on a four-dimensional variational (4DVAR) technique and the atmospheric transport zoom model TM5. We focus in this study on the European domain, utilizing a comprehensive set of quasi-continuous measurements over Europe, complemented by N2O measurements from the Earth System Research Laboratory of the National Oceanic and Atmospheric Administration (NOAA/ESRL) cooperative global air sampling network. Despite ongoing measurement comparisons among networks parallel measurements at a limited number of stations show that significant offsets exist among the different laboratories. Since the spatial gradients of N2O mixing ratios are of the same order of magnitude as these biases, the direct use of these biased datasets would lead to significant errors in the derived emissions. Therefore, in order to also use measurements with unknown offsets, a new bias correction scheme has been implemented within the TM5-4DVAR inverse modelling system, thus allowing the simultaneous assimilation of observations from different networks. The N2O bias corrections determined in the TM5-4DVAR system agree within ~0.1 ppb (dry-air mole fraction) with the bias derived from the measurements at monitoring stations where parallel NOAA discrete air samples are available. The N2O emissions derived for the northwest European and east European countries for 2006 show good agreement with the bottom-up emission inventories reported to the United Nations Framework Convention on Climate Change (UNFCCC). Moreover, the inverse model can significantly narrow the uncertainty range reported in N2O emission inventories for these countries, while the lack of measurements does not allow to reduce the uncertainties of emission estimates in southern Europe. Several sensitivity experiments were performed to test the robustness of the results. It is shown that also inversions without detailed a priori spatio-temporal emission distributions are capable to reproduce major regional emission patterns within the footprint of the existing atmospheric network, demonstrating the strong constraints of the atmospheric observations on the derived emissions.

#### Perfluorocarbon (PFC) emissions from Australian aluminium smelters, 2005-2009 (2011) [link]

Authors: Fraser, Dunse, Steele, Krummel, Derek

This paper uses AGAGE CF4 data from Cape Grim, Tasmania, to derive CF4 emissions and emission factors from three SE Australian aluminium smelters. The derived emissions and emission factors are consistent with what is reported by the Australian government to the UNFCCC, although the rate of decline in CF4 emissions is not as rapid as what has been reported to the UNFCCC.

Authors: Fraser, Krummel, Steele

This paper uses CSIRO and AGAGE carbon dioxide and non-carbon dioxide greenhouse gas data (Cape Grim and global) to derive Southern Hemisphere and global radiative forcing to compare to IPCC estimates reported in recent international assessments of climate change. The radiative forcing calculations were updated to 2010 and reported to the Australian government via the Garnaut review of climate change.

#### The determination of a “regional” atmospheric background mixing ratio for anthropogenic greenhouse gases: A comparison of two independent methods (2011) [link]

Authors: Giostra, Furlani, Arduini, Cava, Manning, O’Doherty, Reimann, Maione

Halocarbons are powerful greenhouse gases capable of significantly influencing the radiative forcing of the Earth’s atmosphere. Halocarbons are monitored in several stations which are globally distributed in order to assess long term atmospheric trends and to identify source regions. However, to achieve these aims the definition of background mixing ratios, i.e. the mixing ratio in a given air mass when the recent contribution of local sources is absent, is necessary. This task can be accomplished using different methods. This paper presents a statistical methodology that has been devised specifically for a mountain site located in Continental Europe (Monte Cimone, Italy), characterised by the vicinity of strong sources. The method involves the decomposition of the observed data distribution into a Gaussian distribution, representative of background values, and a Gamma distribution, ascribable to contribution from stronger sources. The method has been applied to a time series from a European marine remote station (Mace Head, Ireland) as well as to time series from Monte Cimone. A comparison of the methodology described in this paper with a well-established meteorological filtering procedure at Mace Head has shown an excellent agreement. A comparison of the baselines at Mace Head, Mt. Cimone and the Swiss alpine station of the Jungfraujoch highlighted the occurrence of a specific background concentration. Although this paper presents the application of the method to three hydrofluorocarbons, the proposed methodology can be extended to any long lived atmospheric component for which a long term time series is available and at any location even if affected by strong source regions.

#### A five year record of high-frequency in situ measurements of non-methane hydrocarbons at Mace Head, Ireland (2011) [link]

Authors: Grant, Yates, Simmonds, Derwent, Manning, Young, Shallcross, O’Doherty

Continuous high-frequency in situ measurements of a range of non-methane hydrocarbons have been made at Mace Head since January 2005. Mace Head is a background Northern Hemispheric site situated on the eastern edge of the Atlantic. Five year measurements (2005–2009) of six C2–C5 non-methane hydrocarbons have been separated into baseline Northern Hemispheric and European polluted air masses, among other sectors. Seasonal cycles in baseline Northern Hemispheric air masses and European polluted air masses arriving at Mace Head have been studied. Baseline air masses show a broad summer minima between June and September for shorter lived species, longer lived species show summer minima in July/August. All species displayed a winter maxima in February. European air masses showed baseline elevated mole fractions for all non-methane hydrocarbons. Largest elevations (of up to 360 ppt for ethane maxima) from baseline data were observed in winter maxima, with smaller elevations observed during the summer. Analysis of temporal trends using the Mann-Kendall test showed small (

#### The UOW FTIR trace gas analyser: comparison with LoFlo, AGAGE and tank measurements at Cape Grim and GASLAB (2011) [link]

Authors: Griffith, Deutscher, Krummel, Fraser, Steele, van der Schoot, Allison

Accurate baseline measurements of clean air composition are technically demanding, and benefit from advances in instrumentation which improve accuracy and lower the cost and effort of ownership. The University of Wollongong FTIR trace gas analyser for determination of atmospheric trace gas concentrations has been significantly refined in the past decade since its initial development, providing improved accuracy and greater ease of operation. From October 2008 to February 2009 we operated a new analyser at Cape Grim, parallel to the CSIRO LoFlo CO2 analyser and AGAGE automated GC system. The FTIR analyser drew air from the 70-m tower inlet and operated continuously and autonomously for 110 days measuring 10-minute average concentrations of CO2, ∂13C-CO2, CH4, CO and N2O. Here the measurements are compared with LoFlo for CO2, AGAGE for the other gases and isotope ratio mass spectrometry for ∂13C in CO2. The FTIR analyser provided precisions significantly better than those provided by AGAGE for all co-measured species, but less than that of LoFlo for CO2. In March and April 2010 we also operated the same analyser at CSIRO’s Global Atmospheric Sampling Laboratory (GASLAB), making measurements of 36 standard calibration cylinders with well-characterised concentrations. We present the results of this comparison, in which the FTIR shows good precision and linearity over all measured concentration ranges. The FTIR analyser provides a cost-effective, low maintenance solution for the simultaneous measurement of the target species.

#### Results from the first national UK inter-laboratory calibration for very short-lived halocarbons (2011) [link]

Authors: Jones, Andrews, Carpenter, Hogan, Hopkins, Laube, Robinson, Spain, Archer, Harris, Nightingale, O’Doherty, Oram, Pyle, Butler, Hall

Very short-lived halocarbons (VSLH) such as CH3I, CH2Br2 and CHBr3 provide an important source of reactive halogens to the atmosphere, however high spatial and seasonal variability in their ambient mixing ratios and sea-air fluxes gives rise to considerable uncertainty in global scale emission estimates. One solution to improve global flux estimates is to combine the multitude of individually published datasets to produce a database of collated global halocarbon observations. Some progress towards this has already been achieved through the HalOcAt (Halocarbons in the Ocean and Atmosphere) database initiative, however the absence of a common calibration scale for very short-lived halocarbons makes it difficult to distinguish true environmental variations from artefacts arising from differences between calibration methodologies. As such, the lack of inter-calibrations for both air and seawater measurements of very short-lived halocarbons has been identified as a major limitation to current estimations of the global scale impact of these reactive trace gases. Here we present the key findings from the first national UK inter-laboratory comparison for calibrations of the halocarbons CH3I, CH2Br2 and CHBr3. The aim of this inter-calibration was to provide transparency between halocarbon calibrations from major UK research institutions, an important step towards enabling all measurements from these institutions to be treated as one coherent integrated dataset for global source term parameterisations.

#### Evidence for under-reported western European emissions of the potent greenhouse gas HFC-23 (2011) [link]

Authors: Keller, Brunner, Henne, Vollmer, O’Doherty, Reimann

Western European emission inventories of the potent greenhouse gas trifluoromethane (HFC-23) are validated at a country level by combining 2-hourly atmospheric in-situ measurements at Jungfraujoch (Switzerland) and Mace Head (Ireland) with Lagrangian transport simulations. HFC-23 has an atmospheric lifetime of ∼270 yr and a 100-yr global warming potential (GWP) of 14,800 and is unintentionally produced during the manufacture of chlorodifluoromethane (HCFC-22). For the study region we derive emissions of 144–216 Mg/yr for July 2008–July 2010, which are 60–140% higher than the official emissions gathered from the national reports for the year 2009. The largest discrepancy is found for Italy, where our estimate of 26–56 Mg/yr exceeds the national inventory (2.6 Mg/yr) by more than an order of magnitude. These findings suggest that non-reported emissions from Annex 1 countries partly explain the recently derived gap between global bottom-up and top-down HFC-23 emission estimates. The results presented here provide independent information to relevant authorities on effective reporting of HFC-23 emissions, and demonstrate the potential of atmospheric measurements for real-world verification of greenhouse gas emissions.

#### The Antarctic ozone hole during 2010 (2011) [link]

Authors: Klekociuk, Tully, Alexander, Dargaville, Deschamps, Fraser, Gies, Henderson, Javorniczky, Krummel, Petelina, Shanklin, Siddaway, Stone

The Antarctic ozone hole of 2010 is reviewed from a variety of perspectives, making use of various data and analyses. Based on total column ozone metrics, the 2010 ozone hole was one of the smallest in the past fifteen–twenty years. The main influence on the size of the ozone hole was relatively warm temperatures in the Antarctic lower stratosphere which impeded ozone depletion in the austral spring. The warm winter temperatures were associated with a significant dynamical disturbance in the mid- and high latitude upper stratosphere during July which included a substantial warming of the mid- and upper extratropical stratosphere, a deceleration of zonal winds and a cooling in the polar mesosphere. The disturbance was likely influenced by the phase of the Quasi-Biennial Oscillation (QBO) which favoured a weak and disturbed polar vortex in the winter months. The winter warming also resulted in significant off-pole displacement and weakening of the polar vortex in the mid- to upper stratosphere, producing a long-lasting increase in the overburden of ozone and weakening ozone hole metrics based on total column ozone measurements. Ozone loss in the lower stratosphere was less markedly affected by this dynamical activity, and was similar to other recent years. A notable feature was the reduction in dynamical disturbances of the polar vortex after September, when the QBO moved into a strongly eastward phase. During the late spring and early summer, stratospheric temperatures warmed more slowly than in recent years, and this produced one of the longest-lasting ozone holes yet observed which eventually disappeared in the last week of December. The relatively low ozone levels in December resulted in unusually high surface ultraviolet fluxes as measured on the coast of East Antarctica.

#### Three-year observations of halocarbons at the Nepal Climate Observatory at Pyramid (NCO-P, 5079 m a.s.l.) on the Himalayan range (2011) [link]

Authors: Maione, Giostra, Arduini, Furlani, Bonasoni, Cristofanelli, Laj, Vuillermoz

A monitoring programme for halogenated climate-altering gases has been established in the frame of the SHARE EV-K2-CNR project at the Nepal Climate Laboratory – Pyramid in the Himalayan range at the altitude of 5079 m a.s.l. The site is very well located to provide important insights on changes in atmospheric composition in a region that is of great significance for emissions of both anthropogenic and biogenic halogenated compounds. Measurements are performed since March 2006, with grab samples collected on a weekly basis. The first three years of data have been analysed. After the identification of the atmospheric background values for fourteen halocarbons, the frequency of occurrence of pollution events have been compared with the same kind of analysis for data collected at other global background stations. The analysis showed the fully halogenated species, whose production and consumption are regulated under the Montreal Protocol, show a significant occurrence of "above the baseline" values, as a consequence of their current use in the developing countries surrounding the region, meanwhile the hydrogenated gases, more recently introduced into the market, show less frequent spikes. Atmospheric concentration trends have been calculated as well, and they showed a fast increase, ranging from 5.7 to 12.6%, of all the hydrogenated species, and a clear decrease of methyl chloroform (−17.7%). The comparison with time series from other stations has also allowed to derive Meridional gradients, which are absent for long living well mixed species, while for the more reactive species, the gradient increases inversely with respect to their atmospheric lifetime. The effect of long range transport and of local events on the atmospheric composition at the station has been analysed as well, allowing the identification of relevant source regions the Northern half of the Indian sub-continent. Also, at finer spatial scales, a smaller, local contribution of forest fires from the Khumbu valley has been detected.

#### Estimating UK methane and nitrous oxide emissions from 1990 to 2007 using an inversion modeling approach (2011) [link]

Authors: Manning, O’Doherty, Jones, Simmonds, Derwent

Methane (CH4) and nitrous oxide (N2O) have strong radiative properties in the Earth's atmosphere and both are regulated through the United Nations Framework Convention on Climate Change. Through this convention the United Kingdom is obliged to report an inventory of annual emission estimates from 1990. This paper describes a methodology that estimates emissions of CH4 and N2O completely independent of the inventory values. Emissions have been estimated for each year 1990–2007 for the United Kingdom and for NW Europe. The methodology combines high-frequency observations from Mace Head, a monitoring site on the west coast of Ireland, with an atmospheric dispersion model and an inversion system. The sensitivities of the inversion method to the modeling assumptions are reported. The 20 year Northern Hemisphere midlatitude baseline mixing ratios, growth rates, and seasonal cycles of both gases are also presented. The results indicate reasonable agreement between the inventory and inversion results for the United Kingdom for N2O over the entire period. For CH4 the agreement is poor in the 1990s but good in the 2000s. The UK CH4 inventory reported reduction from 1990–1992 to 2005–2007 (over 50%) is dominated by changes to landfill and coal mine emissions and is more than double the corresponding drop in the inversion estimated emissions (24%). The inversion results suggest that the United Kingdom has met its Kyoto commitment (−12.5%) but by a smaller margin (−14.3%) than reported (−17.3%). The results for NW Europe with the United Kingdom removed show reasonable agreement in trend, on average the inversion results for N2O are 25% lower and for CH4 21% higher.

#### Ozone-Depleting Substances (ODSs) and Related Chemicals [Chapter 1] (2011) [link]

Authors: Montzka, Reimann, Engel, Krüger, O’Doherty, Sturges, Blake, Dorf, Fraser, Froidevaux, Jucks, Kreher, Kurylo, Mellouki, Miller, Nielsen, Orkin, Prinn, Rhew, Santee, Stohl, Verdonik

The Scientific Assessment of Ozone Depletion: 2010 made extensive use of AGAGE ODS data and contributions from AGAGE scientists and collaborators (Fraser, Jucks, Kurylo, O’Doherty, Prinn, Reimann).

#### State of the Climate in 2010: [Global Climate, Atmospheric composition] Perfluorocarbons (2011) [link]

Authors: Mühle, Ganesan

Perfluorocarbons (PFCs) are extremely long-lived, potent greenhouse gases. PFC-14 (CF4) and PFC-116 (C2F6) have conservative lower limits for atmospheric lifetimes of 50 000 and 10 000 years, respectively, and global warming potentials (100-year time horizon) of 7390 and 12 200, respectively (Ravishankara et al. 1993; Morris et al. 1995; Forster et al. 2007; Montzka et al. 2011). Anthropogenic PFC-14 and PFC-116 were historically emitted as by-products of aluminum production and are now also emitted from the electronics industry. However, the onset and extent of PFC emissions from the electronics industry is poorly known due to limited reporting (Khalil et al. 2003; Worton et al. 2007; EDGAR 2009; Mühle et al. 2010). A small natural source of PFC-14 from degassing of Earth’s crust has been identified (Harnisch and Eisenhauer 1998; Harnisch et al. 2000), which, because of its extraordinarily long atmospheric lifetime, accounts for its significant pre-industrial abundance (Harnisch et al. 1996a, 1996b) of 34.7 ± 0.2 ppt (Mühle et al. 2010), or ~44% of its 2010 abundance. Global average surface concentrations of PFC-14 and PFC-116, respectively (Fig. 2.51), were 50.8 ± 0.8 ppt and 1.0 ± 0.1 ppt in 1978, 77.7 ± 0.1 ppt and 4.01 ± 0.01 ppt in 2009, and 78.3 ± 0.1 ppt and 4.09 ± 0.02 ppt in 2010 (Mühle et al. 2010). PFC-14 rose at ~1.1 ppt yr-1 from the late 1970s to the early 1990s and by ~0.7 ppt yr-1 since that time. PFC-116 rose at ~0.09 ppt yr-1 from the late-1970s to the mid-1990s followed by an increase to ~0.12 ppt yr-1 until the mid-2000s and a subsequent decline to ~0.09 ppt yr-1 afterwards (Mühle et al. 2010).

#### Exploring causes of interannual variability in the seasonal cycles of tropospheric nitrous oxide (2011) [link]

Authors: Nevison, Dlugokencky, Dutton, Elkins, Fraser, Hall, Krummel, Langenfelds, O’Doherty, Prinn, Steele, Weiss

Seasonal cycles in the mixing ratios of tropospheric nitrous oxide (N2O) are derived by detrending long-term measurements made at sites across four global surface monitoring networks. The detrended monthly data display large interannual variability, which at some sites challenges the concept of a "mean" seasonal cycle. In the Northern Hemisphere, correlations between polar winter lower stratospheric temperature and detrended N2O data, around the month of the seasonal minimum, provide empirical evidence for a stratospheric influence, which varies in strength from year to year and can explain much of the interannual variability in the surface seasonal cycle. Even at sites where a strong, competing, regional N2O source exists, such as from coastal upwelling at Trinidad Head, California, the stratospheric influence must be understood to interpret the biogeochemical signal in monthly mean data. In the Southern Hemisphere, detrended surface N2O monthly means are correlated with polar spring lower stratospheric temperature in months preceding the N2O minimum, providing empirical evidence for a coherent stratospheric influence in that hemisphere as well, in contrast to some recent atmospheric chemical transport model (ACTM) results. Correlations between the phasing of the surface N2O seasonal cycle in both hemispheres and both polar lower stratospheric temperature and polar vortex break-up date provide additional support for a stratospheric influence. The correlations discussed above are generally more evident in high-frequency in situ data than in data from weekly flask samples. Furthermore, the interannual variability in the N2O seasonal cycle is not always correlated among in situ and flask networks that share common sites, nor do the mean seasonal amplitudes always agree. The importance of abiotic influences such as the stratospheric influx and tropospheric transport on N2O seasonal cycles suggests that, at sites remote from local sources, surface N2O mixing ratio data by themselves are unlikely to provide information about seasonality in surface sources, e.g., for atmospheric inversions, unless the ACTMs employed in the inversions accurately account for these influences. An additional abioitc influence is the seasonal ingassing and outgassing of cooling and warming surface waters, which creates a thermal signal in tropospheric N2O that is of particular importance in the extratropical Southern Hemisphere, where it competes with the biological ocean source signal.

#### TransCom model simulations of CH₄ and related species: linking transport, surface flux and chemical loss with CH₄ variability in the troposphere and lower stratosphere (2011) [link]

Authors: Patra, Houweling, Krol, Bousquet, Belikov, Bergmann, Bian, Cameron-Smith, Chipperfield, Corbin, Fortems-Cheiney, Fraser, Gloor, Hess, Ito, Kawa, Law, Loh, Maksyutov, Meng, Palmer, Prinn, Rigby, Saito, Wilson

A chemistry-transport model (CTM) intercomparison experiment (TransCom-CH4) has been designed to investigate the roles of surface emissions, transport and chemical loss in simulating the global methane distribution. Model simulations were conducted using twelve models and four model variants and results were archived for the period of 1990–2007. All but one model transports were driven by reanalysis products from 3 different meteorological agencies. The transport and removal of CH4 in six different emission scenarios were simulated, with net global emissions of 513 ± 9 and 514 ± 14 Tg CH4 yr−1 for the 1990s and 2000s, respectively. Additionally, sulfur hexafluoride (SF6) was simulated to check the interhemispheric transport, radon (222Rn) to check the subgrid scale transport, and methyl chloroform (CH3CCl3) to check the chemical removal by the tropospheric hydroxyl radical (OH). The results are compared to monthly or annual mean time series of CH4, SF6 and CH3CCl3 measurements from 8 selected background sites, and to satellite observations of CH4 in the upper troposphere and stratosphere. Most models adequately capture the vertical gradients in the stratosphere, the average long-term trends, seasonal cycles, interannual variations (IAVs) and interhemispheric (IH) gradients at the surface sites for SF6, CH3CCl3 and CH4. The vertical gradients of all tracers between the surface and the upper troposphere are consistent within the models, revealing vertical transport differences between models. An average IH exchange time of 1.39 ± 0.18 yr is derived from SF6 time series. Sensitivity simulations suggest that the estimated trends in exchange time, over the period of 1996–2007, are caused by a change of SF6 emissions towards the tropics. Using six sets of emission scenarios, we show that the decadal average CH4 growth rate likely reached equilibrium in the early 2000s due to the flattening of anthropogenic emission growth since the late 1990s. Up to 60% of the IAVs in the observed CH4 concentrations can be explained by accounting for the IAVs in emissions, from biomass burning and wetlands, as well as meteorology in the forward models. The modeled CH4 budget is shown to depend strongly on the troposphere-stratosphere exchange rate and thus on the model's vertical grid structure and circulation in the lower stratosphere. The 15-model median CH4 and CH3CCl3 atmospheric lifetimes are estimated to be 9.99 ± 0.08 and 4.61 ± 0.13 yr, respectively, with little IAV due to transport and temperature.

#### Global modelling of H2 mixing ratios and isotopic compositions with the TM5 model (2011) [link]

Authors: Pieterse, Krol, Batenburg, Steele, Krummel, Langenfelds, Röckmann

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

#### Climate and Greenhouse Gases [Chapter 2] (2011) [link]

Authors: Raupach, Fraser

This chapter in Climate Change: Science and Solutions for Australia used AGAGE and CSIRO data from Cape Grim and the global AGAGE network to derive post-AR4 values of radiative forcing for use in a policy-setting Australian environment.

#### Deriving emissions time series from sparse atmospheric mole fractions (2011) [link]

Authors: Rigby, Ganesan, Prinn

A growth-based Bayesian inverse method is presented for deriving emissions of atmospheric trace species from temporally sparse measurements of their mole fractions. This work is motivated by many recent studies that have deduced emissions using archived air samples with measurement intervals of the order of a year or longer in the early part of the record. Several techniques have been used to make this underdetermined problem invertible. These include the incorporation of prior emissions estimates, the smoothing of observations or derived emissions, the approximation of emissions time series by polynomials, or the application of regularization schemes. However, these methods often suffer from limitations, such as the unavailability of independent, unbiased priors, the emergence of unrealistic emissions fluctuations due to measurement outliers, or the subjective choice of measurement or emissions smoothing time scales. This paper presents an alternative solution that reduces the influence of potentially biased priors or measurement outliers by constraining the emissions growth rate around some growth estimate, in conjunction with the model-measurement mismatch.

#### Inversion of long-lived trace gas emissions using combined Eulerian and Lagrangian chemical transport models (2011) [link]

Authors: Rigby, Manning, Prinn

We present a method for estimating emissions of long-lived trace gases from a sparse global network of high-frequency observatories, using both a global Eulerian chemical transport model and Lagrangian particle dispersion model. Emissions are derived in a single step after determining sensitivities of the observations to initial conditions, the high-resolution emissions field close to observation points, and larger regions further from the measurements. This method has the several advantages over inversions using one type of model alone, in that: high-resolution simulations can be carried out in limited domains close to the measurement sites, with lower resolution being used further from them; the influence of errors due to aggregation of emissions close to the measurement sites can be minimized; assumptions about boundary conditions to the Lagrangian model do not need to be made, since the entire emissions field is estimated; any combination of appropriate models can be used, with no code modification. Because the sensitivity to the entire emissions field is derived, the estimation can be carried out using traditional statistical methods without the need for multiple steps in the inversion. We demonstrate the utility of this approach by determining global SF6 emissions using measurements from the Advanced Global Atmospheric Gases Experiment (AGAGE) between 2007 and 2009. The global total and large-scale patterns of the derived emissions agree well with previous studies, whilst allowing emissions to be determined at higher resolution than has previously been possible, and improving the agreement between the modeled and observed mole fractions at some sites.

#### Estimation of hydrogen deposition velocities from 1995–2008 at Mace Head, Ireland using a simple box model and concurrent ozone depositions (2011) [link]

Authors: Simmonds, Derwent, Manning, Grant, O’Doherty, Spain

During stable nocturnal inversions with low wind speeds, we observed strong depletions of both hydrogen and ozone caused by deposition to the peat bogs in the vicinity of the Mace Head Atmospheric Research Station, Connemara, County Galway, Ireland. From these temporally correlated fluxes and using a simple box model, we have estimated the strength of the molecular hydrogen soil sink over a 14-yr period (1995–2008). Over this entire period 269 nocturnal deposition events were identified that satisfied the strict selection criteria. The average hydrogen deposition velocity determined from these events was 0.53 mm s -1 , covering a range of 0.18–1.29 mm s -1 , which is in agreement with the range of deposition velocities reported in the literature for similar peaty biomes. By annually averaging all of the nocturnal inversion events over the most seasonally active period from April–September we reveal a positive correlation with ambient temperature in the relative deposition velocities of hydrogen and ozone, which is not readily apparent in all of the individual events. Furthermore, average hydrogen deposition velocities and accumulated rainfall from 48 h before and during each event were to a reasonable extent anti-correlated. However, due to the large uncertainties in determining monthly mean H 2 deposition velocities there is no statistically significant trend in the hydrogen deposition velocities over time.

#### The Antarctic ozone hole during 2008 and 2009 (2011) [link]

Authors: Tully, Klekociuk, Alexander, Dargaville, Deschamps, Fraser, Gies, Henderson, Javorniczky, Krummel, Petelina, Shanklin, Siddaway, Stone

The Antarctic ozone holes of 2008 and 2009 are reviewed from various perspectives, making use of a range of Australian data and analyses. In both years, ozone holes formed that were fairly typical of those observed since the late 1990s. The ozone hole of 2008 was somewhat larger than that of 2009. In 2009 the ozone hole developed more rapidly, but did not last as long as in 2008, particularly in the lower stratosphere.

#### Atmospheric histories and global emissions of the anthropogenic hydrofluorocarbons HFC-365mfc, HFC-245fa, HFC-227ea, and HFC-236fa (2011) [link]

Authors: Vollmer, Miller, Rigby, Reimann, Mühle, Krummel, O’Doherty, Kim, Rhee, Weiss, Fraser, Simmonds, Salameh, Harth, Wang, Steele, Young, Lunder, Hermansen, Ivy, Arnold, Schmidbauer, Kim, Greally, Hill, Leist, Wenger, Prinn

We report on ground-based atmospheric measurements and emission estimates of the four anthropogenic hydrofluorocarbons (HFCs) HFC-365mfc (CH3CF2CH2CF3, 1,1,1,3,3-pentafluorobutane), HFC-245fa (CHF2CH2CF3, 1,1,1,3,3-pentafluoropropane), HFC-227ea (CF3CHFCF3, 1,1,1,2,3,3,3-heptafluoropropane), and HFC-236fa (CF3CH2CF3, 1,1,1,3,3,3-hexafluoropropane). In situ measurements are from the global monitoring sites of the Advanced Global Atmospheric Gases Experiment (AGAGE), the System for Observations of Halogenated Greenhouse Gases in Europe (SOGE), and Gosan (South Korea). We include the first halocarbon flask sample measurements from the Antarctic research stations King Sejong and Troll. We also present measurements of archived air samples from both hemispheres back to the 1970s. We use a two-dimensional atmospheric transport model to simulate global atmospheric abundances and to estimate global emissions. HFC-365mfc and HFC-245fa first appeared in the atmosphere only ∼1 decade ago; they have grown rapidly to globally averaged dry air mole fractions of 0.53 ppt (in parts per trillion, 10−12) and 1.1 ppt, respectively, by the end of 2010. In contrast, HFC-227ea first appeared in the global atmosphere in the 1980s and has since grown to ∼0.58 ppt. We report the first measurements of HFC-236fa in the atmosphere. This long-lived compound was present in the atmosphere at only 0.074 ppt in 2010. All four substances exhibit yearly growth rates of >8% yr−1 at the end of 2010. We find rapidly increasing emissions for the foam-blowing compounds HFC-365mfc and HFC-245fa starting in ∼2002. After peaking in 2006 (HFC-365mfc: 3.2 kt yr−1, HFC-245fa: 6.5 kt yr−1), emissions began to decline. Our results for these two compounds suggest that recent estimates from long-term projections (to the late 21st century) have strongly overestimated emissions for the early years of the projections (∼2005–2010). Global HFC-227ea and HFC-236fa emissions have grown to average values of 2.4 kt yr−1 and 0.18 kt yr−1 over the 2008–2010 period, respectively.

#### Quantifying greenhouse-gas emissions from atmospheric measurements: a critical reality check for climate legislation (2011) [link]

Authors: Weiss, Prinn

Emissions reduction legislation relies upon ‘bottom-up’ accounting of industrial and biogenic greenhouse-gas (GHG) emissions at their sources. Yet, even for relatively well-constrained industrial GHGs, global emissions based on ‘top-down’ methods that use atmospheric measurements often agree poorly with the reported bottom-up emissions. For emissions reduction legislation to be effective, it is essential that these discrepancies be resolved. Because emissions are regulated nationally or regionally, not globally, top-down estimates must also be determined at these scales. High-frequency atmospheric GHG measurements at well-chosen station locations record ‘pollution events’ above the background values that result from regional emissions. By combining such measurements with inverse methods and atmospheric transport and chemistry models, it is possible to map and quantify regional emissions. Even with the sparse current network of measurement stations and current inverse-modelling techniques, it is possible to rival the accuracies of regional ‘bottom-up’ emission estimates for some GHGs. But meeting the verification goals of emissions reduction legislation will require major increases in the density and types of atmospheric observations, as well as expanded inverse-modelling capabilities. The cost of this effort would be minor when compared with current investments in carbon-equivalent trading, and would reduce the volatility of that market and increase investment in emissions reduction.

#### A new estimation of the recent tropospheric molecular hydrogen budget using atmospheric observations and variational inversion (2011) [link]

Authors: Yver, Pison, Fortems-Cheiney, Schmidt, Chevallier, Ramonet, Jordan, Søvde, Engel, Fisher, Lowry, Nisbet, Levin, Hammer, Necki, Bartyzel, Reimann, Vollmer, Steinbacher, Aalto, Maione, Arduini, O’Doherty, Grant, Sturges, Forster, Lunder, Privalov, Paramonova, Werner, Bousquet

This paper presents an analysis of the recent tropospheric molecular hydrogen (H2) budget with a particular focus on soil uptake and European surface emissions. A variational inversion scheme is combined with observations from the RAMCES and EUROHYDROS atmospheric networks, which include continuous measurements performed between mid-2006 and mid-2009. Net H2 surface flux, then deposition velocity and surface emissions and finally, deposition velocity, biomass burning, anthropogenic and N2 fixation-related emissions were simultaneously inverted in several scenarios. These scenarios have focused on the sensibility of the soil uptake value to different spatio-temporal distributions. The range of variations of these diverse inversion sets generate an estimate of the uncertainty for each term of the H2 budget. The net H2 flux per region (High Northern Hemisphere, Tropics and High Southern Hemisphere) varies between −8 and +8 Tg yr−1. The best inversion in terms of fit to the observations combines updated prior surface emissions and a soil deposition velocity map that is based on bottom-up and top-down estimations. Our estimate of global H2 soil uptake is −59±9 Tg yr−1. Forty per cent of this uptake is located in the High Northern Hemisphere and 55% is located in the Tropics. In terms of surface emissions, seasonality is mainly driven by biomass burning emissions. The inferred European anthropogenic emissions are consistent with independent H2 emissions estimated using a H2/CO mass ratio of 0.034 and CO emissions within the range of their respective uncertainties. Additional constraints, such as isotopic measurements would be needed to infer a more robust partition of H2 sources and sinks.

#### In-situ measurement of atmospheric CFC-11 at the Shangdianzi Global Atmosphere Watch (GAW) Regional Station (2011) [link]

Authors: Zhang, Zhou, Yao, Zhang, Xu, Zhang, Zhou, Dong, Zhou

An in-situ GC-ECD system was used to measure halocarbons at Shangdianzi (SDZ) GAW regional station. In this paper, we reported observational results of atmospheric CFC-11 (CCl3F) mixing ratios from April 2007 to March 2008. The CFC-11 time series showed large variability. Approximately 62% observed values were filtered as non-background data. The median, 10% and 90% percentiles of CFC-11 background mixing ratios were 245.4 ppt (10−12 mol/mol), 244.6 ppt and 246.1 ppt, respectively; whereas those of non-background CFC-11 mixing ratios were 254.7, 246.6 and 272.1 ppt, respectively. Significant differences in background and non-background CFC-11 mixing ratios were observed between summer and autumn, mainly because of the CFC-11 stored in foam being prone to atmospheric release in hot seasons. Comparison of the SDZ data with the five AGAGE stations suggested agreement with mid-high latitude Northern Hemisphere stations MHD, THD and RPB. The SDZ data were higher than that of Southern Hemisphere stations CGO and SMO. Higher CFC-11 mixing ratios measured in different seasons were always associated with winds from the W-WSW-SW sector, indicating that the airflow coming from this wind sector has a positive contribution to CFC-11concentrations. The CFC-11 mixing ratios were higher in autumn and summer than in spring and winter, in which its mixing ratios were very close to the atmospheric background level. This was happened especially when airflow originated from the NNE-NE-ENE-E sector, indicating the air masses coming from these wind directions was relatively clean.

### 2012

#### Estimating emissions of HCFC-22 and CFC-11 in China by atmospheric observations and inverse modeling (2012) [link]

Authors: An, Henne, Yao, Vollmer, Zhou

This paper presents the estimation of Chinese emissions of HCFC-22 and CFC-11 in 2009 by an inverse modeling method based on in-situ measurement data from the Shangdianzi Global Atmosphere Watch (GAW) Regional Station (SDZ) and atmospheric transport simulations. After inversion (a-posteriori) estimates of the Chinese emissions in 2009 increased by 6.6% for HCFC-22 from 91.7 (± 83.6) to 98.3 (± 47.4) kt/yr and by 22.5% for CFC-11 from 13 (±12.6) to 15.8 (±7.2) kt/yr compared to an a-priori emission. While the model simulation with a-priori emissions already captured the main features of the observed variability at the measurement site, the model performance (in terms of correlation and mean-square-error) improved using a-posteriori emissions. The inversion reduced the root-mean-square (RMS) error by 4% and 10% for HCFC-22 and CFC-11, respectively.

#### Automated Measurement of Nitrogen Trifluoride in Ambient Air (2012) [link]

Authors: Arnold, Mühle, Salameh, Harth, Ivy, Weiss

We present an analytical method for the in situ measurement of atmospheric nitrogen trifluoride (NF3), an anthropogenic gas with a 100-year global warming potential of over 16 000. This potent greenhouse gas has a rising atmospheric abundance due to its emission from a growing number of manufacturing processes and an expanding end-use market. Here we present a modified version of the “Medusa” preconcentration gas chromatography/mass spectrometry (GC/MS) system of Miller, B. R.; Weiss, R. F.; Salameh, P. K.; Tanhua, T.; Greally, B. R.; Mühle, J.; Simmonds, P. G. Anal. Chem. 2008, 80 (5), 1536–1545. By altering the techniques of gas separation and chromatography after initial preconcentration, we are now able to make atmospheric measurements of NF3 with relative precision <2% (1σ) for current background clean air samples. Importantly, this method augments the currently operational Medusa system, so that the quality of data for species already being measured is not compromised and NF3 is measured from the same preconcentrated sample. We present the first in situ measurements of NF3 from La Jolla, California made 11 times daily, illustrating how global deployment of this technique within the AGAGE (Advanced Global Atmospheric Gases Experiment) network could facilitate estimation of global and regional NF3 emissions over the coming years.

#### Corrigendum to "Source attribution of the changes in atmospheric methane for 2006–2008" published in Atmos. Chem. Phys., 11, 3689–3700, 2011 (2012) [link]

Authors: Bousquet, Ringeval, Pison, Dlugokencky, Brunke, Carouge, Chevallier, Fortems-Cheiney, Frankenberg, Hauglustaine, Krummel, Langenfelds, Ramonet, Schmidt, Steele, Szopa, Yver, Viovy, Ciais

No abstract available.

#### An extended Kalman-filter for regional scale inverse emission estimation (2012) [link]

Authors: Brunner, Henne, Keller, Reimann, Vollmer, O’Doherty, Maione

A Kalman-filter based inverse emission estimation method for long-lived trace gases is presented for use in conjunction with a Lagrangian particle dispersion model like FLEXPART. The sequential nature of the approach allows tracing slow seasonal and interannual changes rather than estimating a single period-mean emission field. Other important features include the estimation of a slowly varying concentration background at each measurement station, the possibility to constrain the solution to non-negative emissions, the quantification of uncertainties, the consideration of temporal correlations in the residuals, and the applicability to potentially large inversion problems. The method is first demonstrated for a set of synthetic observations created from a prescribed emission field with different levels of (correlated) noise, which closely mimics true observations. It is then applied to real observations of the three halocarbons HFC-125, HFC-152a and HCFC-141b at the remote research stations Jungfraujoch and Mace Head for the quantification of emissions in Western European countries from 2006 to 2010. Estimated HFC-125 emissions are mostly consistent with national totals reported to UNFCCC in the framework of the Kyoto Protocol and show a generally increasing trend over the considered period. Results for HFC-152a are much more variable with estimated emissions being both higher and lower than reported emissions in different countries. The highest emissions of the order of 700–800 Mg yr−1 are estimated for Italy, which so far does not report HFC-152a emissions. Emissions of HCFC-141b show a continuing strong decrease as expected due to its controls in developed countries under the Montreal Protocol. Emissions from France, however, were still rather large, in the range of 700–1000 Mg yr−1 in the years 2006 and 2007 but strongly declined thereafter.

#### Gas transport in firn: multiple-tracer characterisation and model intercomparison for NEEM, Northern Greenland (2012) [link]

Authors: Buizert, Martinerie, Petrenko, Severinghaus, Trudinger, Witrant, Rosen, Orsi, Rubino, Etheridge, Steele, Hogan, Laube, Sturges, Levchenko, Smith, Levin, Conway, Dlugokencky, Lang, Kawamura, Jenk, White, Sowers, Schwander, Blunier

Air was sampled from the porous firn layer at the NEEM site in Northern Greenland. We use an ensemble of ten reference tracers of known atmospheric history to characterise the transport properties of the site. By analysing uncertainties in both data and the reference gas atmospheric histories, we can objectively assign weights to each of the gases used for the depth-diffusivity reconstruction. We define an objective root mean square criterion that is minimised in the model tuning procedure. Each tracer constrains the firn profile differently through its unique atmospheric history and free air diffusivity, making our multiple-tracer characterisation method a clear improvement over the commonly used single-tracer tuning. Six firn air transport models are tuned to the NEEM site; all models successfully reproduce the data within a 1σ Gaussian distribution. A comparison between two replicate boreholes drilled 64 m apart shows differences in measured mixing ratio profiles that exceed the experimental error. We find evidence that diffusivity does not vanish completely in the lock-in zone, as is commonly assumed. The ice age- gas age difference (Δage) at the firn-ice transition is calculated to be 182+3−9 yr. We further present the first intercomparison study of firn air models, where we introduce diagnostic scenarios designed to probe specific aspects of the model physics. Our results show that there are major differences in the way the models handle advective transport. Furthermore, diffusive fractionation of isotopes in the firn is poorly constrained by the models, which has consequences for attempts to reconstruct the isotopic composition of trace gases back in time using firn air and ice core records.

#### Seasonal cycles in short-lived hydrocarbons in baseline air masses arriving at Mace Head, Ireland (2012) [link]

Authors: Derwent, Simmonds, O’Doherty, Grant, Young, Cooke, Manning, Utembe, Jenkin, Shallcross

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.

#### Future Emissions and Atmospheric Fate of HFC-1234yf from Mobile Air Conditioners in Europe (2012) [link]

Authors: Henne, Shallcross, Reimann, Xiao, Brunner, O’Doherty, Buchmann

HFC-1234yf (2,3,3,3-tetrafluoropropene) is under discussion for replacing HFC-134a (1,1,1,2-tetrafluoroethane) as a cooling agent in mobile air conditioners (MACs) in the European vehicle fleet. Some HFC-1234yf will be released into the atmosphere, where it is almost completely transformed to the persistent trifluoroacetic acid (TFA). Future emissions of HFC-1234yf after a complete conversion of the European vehicle fleet were assessed. Taking current day leakage rates and predicted vehicle numbers for the year 2020 into account, European total HFC-1234yf emissions from MACs were predicted to range between 11.0 and 19.2 Gg yr(-1). Resulting TFA deposition rates and rainwater concentrations over Europe were assessed with two Lagrangian chemistry transport models. Mean European summer-time TFA mixing ratios of about 0.15 ppt (high emission scenario) will surpass previously measured levels in background air in Germany and Switzerland by more than a factor of 10. Mean deposition rates (wet + dry) of TFA were estimated to be 0.65-0.76 kg km(-2) yr(-1), with a maxium of ∼2.0 kg km(-2) yr(-1) occurring in Northern Italy. About 30-40% of the European HFC-1234yf emissions were deposited as TFA within Europe, while the remaining fraction was exported toward the Atlantic Ocean, Central Asia, Northern, and Tropical Africa. Largest annual mean TFA concentrations in rainwater were simulated over the Mediterranean and Northern Africa, reaching up to 2500 ng L(-1), while maxima over the continent of about 2000 ng L(-1) occurred in the Czech Republic and Southern Germany. These highest annual mean concentrations are at least 60 times lower than previously determined to be a safe level for the most sensitive aquatic life-forms. Rainwater concentrations during individual rain events would still be 1 order of magnitude lower than the no effect level. To verify these results future occasional sampling of TFA in the atmospheric environment should be considered. If future HFC-1234yf emissions surpass amounts used here studies of TFA accumulation in endorheic basins and other sensitive areas should be aspired.

#### Atmospheric histories and growth trends of C₄F₁₀, C₅F₁₂, C₆F₁₄, C₇F₁₆ and C₈F₁₈ (2012) [link]

Authors: Ivy, Arnold, Harth, Steele, Mühle, Rigby, Salameh, Leist, Krummel, Fraser, Weiss, Prinn

Atmospheric observations and trends are presented for the high molecular weight perfluorocarbons (PFCs): decafluorobutane (C4F10), dodecafluoropentane (C5F12), tetradecafluorohexane (C6F14), hexadecafluoroheptane (C7F16) and octadecafluorooctane (C8F18). Their atmospheric histories are based on measurements of 36 Northern Hemisphere and 46 Southern Hemisphere archived air samples collected between 1973 to 2011 using the Advanced Global Atmospheric Gases Experiment (AGAGE) "Medusa" preconcentration gas chromatography-mass spectrometry systems. A new calibration scale was prepared for each PFC, with estimated accuracies of 6.8% for C4F10, 7.8% for C5F12, 4.0% for C6F14, 6.6% for C7F16 and 7.9% for C8F18. Based on our observations the 2011 globally averaged dry air mole fractions of these heavy PFCs are: 0.17 parts-per-trillion (ppt, i.e., parts per 1012) for C4F10, 0.12 ppt for C5F12, 0.27 ppt for C6F14, 0.12 ppt for C7F16 and 0.09 ppt for C8F18. These atmospheric mole fractions combine to contribute to a global average radiative forcing of 0.35 mW m−2, which is 6% of the total anthropogenic PFC radiative forcing (Montzka and Reimann, 2011; Oram et al., 2012). The growth rates of the heavy perfluorocarbons were largest in the late 1990s peaking at 6.2 parts per quadrillion (ppq, i.e., parts per 1015) per year (yr) for C4F10, at 5.0 ppq yr−1 for C5F12 and 16.6 ppq yr−1 for C6F14 and in the early 1990s for C7F16 at 4.7 ppq yr−1 and in the mid 1990s for C8F18 at 4.8 ppq yr−1. The 2011 globally averaged mean atmospheric growth rates of these PFCs are subsequently lower at 2.2 ppq yr−1 for C4F10, 1.4 ppq yr−1 for C5F12, 5.0 ppq yr−1 for C6F14, 3.4 ppq yr−1 for C7F16 and 0.9 ppq yr−1 for C8F18. The more recent slowdown in the growth rates suggests that emissions are declining as compared to the 1980s and 1990s.

#### Global emission estimates and radiative impact of C₄F₁₀, C₅F₁₂, C₆F₁₄, C₇F₁₆ and C₈F₁₈ (2012) [link]

Authors: Ivy, Rigby, Baasandorj, Burkholder, Prinn

Global emission estimates based on new atmospheric observations are presented for the acylic high molecular weight perfluorocarbons (PFCs): decafluorobutane (C4F10), dodecafluoropentane (C5F12), tetradecafluorohexane (C6F14), hexadecafluoroheptane (C7F16) and octadecafluorooctane (C8F18). Emissions are estimated using a 3-dimensional chemical transport model and an inverse method that includes a growth constraint on emissions. The observations used in the inversion are based on newly measured archived air samples that cover a 39-yr period, from 1973 to 2011, and include 36 Northern Hemispheric and 46 Southern Hemispheric samples. The derived emission estimates show that global emission rates were largest in the 1980s and 1990s for C4F10 and C5F12, and in the 1990s for C6F14, C7F16 and C8F18. After a subsequent decline, emissions have remained relatively stable, within 20%, for the last 5 yr. Bottom-up emission estimates are available from the Emission Database for Global Atmospheric Research version 4.2 (EDGARv4.2) for C4F10, C5F12, C6F14 and C7F16, and inventories of C4F10, C5F12 and C6F14 are reported to the United Nations' Framework Convention on Climate Change (UNFCCC) by Annex 1 countries that have ratified the Kyoto Protocol. The atmospheric measurement-based emission estimates are 20 times larger than EDGARv4.2 for C4F10 and over three orders of magnitude larger for C5F12 (with 2008 EDGARv4.2 estimates for C5F12 at 9.6 kg yr−1, as compared to 67±53 t yr−1 as derived in this study). The derived emission estimates for C6F14 largely agree with the bottom-up estimates from EDGARv4.2. Moreover, the C7F16 emission estimates are comparable to those of EDGARv4.2 at their peak in the 1990s, albeit significant underestimation for the other time periods. There are no bottom-up emission estimates for C8F18, thus the emission rates reported here are the first for C8F18. The reported inventories for C4F10, C5F12 and C6F14 to UNFCCC are five to ten times lower than those estimated in this study.

In addition, we present measured infrared absorption spectra for C7F16 and C8F18, and estimate their radiative efficiencies and global warming potentials (GWPs). We find that C8F18's radiative efficiency is similar to trifluoromethyl sulfur pentafluoride's (SF5F3) at 0.57 W m−2 ppb−1, which is the highest radiative efficiency of any measured atmospheric species. Using the 100-yr time horizon GWPs, the total radiative impact of the high molecular weight perfluorocarbons emissions are also estimated; we find the high molecular weight PFCs peak contribution was in 1997 at 24 000 Gg of carbon dioxide (CO2) equivalents and has decreased by a factor of three to 7300 Gg of CO2 equivalents in 2010. This 2010 cumulative emission rate for the high molecular weight PFCs is comparable to: 0.02% of the total CO2 emissions, 0.81% of the total hydrofluorocarbon emissions, or 1.07% of the total chlorofluorocarbon emissions projected for 2010 (Velders et al., 2009). In terms of the total PFC emission budget, including the lower molecular weight PFCs, the high molecular weight PFCs peak contribution was also in 1997 at 15.4% and was 6% of the total PFC emissions in CO2 equivalents in 2009.

#### European Emissions of Halogenated Greenhouse Gases Inferred from Atmospheric Measurements (2012) [link]

Authors: Keller, Hill, Vollmer, Henne, Brunner, Reimann, O’Doherty, Arduini, Maione, Ferenczi, Haszpra, Manning, Peter

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 CO2 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.

#### Overview of the findings from measurements of halogenated compounds at Gosan (Jeju Island, Korea) quantifying emissions in East Asia (2012) [link]

Authors: Kim, Mühle, Stohl, Kim, Park, Park, Weiss, Kim

With increased economic growth in East Asia, regional emissions of many anthropogenic halogenated compounds now constitute a substantial fraction of the global totals. Here, we summarize recently reported findings from measurements of a wide range of chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs), hydrofluorocarbons (HFCs), perfluorocarbons (PFCs), sulfur hexafluoride (SF6), and other halogenated compounds at Gosan (Jeju Island, Korea) within the advanced global atmospheric gases experiment (AGAGE). General wind patterns at Gosan bring air masses from the surrounding areas, allowing the monitoring of both clean baseline and polluted air masses. We have analyzed our measurements since November 2007 both with an interspecies correlation method and with an inversion method based on the FLEXPART Lagrangian particle dispersion model to estimate these regional emissions. The results show that emissions of halogenated compounds in East Asia account for over 20% of global emissions, both in terms of ozone depletion potential (ODP) and global warming potential (GWP), and emphasize the importance of atmospheric measurements for quantifying emissions of these compounds in this region.

#### Distributions, long term trends and emissions of four perfluorocarbons in remote parts of the atmosphere and firn air (2012) [link]

Authors: Laube, Hogan, Newland, Mani, Fraser, Brenninkmeijer, Martinerie, Oram, Röckmann, Schwander, Witrant, Mills, Reeves, Sturges

We report the first data set of atmospheric abundances for the following four perfluoroalkanes: n-decafluorobutane (n-C4F10), n-dodecafluoropentane (n-C5F12), n-tetradecafluorohexane (n-C6F14) and n-hexadecafluoroheptane (n-C7F16). All four compounds could be detected and quantified in air samples from remote locations in the Southern Hemisphere (at Cape Grim, Tasmania, archived samples dating back to 1978) and the upper troposphere (a passenger aircraft flying from Germany to South Africa). Further observations originate from air samples extracted from deep firn in Greenland and allow trends of atmospheric abundances in the earlier 20th century to be inferred. All four compounds were not present in the atmosphere prior to the 1960s. n-C4F10 and n-C5F12 were also measured in samples collected in the stratosphere with the data indicating that they have no significant sinks in this region. Emissions were inferred from these observations and found to be comparable with emissions from the EDGAR database for n-C6F14. However, emissions of n-C4F10, n-C5F12 and n-C7F16 were found to differ by up to five orders of magnitude between our approach and the database. Although the abundances of the four perfluorocarbons reported here are currently small (less than 0.3 parts per trillion) they have strong Global Warming Potentials several thousand times higher than carbon dioxide (on a 100-yr time horizon) and continue to increase in the atmosphere. We estimate that the sum of their cumulative emissions reached 325 million metric tonnes CO2 equivalent at the end of 2009.

#### Perfluorocarbons [Global Climate, Atmospheric composition] (2012) [link]

Authors: Mühle

No abstract available.

#### State of the Climate in 2011: [Global Climate, Atmospheric composition] Perfluorocarbons (2012) [link]

Authors: Mühle

Perfluorocarbons (PFCs) are extremely long-lived, potent greenhouse gases. PFC-14 (CF4) and PFC-116 (C2F6) have lower limits for atmospheric lifetimes of 50 000 and 10 000 years, respectively, and global warming potentials (100-year time horizon) of 7390 and 12 200, respectively (Montzka et al. 2011). Anthropogenic PFC-14 and PFC-116 were historically emitted as by-products of aluminum production (IAI 2011) and are also emitted from the electronics industry. However, the onset and extent of PFC emissions from the electronics industry is poorly known due to limited reporting (Worton et al. 2007; Mühle et al. 2010). A small natural source of CF4 from degassing of Earth’s crust has been identified (Harnisch and Eisenhauer 1998; Harnisch et al. 2000), which, because of its extraordinarily long atmospheric lifetime, accounts for its significant preindustrial abundance (Harnisch et al. 1996a,b) of 34.7 ± 0.2 ppt (Mühle et al. 2010), or ~44% of its 2011 abundance. Based on preliminary data, global average surface mixing ratios of PFC-14 and PFC-116 were ~79 ppt and ~4.2 ppt in 2011, respectively (Fig. 2.44). Mixing ratios of PFC-14 rose at ~1.1 ppt yr-1 from the late 1970s to the early 1990s and by ~0.7 ppt yr-1 after- wards. Mixing ratios of PFC-116 rose at ~0.09 ppt yr-1 from the late 1970s to the mid-1990s, at ~0.12 ppt yr-1 until the mid-2000s, and at ~0.08 ppt yr-1 in recent years (Mühle et al. 2010 and preliminary data).

#### Long-term tropospheric trend of octafluorocyclobutane (c-C4F8 or PFC-318) (2012) [link]

Authors: Oram, Mani, Laube, Newland, Reeves, Sturges, Penkett, Brenninkmeijer, Röckmann, Fraser

Air samples collected at Cape Grim, Tasmania between 1978 and 2008 and during a series of more recent aircraft sampling programmes have been analysed to determine the atmospheric abundance and trend of octafluorocyclobutane (c-C4F8 or PFC-318). c-C4F8 has an atmospheric lifetime in excess of 3000 yr and a global warming potential (GWP) of 10 300 (100 yr time horizon), making it one of the most potent greenhouse gases detected in the atmosphere to date. The abundance of c-C4F8 in the Southern Hemisphere has risen from 0.35 ppt in 1978 to 1.2 ppt in 2010, and is currently increasing at a rate of around 0.03 ppt yr−1. It is the third most abundant perfluorocarbon (PFC) in the present day atmosphere, behind CF4 (~75 ppt) and C2F6 (~4 ppt). Although a number of potential sources of c-C4F8 have been reported, including the electronics and semi-conductor industries, there remains a large discrepancy in the atmospheric budget. Using a 2-D global model to derive top-down global emissions based on the Cape Grim measurements yields a recent (2007) emission rate of around 1.1 Gg yr−1 and a cumulative emission up to and including 2007 of 38.1 Gg. Emissions reported on the EDGAR emissions database for the period 1986–2005 represent less than 1% of the top-down emissions for the same period, which suggests there is a large unaccounted for source of this compound. It is also apparent that the magnitude of this source has varied considerably over the past 30 yr, declining sharply in the late 1980s before increasing again in the mid-1990s.

#### Trends and seasonal cycles in the isotopic composition of nitrous oxide since 1940 (2012) [link]

Authors: Park, Croteau, Boering, Etheridge, Ferretti, Fraser, Kim, Krummel, Langenfelds, van Ommen, Steele, Trudinger

The atmospheric nitrous oxide mixing ratio has increased by 20% since 1750 (ref. 1). Given that nitrous oxide is both a long-lived greenhouse gas and a stratospheric ozone-depleting substance, this increase is of global concern. However, the magnitude and geographic distribution of nitrous oxide sources, and how they have changed over time, is uncertain. A key unknown is the influence of the stratospheric circulation, which brings air depleted in nitrous oxide to the surface. Here, we report the oxygen and intramolecular nitrogen isotopic compositions of nitrous oxide in firn air samples from Antarctica and archived air samples from Cape Grim, Tasmania, spanning 1940–2005. We detect seasonal cycles in the isotopic composition of nitrous oxide at Cape Grim. The phases and amplitudes of these seasonal cycles allow us to distinguish between the influence of the stratospheric sink and the oceanic source at this site, demonstrating that isotope measurements can help in the attribution and quantification of surface sources in general. Large interannual variations and long-term decreasing trends in isotope composition are also apparent. These long-term trends allow us to distinguish between natural and anthropogenic sources of nitrous oxide, and confirm that the rise in atmospheric nitrous oxide levels is largely the result of an increased reliance on nitrogen-based fertilizers.

#### The value of high-frequency, high-precision methane isotopologue measurements for source and sink estimation (2012) [link]

Authors: Rigby, Manning, Prinn

We present an observing system simulation experiment examining the potential benefits of new methane isotopologues measurements for global- and national-scale source and sink inversions. New measurements are expected in the coming years, using quantum cascade laser spectroscopy with sample preconcentration, that will allow observations ofδ13C - CH4 and δD - CH4at approximately hourly intervals and higher precision than previously possible. Using model-generated ‘pseudo-data’, we predict the variability that these new systems should encounter in the atmosphere, and estimate the additional uncertainty reduction that should result from their use in source and sink inversions. We find that much of theδ-value variability from seasonal to daily timescales should be resolvable at the target precision of the new observations. For global source estimation, we find additional uncertainty reductions of between 3–9 Tg/year for four major source categories (microbial, biomass burning, landfill and fossil fuel), compared to mole fraction-only inversions, if the higher end of the anticipated isotopologue-measurement precisions can be achieved. On national scales, we obtain average uncertainty reductions of ∼10% of the source strength for countries close to high-frequency monitoring sites, although the degree of uncertainty reduction on such small scales varies significantly (from close to 0% to almost 50%) for different sources and countries.

#### Robust extraction of baseline signal of atmospheric trace species using local regression (2012) [link]

Authors: Ruckstuhl, Henne, Reimann, Steinbacher, Vollmer, O’Doherty, Buchmann, Hueglin

The identification of atmospheric trace species measurements that are representative of well-mixed background air masses is required for monitoring atmospheric composition change at background sites. We present a statistical method based on robust local regression that is well suited for the selection of background measurements and the estimation of associated baseline curves. The bootstrap technique is applied to calculate the uncertainty in the resulting baseline curve. The non-parametric nature of the proposed approach makes it a very flexible data filtering method. Application to carbon monoxide (CO) measured from 1996 to 2009 at the high-alpine site Jungfraujoch (Switzerland, 3580 m a.s.l.), and to measurements of 1,1-difluoroethane (HFC-152a) from Jungfraujoch (2000 to 2009) and Mace Head (Ireland, 1995 to 2009) demonstrates the feasibility and usefulness of the proposed approach. The determined average annual change of CO at Jungfraujoch for the 1996 to 2009 period as estimated from filtered annual mean CO concentrations is −2.2 ± 1.1 ppb yr−1. For comparison, the linear trend of unfiltered CO measurements at Jungfraujoch for this time period is −2.9 ± 1.3 ppb yr−1.

#### Global and regional emission estimates for HCFC-22 (2012) [link]

Authors: Saikawa, Rigby, Prinn, Montzka, Miller, Kuijpers, Fraser, Vollmer, Saito, Yokouchi, Harth, Mühle, Weiss, Salameh, Kim, Li, Park, Kim, Young, O’Doherty, Simmonds, McCulloch, Krummel, Steele, Lunder, Hermansen, Maione, Arduini, Yao, Zhou, Wang, Elkins, Hall

HCFC-22 (CHClF2, chlorodifluoromethane) is an ozone-depleting substance (ODS) as well as a significant greenhouse gas (GHG). HCFC-22 has been used widely as a refrigerant fluid in cooling and air-conditioning equipment since the 1960s, and it has also served as a traditional substitute for some chlorofluorocarbons (CFCs) controlled under the Montreal Protocol. A low frequency record on tropospheric HCFC-22 since the late 1970s is available from measurements of the Southern Hemisphere Cape Grim Air Archive (CGAA) and a few Northern Hemisphere air samples (mostly from Trinidad Head) using the Advanced Global Atmospheric Gases Experiment (AGAGE) instrumentation and calibrations. Since the 1990s high-frequency, high-precision, in situ HCFC-22 measurements have been collected at these AGAGE stations. Since 1992, the Global Monitoring Division of the National Oceanic and Atmospheric Administration/Earth System Research Laboratory (NOAA/ESRL) has also collected flasks on a weekly basis from remote sites across the globe and analyzed them for a suite of halocarbons including HCFC-22. Additionally, since 2006 flasks have been collected approximately daily at a number of tower sites across the US and analyzed for halocarbons and other gases at NOAA. All results show an increase in the atmospheric mole fractions of HCFC-22, and recent data show a growth rate of approximately 4% per year, resulting in an increase in the background atmospheric mole fraction by a factor of 1.7 from 1995 to 2009. Using data on HCFC-22 consumption submitted to the United Nations Environment Programme (UNEP), as well as existing bottom-up emission estimates, we first create globally-gridded a priori HCFC-22 emissions over the 15 yr since 1995. 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. Our inversion indicates that the global HCFC-22 emissions have an increasing trend between 1995 and 2009. We further find a surge in HCFC-22 emissions between 2005 and 2009 from developing countries in Asia – the largest emitting region including China and India. Globally, substantial emissions continue despite production and consumption being phased out in developed countries currently.

#### Emissions halted of the potent greenhouse gas SF5CF3 (2012) [link]

Authors: Sturges, Oram, Laube, Reeves, Newland, Hogan, Martinerie, Witrant, Brenninkmeijer, Schuck, Fraser

Long term measurements in background air (Cape Grim, Tasmania) and firn air (NEEM, Greenland) of the potent long-lived greenhouse gas SF5CF3 show that emissions declined after the late 1990s, having grown since the 1950s, and became indistinguishable from zero after 2003. The timing of this decline suggests that emissions of this gas may have been related to the production of certain fluorochemicals; production of which have been recently phased out. An earlier observation of closely correlated atmospheric abundances of SF5CF3 and SF6 are shown here to have likely been purely coincidental, as their respective trends diverged after 2002. Due to its long lifetime (ca. 900 yr), atmospheric concentrations of SF5CF3 have not declined, and it is now well mixed between hemispheres, as is also shown here from interhemispheric aircraft measurements. Total cumulative emissions of SF5CF3 amount to around 5 kT.

#### An assessment of the surface ozone trend in Ireland relevant to air pollution and environmental protection (2012) [link]

Authors: Tripathi, Jennings, O'Dowd, O'Leary, Lambkin, Moran, O’Doherty, Spain

Hourly data (1994–2009) of surface ozone concentrations at eight monitoring sites have been investigated to assess target level and long–term objective exceedances and their trends. The European Union (EU) ozone target value for human health (60 ppb–maximum daily 8–hour running mean) has been exceeded for a number of years for almost all sites but never exceeded the set limit of 25 exceedances in one year. Second highest annual hourly and 4th highest annual 8–hourly mean ozone concentrations have shown a statistically significant negative trend for in–land sites of Cork–Glashaboy, Monaghan and Lough Navar and no significant trend for the Mace Head site. Peak afternoon ozone concentrations averaged over a three year period from 2007 to 2009 have been found to be lower than corresponding values over a three–year period from 1996 to 1998 for two sites: Cork–Glashaboy and Lough Navar sites. The EU long–term objective value of AOT40 (Accumulated Ozone Exposure over a threshold of 40 ppb) for protection of vegetation (3 ppm–hour, calculated from May to July) has been exceeded, on an individual year basis, for two sites: Mace Head and Valentia. The critical level for the protection of forest (10 ppm–hour from April to September) has not been exceeded for any site except at Valentia in the year 2003. AOT40–Vegetation shows a significant negative trend for a 3–year running average at Cork–Glashaboy (–0.13±0.02 ppm–hour per year), at Lough Navar (–0.05±0.02 ppm–hour per year) and at Monaghan (–0.03±0.03 ppm–hour per year–not statistically significant) sites. No statistically significant trend was observed for the coastal site of Mace head. Overall, with the exception of the Mace Head and Monaghan sites, ozone measurement records at Irish sites show a downward negative trend in peak values that affect human health and vegetation.

#### A new multi-gas constrained model of trace gas non-homogeneous transport in firn: evaluation and behaviour at eleven polar sites (2012) [link]

Authors: Witrant, Martinerie, Hogan, Laube, Kawamura, Capron, Montzka, Dlugokencky, Etheridge, Blunier, Sturges

Insoluble trace gases are trapped in polar ice at the firn-ice transition, at approximately 50 to 100 m below the surface, depending primarily on the site temperature and snow accumulation. Models of trace gas transport in polar firn are used to relate firn air and ice core records of trace gases to their atmospheric history. We propose a new model based on the following contributions. First, the firn air transport model is revised in a poromechanics framework with emphasis on the non-homogeneous properties and the treatment of gravitational settling. We then derive a nonlinear least square multi-gas optimisation scheme to calculate the effective firn diffusivity (automatic diffusivity tuning). The improvements gained by the multi-gas approach are investigated (up to ten gases for a single site are included in the optimisation process). We apply the model to four Arctic (Devon Island, NEEM, North GRIP, Summit) and seven Antarctic (DE08, Berkner Island, Siple Dome, Dronning Maud Land, South Pole, Dome C, Vostok) sites and calculate their respective depth-dependent diffusivity profiles. Among these different sites, a relationship is inferred between the snow accumulation rate and an increasing thickness of the lock-in zone defined from the isotopic composition of molecular nitrogen in firn air (denoted δ15N). It is associated with a reduced diffusivity value and an increased ratio of advective to diffusive flux in deep firn, which is particularly important at high accumulation rate sites. This has implications for the understanding of δ15N of N2 records in ice cores, in relation with past variations of the snow accumulation rate. As the snow accumulation rate is clearly a primary control on the thickness of the lock-in zone, our new approach that allows for the estimation of the lock-in zone width as a function of accumulation may lead to a better constraint on the age difference between the ice and entrapped gases.

#### A study of four-year HCFC-22 and HCFC-142b in-situ measurements at the Shangdianzi regional background station in China (2012) [link]

Authors: Yao, Vollmer, Xia, Zhou, Simmonds, Stordal, Maione, Reimann, O’Doherty

Atmospheric HCFC-22 (CHClF2) and HCFC-142b (CH3CClF2) in-situ measurements have been recorded by an automated gas chromatograph-electron capture detectors (GC-ECDs) system and a gas chromatography/mass spectrometry (Medusa-GC/MS) system at the Global Atmosphere Watch (GAW) regional background station Shangdianzi (SDZ), China. The mixing ratios of the two HCFCs at SDZ show frequent events with elevated concentrations due to polluted air from urban or industrialized areas. The mean background mixing ratios for HCFC-22 and HCFC-142b were 205.3 ppt (parts per trillion, 10−12, molar) and 20.7 ppt, respectively, for the study period (March 2007–February 2011). The yearly background mixing ratios for the two HCFCs at SDZ are similar to those measured at Trinidad Head and Mace Head located in the Northern Hemisphere (NH), but larger than Cape Grim and Cape Matatula (located in the Southern Hemisphere) due to inter-hemispheric differences caused by predominantly NH emissions. During the study period, background mixing ratios exhibited positive growth rates of 8.7 ppt yr−1 for HCFC-22 and 0.95 ppt yr−1 for HCFC-142b. HCFC’s seasonality exhibits a summer/autumn maximum and a winter minimum. 4-year averaged background seasonal amplitudes (maximum–minimum) are 6.0 ppt for HCFC-22 and 0.9 ppt for HCFC-142b. The seasonal fluctuations (maximum–minimum) in polluted events are 105.4 ppt for HCFC-22 and 29.1 ppt for HCFC-142b, which are much stronger than the fluctuations under background conditions. However, both HCFC-22 and HCFC-142b show summer minima in 2008, which is most likely due to emission control regulations when the Olympic Games were held in Beijing.

#### In-situ measurements of atmospheric hydrofluorocarbons (HFCs) and perfluorocarbons (PFCs) at the Shangdianzi regional background station, China (2012) [link]

Authors: Yao, Vollmer, Zhou, Henne, Reimann, Li, Wenger, Hill

Atmospheric hydrofluorocarbons (HFCs) and perfluorocarbons (PFCs) were measured in-situ at the Shangdianzi (SDZ) Global Atmosphere Watch (GAW) regional background station, China, from May 2010 to May 2011. The time series for five HFCs and three PFCs showed occasionally high-concentration events while background conditions occurred for 36% (HFC-32) to 83% (PFC-218) of all measurements. The mean mixing ratios during background conditions were 24.5 ppt (parts per trillion, 10−12, molar) for HFC-23, 5.86 ppt for HFC-32, 9.97 ppt for HFC-125, 66.0 ppt for HFC-134a, 9.77 ppt for HFC-152a, 79.1 ppt for CF4, 4.22 ppt for PFC-116, and 0.56 ppt for PFC-218. The background mixing ratios for the compounds at SDZ are consistent with those obtained at mid to high latitude sites in the Northern Hemisphere. North-easterly winds were associated with negative contributions to atmospheric HFC and PFC loadings (mixing ratio anomalies weighted by time associated with winds in a given sector), whereas south-westerly advection (urban sector) showed positive loadings. Chinese emissions estimated by a tracer ratio method using carbon monoxide as tracer were 3.6 ± 3.2 kt yr−1 for HFC-23, 4.3 ± 3.6 kt yr−1 for HFC-32, 2.7 ± 2.3 kt yr−1 for HFC-125, 6.0 ± 5.6 kt yr−1 for HFC-134a, 2.0 ± 1.8 kt yr−1 for HFC-152a, 2.4 ± 2.1 kt yr−1 for CF4, 0.27 ± 0.26 kt yr−1 for PFC-116, and 0.061 ± 0.095 kt yr−1 for PFC-218. The lower HFC-23 emissions compared to earlier studies may be a result of the HFC-23 abatement measures taken as part of Clean Development Mechanism (CDM) projects that started in 2005.

#### Long-term variation of atmospheric methyl iodide and its link to global environmental change (2012) [link]

Authors: Yokouchi, Nojiri, Toom-Sauntry, Fraser, Inuzuka, Tanimoto, Nara, Murakami, Mukai

It has been suggested that the emissions of volatile organic compounds (VOCs) from the ocean could be affected by global warming, with feedback effects on the climate. In order to detect changes in their emissions as a response to global environmental change, long-term observations are required. Here we report for the first time long-term variations of atmospheric methyl iodide (CH3I), the most abundant iodine-containing compound predominantly emitted from the ocean. We monitored its concentration periodically at five remote sites covering 82.5°N–40.4°S and over the western and northern Pacific Ocean from the late 1990s to 2011. At most observation sites, CH3I increased from 2003/2004 to 2009/2010 by several tens of per cent, with a decreasing trend before 2003. The inter-annual variation pattern is well approximated by a sine curve with a period of 11 years and showed a good correlation with the Pacific Decadal Oscillation (PDO), suggesting that CH3I emissions are affected by global-scale, sea surface temperature (SST)-related, decadal anomalies. The influence of natural oscillations or environmental change on trace gas emissions from the ocean may be greater than has been thought previously, and these emissions may thus be sensitive to future climate change.

### 2013

#### Nitrogen trifluoride global emissions estimated from updated atmospheric measurements (2013) [link]

Authors: Arnold, Harth, Mühle, Manning, Salameh, Kim, Ivy, Steele, Petrenko, Severinghaus, Baggenstos, Weiss

Nitrogen trifluoride (NF3) has potential to make a growing contribution to the Earth’s radiative budget; however, our understanding of its atmospheric burden and emission rates has been limited. Based on a revision of our previous calibration and using an expanded set of atmospheric measurements together with an atmospheric model and inverse method, we estimate that the global emissions of NF3 in 2011 were 1.18 ± 0.21 Gg⋅y−1, or ∼20 Tg CO2-eq⋅y−1 (carbon dioxide equivalent emissions based on a 100-y global warming potential of 16,600 for NF3). The 2011 global mean tropospheric dry air mole fraction was 0.86 ± 0.04 parts per trillion, resulting from an average emissions growth rate of 0.09 Gg⋅y−2 over the prior decade. In terms of CO2 equivalents, current NF3 emissions represent between 17% and 36% of the emissions of other long-lived fluorinated compounds from electronics manufacture. We also estimate that the emissions benefit of using NF3 over hexafluoroethane (C2F6) in electronics manufacture is significant—emissions of between 53 and 220 Tg CO2-eq⋅y−1 were avoided during 2011. Despite these savings, total NF3 emissions, currently ∼10% of production, are still significantly larger than expected assuming global implementation of ideal industrial practices. As such, there is a continuing need for improvements in NF3 emissions reduction strategies to keep pace with its increasing use and to slow its rising contribution to anthropogenic climate forcing.

#### Off-line algorithm for calculation of vertical tracer transport in the troposphere due to deep convection (2013) [link]

Authors: Belikov, Maksyutov, Krol, Fraser, Rigby, Bian, Agusti-Panareda, Bergmann, Bousquet, Cameron-Smith, Chipperfield, Fortems-Cheiney, Gloor, Haynes, Hess, Houweling, Kawa, Law, Loh, Meng, Palmer, Patra, Prinn, Saito, Wilson

A modified cumulus convection parametrisation scheme is presented. This scheme computes the mass of air transported upward in a cumulus cell using conservation of moisture and a detailed distribution of convective precipitation provided by a reanalysis dataset. The representation of vertical transport within the scheme includes entrainment and detrainment processes in convective updrafts and downdrafts. Output from the proposed parametrisation scheme is employed in the National Institute for Environmental Studies (NIES) global chemical transport model driven by JRA-25/JCDAS reanalysis. The simulated convective precipitation rate and mass fluxes are compared with observations and reanalysis data. A simulation of the short-lived tracer 222Rn is used to further evaluate the performance of the cumulus convection scheme. Simulated distributions of 222Rn are evaluated against observations at the surface and in the free troposphere, and compared with output from models that participated in the TransCom-CH4 Transport Model Intercomparison. From this comparison, we demonstrate that the proposed convective scheme in general is consistent with observed and modeled results.

#### Analysis and interpretation of 25 years of ozone observations at the Mace Head Atmospheric Research Station on the Atlantic Ocean coast of Ireland from 1987 to 2012 (2013) [link]

Authors: Derwent, Manning, Simmonds, Spain, O’Doherty

Observations of surface ozone have been made at the Mace Head Atmospheric Research Station on the Atlantic Ocean coastline of Ireland from April 1987 through to December 2012. Using meteorological analyses and a sophisticated Lagrangian dispersion model, the hourly observations have been sorted into baseline northern hemisphere mid-latitude, European regionally-polluted and southerly sub-tropical maritime air masses. Baseline monthly average levels showed a pronounced seasonal cycle with spring maxima and summer minima. Baseline levels have shown an average annual increase of +0.25 ± 0.09 ppb year−1 which has been stronger in the winter and spring and weaker in the summer months. The rate of this annual increase has slowed over the last decade to the extent that annual levels have been relatively constant through the 2000s. Annual mean O3 levels in European air masses have shown much reduced upwards trends compared with baseline air masses. European levels show a seasonal cycle with a spring maxima and a winter minima. Policy actions to reduce European regional-scale NOx emissions have led to an increase in wintertime O3 levels and a decrease in summertime peak levels. Levels in southerly sub-tropical maritime air masses have shown different seasonal cycles, different seasonal trends and systematically lower levels compared with baseline air masses. The baseline observations have been compared against a number of policy-relevant O3 metrics and these have demonstrated the potential importance of the growing northern hemisphere O3 baseline levels over the 25 year study period.

#### HCFC-22 emissions at global and regional scales between 1995 and 2010: Trends and variability (2013) [link]

Authors: Fortems-Cheiney, Chevallier, Saunois, Pison, Bousquet, Cressot, Wang, Yokouchi, Artuso

HCFC‒22 (CHClF2, chlorodifluoromethane) is an ozone‒depleting substance, the consumption of which is controlled under the Montreal Protocol. Within a Bayesian inversion framework, we use measurements of HCFC‒22 atmospheric concentrations to constrain estimates of HCFC‒22 emissions, at the grid point 3.75°×2.5° and 8 day resolution, from January 1995 to December 2010. Starting from a new gridded bottom‒up inventory which is then optimized, our method shows continuously rising global emissions, from 182±11 Gg in 1995 to the maximum of 410±9 Gg in 2009. This is mainly due to an increase of emissions in developing regions, particularly in Eastern Asia, and occurs despite the current phase‒out in developed countries. The high temporal resolution of our inversion (8 day) allows to reveal some of the emission seasonality, the global posterior sources ranging from 25 Gg/month in November to 42 Gg/month in July, for example, in 2010.

#### Estimating regional methane surface fluxes: the relative importance of surface and GOSAT mole fraction measurements (2013) [link]

Authors: Fraser, Palmer, Feng, Boesch, Cogan, Parker, Dlugokencky, Fraser, Krummel, Langenfelds, O’Doherty, Prinn, Steele, van der Schoot, Weiss

We use an ensemble Kalman filter (EnKF), together with the GEOS-Chem chemistry transport model, to estimate regional monthly methane (CH4) fluxes for the period June 2009–December 2010 using proxy dry-air column-averaged mole fractions of methane (XCH4) from GOSAT (Greenhouse gases Observing SATellite) and/or NOAA ESRL (Earth System Research Laboratory) and CSIRO GASLAB (Global Atmospheric Sampling Laboratory) CH4 surface mole fraction measurements. Global posterior estimates using GOSAT and/or surface measurements are between 510–516 Tg yr−1, which is less than, though within the uncertainty of, the prior global flux of 529 ± 25 Tg yr−1. We find larger differences between regional prior and posterior fluxes, with the largest changes in monthly emissions (75 Tg yr−1) occurring in Temperate Eurasia. In non-boreal regions the error reductions for inversions using the GOSAT data are at least three times larger (up to 45%) than if only surface data are assimilated, a reflection of the greater spatial coverage of GOSAT, with the two exceptions of latitudes >60° associated with a data filter and over Europe where the surface network adequately describes fluxes on our model spatial and temporal grid. We use CarbonTracker and GEOS-Chem XCO2 model output to investigate model error on quantifying proxy GOSAT XCH4 (involving model XCO2) and inferring methane flux estimates from surface mole fraction data and show similar resulting fluxes, with differences reflecting initial differences in the proxy value. Using a series of observing system simulation experiments (OSSEs) we characterize the posterior flux error introduced by non-uniform atmospheric sampling by GOSAT. We show that clear-sky measurements can theoretically reproduce fluxes within 10% of true values, with the exception of tropical regions where, due to a large seasonal cycle in the number of measurements because of clouds and aerosols, fluxes are within 15% of true fluxes. We evaluate our posterior methane fluxes by incorporating them into GEOS-Chem and sampling the model at the location and time of surface CH4 measurements from the AGAGE (Advanced Global Atmospheric Gases Experiment) network and column XCH4 measurements from TCCON (Total Carbon Column Observing Network). The posterior fluxes modestly improve the model agreement with AGAGE and TCCON data relative to prior fluxes, with the correlation coefficients (r2) increasing by a mean of 0.04 (range: −0.17 to 0.23) and the biases decreasing by a mean of 0.4 ppb (range: −8.9 to 8.4 ppb).

#### PFC and Carbon Dioxide Emissions from an Australian Aluminium Smelter Using Time-Integrated Stack Sampling and GC-MS, GC-FID Analysis (2013) [link]

Authors: Fraser, Steele, Cooksey

PFC (CF4, C2F6, C3F8), HFC (CHF3) and CO2 emissions were estimated from two potlines of the Hydro Australia Kurri Kurri aluminium smelter in the Hunter Valley, NSW, in 2009. Emissions were estimated using integrated sampling over a two week period followed by laboratory analysis for PFCs, HFCs and CO2. The PFC emission factors were similar to, but significantly more accurate than, annual PFC emission factors found for other Australian aluminium smelters (Bell Bay, Tasmania; Portland and Pt Henry, Victoria) in 2009, based on in situ PFC data measurements at Cape Grim, Tasmania. The CF4 and CO2 emission factors at Kurri Kurri are significantly larger than the Australian average CF4 and CO2 emission factors reported to the UNFCCC for 2009. C3F8 and CHF3 emissions at Kurri Kurri are low and do not significantly add to GHG emissions from an aluminium smelter.

#### The variability of methane, nitrous oxide and sulfur hexafluoride in Northeast India (2013) [link]

Authors: Ganesan, Chatterjee, Prinn, Harth, Salameh, Manning, Hall, Mühle, Meredith, Weiss, O’Doherty, Young

High-frequency atmospheric measurements of methane (CH4), nitrous oxide (N2O) and sulfur hexafluoride (SF6) from Darjeeling, India are presented from December 2011 (CH4)/March 2012 (N2O and SF6) 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 CH4, N2O and SF6, respectively. The observations show large variability and frequent pollution events in CH4 and N2O mole fractions, suggesting significant sources in the regions sampled by Darjeeling throughout the year. By contrast, SF6 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 CH4 and N2O 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 (

#### State of the Climate in 2012: [Global Climate, Atmospheric composition, Atmospheric Chemical Composition] Long-lived greenhouse gases (2013) [link]

Authors: Hall, Dlugokencky, Montzka, Dutton, Mühle, Elkins

#### State of the Climate in 2012: [Global Climate, Atmospheric composition, Atmospheric Chemical Composition] Ozone-depleting gases (2013) [link]

Authors: Hall, Montzka, Dutton, Elkins

In addition to their direct radiative forcing, long-lived gases containing chlorine and bromine also influence RF indirectly through destruction of stratospheric ozone. Production of many halocarbons has been substantially reduced in recent years through amendments and adjustments to the 1987 Montreal Protocol on Substances that Deplete the Ozone Layer. As a result, atmospheric mole fractions of many of the most potent ozone-depleting gases have been declining at Earth's surface (Figs. 2.30d, 2.31). While mole fractions of many ozone-depleting substances (ODS) are declining, those of some halogenated gases continue to increase globally (Fig. 2.31). The most rapid increases are observed for hydrochlorofluorocarbons (HCFCs) and hydrofluorocarbons (HFCs), which are common replacements for chlorofluorocarbons (CFCs), and halons. HCFCs contain chlorine and contribute to ozone depletion, while HFCs do not. Progress towards stratospheric halogen declining back to the 1980 level, often used as a benchmark, can be assessed with the NOAA Ozone-Depleting Gas Index (ODGI; Table 2.6; Hofmann and Montzka 2009). This index is derived from surface measurements of ozone-depleting substances together with an estimate of their potential to destroy stratospheric ozone, for example bromine is 60-65 times more effective than chlorine (Montzka et al. 2011). Factors also include transit time from Earth's surface to the stratosphere, mixing during transit, and photolytic reactivity (Schauffler et al. 2003; Newman et al. 2007). The weighted sum of chlorine and bromine, combined with these factors yields a quantity known as Equivalent Effective Stratospheric Chlorine (EESC), which is an estimate of reactive halogen mole fraction in the stratosphere (Fig. 2.33a). The ODGI is the change in EESC from its peak, relative to that needed to reach the 1980 value (Fig. 2.33b). An updated NOAA ODGI was released in January 2013. The update includes improved methods of accounting for transport and reactions with solar radiation to form reactive halogen in the stratosphere (see http://www.esrl.noaa.gov.libproxy.mit.edu/gmd/odgi/).

The EESC is calculated for two stratospheric regions: Antarctica and midlatitudes. EESC was -1670 ppt and -3900 ppt at the beginning of 2012 for the midlatitudes and Antarctica, respectively. Current EESC values in the midlatitudes are smaller than those in the Antarctic because the liberation of reactive halogen from halocarbons is substantially less in the midlatitude stratosphere compared to the Antarctic. The ODGI for Antarctica was 87.2 at the beginning of 2012 (Fig. 2.33b). Thus, reactive halogen levels in the Antarctic stratosphere have progressed 13% of the way towards the 1980 benchmark. By contrast, the ODGI for midlatitudes was 65.4, indicating substantial progress towards the 1980 benchmark.

#### Observations: Atmosphere and Surface [Chapter 2] (2013) [link]

Authors: Hartmann, Klein Tank, Rusticucci

Climate Change 2013: The Physical Science Basis made extensive use of AGAGE data, with contributions from AGAGE scientists and collaborators (Montzka, Rigby, Weiss).

Authors: Kirschke, Bousquet, Ciais, Saunois, Canadell, Dlugokencky, Bergamaschi, Bergmann, Blake, Bruhwiler, Cameron-Smith, Castaldi, Chevallier, Feng, Fraser, Heimann, Hodson, Houweling, Josse, Fraser, Krummel, Lamarque, Langenfelds, Le Quéré, Naik, O’Doherty, Palmer, Pison, Plummer, Poulter, Prinn, Rigby, Ringeval, Santini, Schmidt, Shindell, Simpson, Spahni, Steele, Strode, Sudo, Szopa, van der Werf, Voulgarakis, van Weele, Weiss, Williams, Zeng

Methane is an important greenhouse gas, responsible for about 20% of the warming induced by long-lived greenhouse gases since pre-industrial times. By reacting with hydroxyl radicals, methane reduces the oxidizing capacity of the atmosphere and generates ozone in the troposphere. Although most sources and sinks of methane have been identified, their relative contributions to atmospheric methane levels are highly uncertain. As such, the factors responsible for the observed stabilization of atmospheric methane levels in the early 2000s, and the renewed rise after 2006, remain unclear. Here, we construct decadal budgets for methane sources and sinks between 1980 and 2010, using a combination of atmospheric measurements and results from chemical transport models, ecosystem models, climate chemistry models and inventories of anthropogenic emissions. The resultant budgets suggest that data-driven approaches and ecosystem models overestimate total natural emissions. We build three contrasting emission scenarios — which differ in fossil fuel and microbial emissions — to explain the decadal variability in atmospheric methane levels detected, here and in previous studies, since 1985. Although uncertainties in emission trends do not allow definitive conclusions to be drawn, we show that the observed stabilization of methane levels between 1999 and 2006 can potentially be explained by decreasing-to-stable fossil fuel emissions, combined with stable-to-increasing microbial emissions. We show that a rise in natural wetland emissions and fossil fuel emissions probably accounts for the renewed increase in global methane levels after 2006, although the relative contribution of these two sources remains uncertain.

#### Supplementary information to 'Observation-based assessment of stratospheric fractional release, lifetimes and Ozone Depletion Potentials of ten important source gases' (2013) [link]

Authors: Laube, Kiel, Bönisch, Engel, Röckmann, Volk, Sturges, Fraser, Oram

Supplement to article:

Laube, J. C., Keil, A., Bönisch, H., Engel, A., Röckmann, T., Volk, C. M., and Sturges, W. T.: Observation-based assessment of stratospheric fractional release, lifetimes, and ozone depletion potentials of ten important source gases, Atmos. Chem. Phys., 13, 2779-2791, doi:10.5194/acp-13-2779-2013, 2013.

#### Impact of transport model errors on the global and regional methane emissions estimated by inverse modelling (2013) [link]

Authors: Locatelli, Bousquet, Chevallier, Fortems-Cheiney, Szopa, Saunois, Agusti-Panareda, Bergmann, Bian, Cameron-Smith, Chipperfield, Gloor, Houweling, Kawa, Krol, Patra, Prinn, Rigby, Saito, Wilson

A modelling experiment has been conceived to assess the impact of transport model errors on methane emissions estimated in an atmospheric inversion system. Synthetic methane observations, obtained from 10 different model outputs from the international TransCom-CH4 model inter-comparison exercise, are combined with a prior scenario of methane emissions and sinks, and integrated into the three-component PYVAR-LMDZ-SACS (PYthon VARiational-Laboratoire de Météorologie Dynamique model with Zooming capability-Simplified Atmospheric Chemistry System) inversion system to produce 10 different methane emission estimates at the global scale for the year 2005. The same methane sinks, emissions and initial conditions have been applied to produce the 10 synthetic observation datasets. The same inversion set-up (statistical errors, prior emissions, inverse procedure) is then applied to derive flux estimates by inverse modelling. Consequently, only differences in the modelling of atmospheric transport may cause differences in the estimated fluxes. In our framework, we show that transport model errors lead to a discrepancy of 27 Tg yr−1 at the global scale, representing 5% of total methane emissions. At continental and annual scales, transport model errors are proportionally larger than at the global scale, with errors ranging from 36 Tg yr−1 in North America to 7 Tg yr−1 in Boreal Eurasia (from 23 to 48%, respectively). At the model grid-scale, the spread of inverse estimates can reach 150% of the prior flux. Therefore, transport model errors contribute significantly to overall uncertainties in emission estimates by inverse modelling, especially when small spatial scales are examined. Sensitivity tests have been carried out to estimate the impact of the measurement network and the advantage of higher horizontal resolution in transport models. The large differences found between methane flux estimates inferred in these different configurations highly question the consistency of transport model errors in current inverse systems.
Future inversions should include more accurately prescribed observation covariances matrices in order to limit the impact of transport model errors on estimated methane fluxes.

#### Ten years of continuous observations of stratospheric ozone depleting gases at Monte Cimone (Italy) — Comments on the effectiveness of the Montreal Protocol from a regional perspective (2013) [link]

Authors: Maione, Giostra, Arduini, Furlani, Graziosi, Vullo, Bonasoni

Halogenated gases potentially harmful to the stratospheric ozone layer are monitored worldwide in order to assess compliance with the Montreal Protocol requiring a phase out of these compounds on a global scale. We present the results of long term (2002–2011) continuous observation conducted at the Mt. Cimone GAW Global Station located on the highest peak of the Italian Northern Apennines, at the border of two important regions: the Po Valley (and the Alps) to the North and the Mediterranean Basin to the South. Bi-hourly air samples of CFC-12, CFC-11, CFC-114, CFC-115, H-1211, H-1301, methyl chloroform, carbon tetrachloride, HCFC-22, HCFC-142b, HCFC-124 and methyl bromide are collected and analysed using a gas chromatograph–mass spectrometer, providing multi annual time series. In order to appreciate the effectiveness of the Montreal Protocol from a regional perspective, trends and annual growth rates of halogenated species have been calculated after identification of their baseline values. A comparison with results from other international observation programmes is also presented. Our data show that the peak in the atmospheric mixing ratios of four chlorofluorocarbons, two halons and two chlorocarbons has been reached and all these species now show a negative atmospheric trend. Pollution episodes are still occurring for species like halon-1211, methyl chloroform and carbon tetrachloride, indicating fresh emissions from the site domain which could be ascribed both to fugitive un-reported uses of the compounds and/or emissions from banks. For the hydrofluorocarbons changes in the baseline are affected by emissions from fast developing Countries in East Asia. Fresh emissions from the site domain are clearly declining. Methyl bromide, for which the Mediterranean area is an important source region, shows, in a generally decreasing trend, an emission pattern that is not consistent with the phase-out schedule of this compound, with a renewed increase in the last two years of pollution episodes.

#### Southern hemispheric halon trends and global halon emissions, 1978–2011 (2013) [link]

Authors: Newland, Reeves, Oram, Laube, Sturges, Hogan, Begley, Fraser

The atmospheric records of four halons, H-1211 (CBrClF2), H-1301 (CBrF3), H-2402 (CBrF2CBrF2) and H-1202 (CBr2F2), measured from air collected at Cape Grim, Tasmania, between 1978 and 2011, are reported. Mixing ratios of H-1211, H-2402 and H-1202 began to decline in the early to mid-2000s, but those of H-1301 continue to increase up to mid-2011. These trends are compared to those reported by NOAA (National Oceanic and Atmospheric Administration) and AGAGE (Advanced Global Atmospheric Experiment). The observations suggest that the contribution of the halons to total tropospheric bromine at Cape Grim has begun to decline from a peak in 2008 of about 8.1 ppt. An extrapolation of halon mixing ratios to 2060, based on reported banks and predicted release factors, shows this decline becoming more rapid in the coming decades, with a contribution to total tropospheric bromine of about 3 ppt in 2060. Top-down global annual emissions of the halons were derived using a two-dimensional atmospheric model. The emissions of all four have decreased since peaking in the late 1980s–mid-1990s, but this decline has slowed recently, particularly for H-1301 and H-2402 which have shown no decrease in emissions over the past five years. The UEA (University of East Anglia) top-down model-derived emissions are compared to those reported using a top-down approach by NOAA and AGAGE and the bottom-up estimates of HTOC (Halons Technical Options Committee). The implications of an alternative set of steady-state atmospheric lifetimes are discussed. Using a lifetime of 14 yr or less for H-1211 to calculate top-down emissions estimates would lead to small, or even negative, estimated banks given reported production data. Finally emissions of H-1202, a product of over-bromination during the production process of H-1211, have continued despite reported production of H-1211 ceasing in 2010. This raises questions as to the source of these H-1202 emissions.

#### High-precision 14C measurements demonstrate production of in situ cosmogenic 14CH4 and rapid loss of in situ cosmogenic 14CO in shallow Greenland firn (2013) [link]

Authors: Petrenko, Severinghaus, Smith, Riedel, Baggenstos, Harth, Orsi, Hua, Franz, Takeshita, Brailsford, Weiss, Buizert, Dickson, Schaefer

Measurements of radiocarbon (14C) in carbon dioxide (CO2), methane (CH4) and carbon monoxide (CO) from glacial ice are potentially useful for absolute dating of ice cores, studies of the past atmospheric CH4 budget and for reconstructing the past cosmic ray flux and solar activity. Interpretation of 14C signals in ice is complicated by the fact that the two major 14C components—trapped atmospheric and in situ cosmogenic—are present in a combined form, as well as by a very limited understanding of the in situ component. This study measured 14CH4 and 14CO content in glacial firn with unprecedented precision to advance understanding of the in situ 14C component. 14CH4 and 14CO were melt-extracted on site at Summit, Greenland from three very large (∼1000 kg each) replicate samples of firn that spanned a depth range of 3.6–5.6 m. Non-cosmogenic 14C contributions were carefully characterized through simulated extractions and a suite of supporting measurements. In situ cosmogenic 14CO was quantified to better than ±0.6 molecules g−1 ice, improving on the precision of the best prior ice 14CO measurements by an order of magnitude. The 14CO measurements indicate that most (>99%) of the in situ cosmogenic 14C is rapidly lost from shallow Summit firn to the atmosphere. Despite this rapid 14C loss, our measurements successfully quantified 14CH4 in the retained fraction of cosmogenic 14C (to ±0.01 molecules g−1 ice or better), and demonstrate for the first time that a significant amount of 14CH4 is produced by cosmic rays in natural ice. This conclusion increases the confidence in the results of an earlier study that used measurements of 14CH4 in glacial ice to show that wetlands were the likely main driver of the large and rapid atmospheric CH4 increase approximately 11.6 kyr ago.

#### A 60 yr record of atmospheric carbon monoxide reconstructed from Greenland firn air (2013) [link]

Authors: Petrenko, Martinerie, Novelli, Etheridge, Levin, Wang, Blunier, Chappellaz, Kaiser, Lang, Steele, Hammer, Mak, Langenfelds, Schwander, Severinghaus, Witrant, Petron, Battle, Forster, Sturges, Lamarque, Steffen, White

We present the first reconstruction of the Northern Hemisphere (NH) high latitude atmospheric carbon monoxide (CO) mole fraction from Greenland firn air. Firn air samples were collected at three deep ice core sites in Greenland (NGRIP in 2001, Summit in 2006 and NEEM in 2008). CO records from the three sites agree well with each other as well as with recent atmospheric measurements, indicating that CO is well preserved in the firn at these sites. CO atmospheric history was reconstructed back to the year 1950 from the measurements using a combination of two forward models of gas transport in firn and an inverse model. The reconstructed history suggests that Arctic CO in 1950 was 140–150 nmol mol−1, which is higher than today's values. CO mole fractions rose by 10–15 nmol mol−1 from 1950 to the 1970s and peaked in the 1970s or early 1980s, followed by a ≈ 30 nmol mol−1 decline to today's levels. We compare the CO history with the atmospheric histories of methane, light hydrocarbons, molecular hydrogen, CO stable isotopes and hydroxyl radicals (OH), as well as with published CO emission inventories and results of a historical run from a chemistry-transport model. We find that the reconstructed Greenland CO history cannot be reconciled with available emission inventories unless unrealistically large changes in OH are assumed. We argue that the available CO emission inventories strongly underestimate historical NH emissions, and fail to capture the emission decline starting in the late 1970s, which was most likely due to reduced emissions from road transportation in North America and Europe.

#### Reassessing the variability in atmospheric H2 using the two-way nested TM5 model (2013) [link]

Authors: Pieterse, Krol, Batenburg, Brenninkmeijer, Popa, O’Doherty, Grant, Steele, Krummel, Langenfelds, Wang, Vermeulen, Schmidt, Yver, Jordan, Engel, Fisher, Lowry, Nisbet, Reimann, Vollmer, Steinbacher, Hammer, Forster, Sturges, Röckmann

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 1–2 h are asserted for the transport of H2 through the canopies of densely vegetated regions. The global scale variability of H2 and δ[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±8 Tg H2. The removal rates of H2 by deposition and photochemical oxidation are estimated at 53±4 and 23±2 Tg H2/yr, resulting in a tropospheric lifetime of 2.2±0.2 year.

#### Fully automated, high-precision instrumentation for the isotopic analysis of tropospheric N2O using continuous flow isotope ratio mass spectrometry (2013) [link]

Authors: Potter, Ono, Prinn

RATIONALE
Measurements of the isotopic composition of nitrous oxide in the troposphere have the potential to bring new information about the uncertain N2O budget, which mole fraction data alone have not been able to resolve. Characterizing the expected subtle variations in tropospheric N2O isotopic composition demands high-precision and high-frequency measurements. To enable useful observations of N2O isotopic composition in tropospheric air to reduce N2O source and sink uncertainty, it was necessary to develop a high-precision measurement system with fully automated capabilities for autonomous deployment at remote research stations.

METHODS
A fully automated pre-concentration system for high-precision measurements of N2O isotopic composition (δ15Nβ, δ15Nα, δ18O) in tropospheric air has been developed which combines a custom liquid-cryogen-free cryo-trapping system and gas chromatograph interfaced to a continuous flow isotope ratio mass spectrometry (IRMS) system. A quadrupole mass spectrometer was coupled in parallel to the IRMS system during development to evaluate peak interference. Multi-port inlet and fully-automated capabilities allow streamlined analyses between in situ air inlet, air standards, flask air sample, or other gas source in exactly replicated analysis sequences.

RESULTS
The system has the highest precision to date for 15N site-specific composition results (δ15Nα ±0.11‰, δ15Nβ ±0.14‰ (1σ)), attributed mostly to uniformity of analytical cycles and particular attention to fluorocarbon interference noted for 15N site-specific measurements by IRMS. Air measurements demonstrated the fully automated capacity and performance.

CONCLUSIONS
The system makes substantial headway in measurement precision, possibly defining the limits of IRMS measurement capabilities in low concentration N2O air samples, with fully automated capabilities to enable high-frequency in situ measurements. Copyright © 2013 John Wiley & Sons, Ltd.

#### Re-evaluation of the lifetimes of the major CFCs and CH3CCl3 using atmospheric trends (2013) [link]

Authors: Rigby, Prinn, O’Doherty, Montzka, McCulloch, Harth, Mühle, Salameh, Weiss, Young, Simmonds, Hall, Dutton, Nance, Mondeel, Elkins, Krummel, Steele, Fraser

#### Global modeling of soil nitrous oxide emissions from natural processes (2013) [link]

Authors: Saikawa, Schlosser, Prinn

Nitrous oxide is an important greenhouse gas and is a major ozone‒depleting substance. To understand and quantify soil nitrous oxide emissions, we expanded the Community Land Model with coupled Carbon and Nitrogen cycles version 3.5 by inserting a module to estimate monthly varying nitrous oxide emissions between 1975 and 2008. We evaluate our soil N2O emission estimates against existing emissions inventories, other process‒based model estimates, and observations from sites in the Amazon, North America, Central America, Asia, Oceania, Africa, and in Europe. The model reproduces precipitation, soil temperature, and observations of N2O emissions well at some but not at all sites and especially not during winter in the higher latitudes. Applying this model to estimate the past 24 years of global soil N2O emissions, we find that there is a significant decrease (increase) in soil N2O emissions associated with El Niño (La Niña) events.

#### TransCom model simulations of methane: Comparison of vertical profiles with aircraft measurements (2013) [link]

Authors: Saito, Patra, Sweeney, Machida, Krol, Houweling, Bousquet, Agusti-Panareda, Belikov, Bergmann, Bian, Cameron-Smith, Chipperfield, Fortems-Cheiney, Fraser, Gatti, Gloor, Hess, Kawa, Law, Locatelli, Loh, Maksyutov, Meng, Miller, Palmer, Prinn, Rigby, Wilson

To assess horizontal and vertical transports of methane (CH4) concentrations at different heights within the troposphere, we analyzed simulations by 12 chemistry transport models (CTMs) that participated in the TransCom-CH4 intercomparison experiment. Model results are compared with aircraft measurements at 13 sites in Amazon/Brazil, Mongolia, Pacific Ocean, Siberia/Russia, and United States during the period of 2001–2007. The simulations generally show good agreement with observations for seasonal cycles and vertical gradients. The correlation coefficients of the daily averaged model and observed CH4 time series for the analyzed years are generally larger than 0.5, and the observed seasonal cycle amplitudes are simulated well at most sites, considering the between-model variances. However, larger deviations show up below 2 km for the model-observation differences in vertical profiles at some locations, e.g., at Santarem, Brazil, and in the upper troposphere, e.g., at Surgut, Russia. Vertical gradients and concentrations are underestimated at Southern Great Planes, United States, and Santarem and overestimated at Surgut. Systematic overestimation and underestimation of vertical gradients are mainly attributed to inaccurate emission and only partly to the transport uncertainties. However, large differences in model simulations are found over the regions/seasons of strong convection, which is poorly represented in the models. Overall, the zonal and latitudinal variations in CH4 are controlled by surface emissions below 2.5 km and transport patterns in the middle and upper troposphere. We show that the models with larger vertical gradients, coupled with slower horizontal transport, exhibit greater CH4 interhemispheric gradients in the lower troposphere. These findings have significant implications for the future development of more accurate CTMs with the possibility of reducing biases in estimated surface fluxes by inverse modeling.

#### Can the carbon isotopic composition of methane be reconstructed from multi-site firn air measurements? (2013) [link]

Authors: Sapart, Martinerie, Witrant, Chappellaz, van de Wal, Sperlich, van der Veen, Bernard, Sturges, Blunier, Schwander, Etheridge, Röckmann

Methane is a strong greenhouse gas and large uncertainties exist concerning the future evolution of its atmospheric abundance. Analyzing methane atmospheric mixing and stable isotope ratios in air trapped in polar ice sheets helps in reconstructing the evolution of its sources and sinks in the past. This is important to improve predictions of atmospheric CH4 mixing ratios in the future under the influence of a changing climate. The aim of this study is to assess whether past atmospheric δ13C(CH4) variations can be reliably reconstructed from firn air measurements. Isotope reconstructions obtained with a state of the art firn model from different individual sites show unexpectedly large discrepancies and are mutually inconsistent. We show that small changes in the diffusivity profiles at individual sites lead to strong differences in the firn fractionation, which can explain a large part of these discrepancies. Using slightly modified diffusivities for some sites, and neglecting samples for which the firn fractionation signals are strongest, a combined multi-site inversion can be performed, which returns an isotope reconstruction that is consistent with firn data. However, the isotope trends are lower than what has been concluded from Southern Hemisphere (SH) archived air samples and high-accumulation ice core data. We conclude that with the current datasets and understanding of firn air transport, a high precision reconstruction of δ13C of CH4 from firn air samples is not possible, because reconstructed atmospheric trends over the last 50 yr of 0.3–1.5 ‰ are of the same magnitude as inherent uncertainties in the method, which are the firn fractionation correction (up to ~2 ‰ at individual sites), the Kr isobaric interference (up to ~0.8 ‰, system dependent), inter-laboratory calibration offsets (~0.2 ‰) and uncertainties in past CH4 levels (~0.5 ‰).

#### Interannual fluctuations in the seasonal cycle of nitrous oxide and chlorofluorocarbons due to the Brewer-Dobson circulation (2013) [link]

Authors: Simmonds, Manning, Athanassiadou, Scaife, Derwent, O’Doherty, Harth, Weiss, Dutton, Hall, Sweeney, Elkins

The tropospheric seasonal cycles of N2O, CFC-11 (CCl3F), and CFC-12 (CCl2F2) are influenced by atmospheric dynamics. The interannually varying summertime minima in mole fractions of these trace gases have been attributed to interannual variations in mixing of stratospheric air (depleted in CFCs and N2O) with tropospheric air with a few months lag. The amount of wave activity that drives the stratospheric circulation and influences the winter stratospheric jet and subsequent mass transport across the tropopause appears to be the primary cause of this interannual variability. We relate the observed seasonal minima of species at three Northern Hemisphere sites (Mace Head, Ireland; Trinidad Head, U.S.; and Barrow, Alaska) with the behavior of the winter stratospheric jet. As a result, a good correlation is obtained between zonal winds in winter at 10 hPa, 58°N–68°N, and the detrended seasonal minima in the stratosphere-influenced tracers. For these three tracers, individual Pearson correlation coefficients (r) between 0.51 and 0.71 were found, with overall correlations of between 0.67 and 0.77 when “composite species” were considered. Finally, we note that the long-term observations of CFCs and N2O in the troposphere provide an independent monitoring method complementary to satellite data. Furthermore, they could provide a useful observational measure of the strength of stratosphere-troposphere exchange and, thus, could be used to monitor any long-term trend in the Brewer-Dobson circulation which is predicted by climate models to increase over the coming decades.

#### Interannual variability in tropospheric nitrous oxide (2013) [link]

Authors: Thompson, Dlugokencky, Chevallier, Ciais, Dutton, Elkins, Langenfelds, Prinn, Weiss, Tohjima, O’Doherty, Krummel, Fraser, Steele

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.

#### Characterizing sampling biases in the trace gas climatologies of the SPARC Data Initiative: SAMPLING BIASES IN CLIMATOLOGIES (2013) [link]

Authors: Toohey, Hegglin, Tegtmeier, Anderson, Añel, Bourassa, Brohede, Degenstein, Froidevaux, Fuller, Funke, Gille, Jones, Kasai, Krüger, Kyrölä, Neu, Rozanov, Smith, Urban, von Clarmann, Walker, Wang

Monthly zonal mean climatologies of atmospheric measurements from satellite instruments can have biases due to the nonuniform sampling of the atmosphere by the instruments. We characterize potential sampling biases in stratospheric trace gas climatologies of the Stratospheric Processes and Their Role in Climate (SPARC) Data Initiative using chemical fields from a chemistry climate model simulation and sampling patterns from 16 satellite-borne instruments. The exercise is performed for the long-lived stratospheric trace gases O3 and H2O. Monthly sampling biases for O3 exceed 10% for many instruments in the high-latitude stratosphere and in the upper troposphere/lower stratosphere, while annual mean sampling biases reach values of up to 20% in the same regions for some instruments. Sampling biases for H2O are generally smaller than for O3, although still notable in the upper troposphere/lower stratosphere and Southern Hemisphere high latitudes. The most important mechanism leading to monthly sampling bias is nonuniform temporal sampling, i.e., the fact that for many instruments, monthly means are produced from measurements which span less than the full month in question. Similarly, annual mean sampling biases are well explained by nonuniformity in the month-to-month sampling by different instruments. Nonuniform sampling in latitude and longitude are shown to also lead to nonnegligible sampling biases, which are most relevant for climatologies which are otherwise free of biases due to nonuniform temporal sampling.

#### How well do different tracers constrain the firn diffusivity profile? (2013) [link]

Authors: Trudinger, Enting, Rayner, Etheridge, Buizert, Rubino, Krummel, Blunier

Firn air transport models are used to interpret measurements of the composition of air in firn and bubbles trapped in ice in order to reconstruct past atmospheric composition. The diffusivity profile in the firn is usually calibrated by comparing modelled and measured concentrations for tracers with known atmospheric history. However, in most cases this is an under-determined inverse problem, often with multiple solutions giving an adequate fit to the data (this is known as equifinality). Here we describe a method to estimate the firn diffusivity profile that allows multiple solutions to be identified, in order to quantify the uncertainty in diffusivity due to equifinality. We then look at how well different combinations of tracers constrain the firn diffusivity profile. Tracers with rapid atmospheric variations like CH3CCl3, HFCs and 14CO2 are most useful for constraining molecular diffusivity, while &delta:15N2 is useful for constraining parameters related to convective mixing near the surface. When errors in the observations are small and Gaussian, three carefully selected tracers are able to constrain the molecular diffusivity profile well with minimal equifinality. However, with realistic data errors or additional processes to constrain, there is benefit to including as many tracers as possible to reduce the uncertainties. We calculate CO2 age distributions and their spectral widths with uncertainties for five firn sites (NEEM, DE08-2, DSSW20K, South Pole 1995 and South Pole 2001) with quite different characteristics and tracers available for calibration. We recommend moving away from the use of a firn model with one calibrated parameter set to infer atmospheric histories, and instead suggest using multiple parameter sets, preferably with multiple representations of uncertain processes, to assist in quantification of the uncertainties.

#### Evaluating transport in the WRF model along the California coast (2013) [link]

Authors: Yver, Graven, Lucas, Cameron-Smith, Keeling, Weiss

This paper presents a step in the development of a top-down method to complement the bottom-up inventories of halocarbon emissions in California using high frequency observations, forward simulations and inverse methods. The Scripps Institution of Oceanography high-frequency atmospheric halocarbons measurement sites are located along the California coast and therefore the evaluation of transport in the chosen Weather Research Forecast (WRF) model at these sites is crucial for inverse modeling. The performance of the transport model has been investigated by comparing the wind direction and speed and temperature at four locations using aircraft weather reports as well at all METAR weather stations in our domain for hourly variations. Different planetary boundary layer (PBL) schemes, horizontal resolutions (achieved through nesting) and two meteorological datasets have been tested. Finally, simulated concentration of an inert tracer has been briefly investigated. All the PBL schemes present similar results that generally agree with observations, except in summer when the model sea breeze is too strong. At the coarse 12 km resolution, using ERA-interim (ECMWF Re-Analysis) as initial and boundary conditions leads to improvements compared to using the North American Model (NAM) dataset. Adding higher resolution nests also improves the match with the observations. However, no further improvement is observed from increasing the nest resolution from 4 km to 0.8 km. Once optimized, the model is able to reproduce tracer measurements during typical winter California large-scale events (Santa Ana). Furthermore, with the WRF/CHEM chemistry module and the European Database for Global Atmospheric Research (EDGAR) version 4.1 emissions for HFC-134a, we find that using a simple emission scaling factor is not sufficient to infer emissions, which highlights the need for more complex inversions.

#### Response of global soil consumption of atmospheric methane to changes in atmospheric climate and nitrogen deposition (2013) [link]

Authors: Zhuang, Chen, Xu, Tang, Saikawa, Lu, Melillo, Prinn, McGuire

Soil consumption of atmospheric methane plays an important secondary role in regulating the atmospheric CH4 budget, next to the dominant loss mechanism involving reaction with the hydroxyl radical (OH). Here we used a process-based biogeochemistry model to quantify soil consumption during the 20th and 21st centuries. We estimated that global soils consumed 32–36 Tg CH4 yr−1 during the 1990s. Natural ecosystems accounted for 84% of the total consumption, and agricultural ecosystems only consumed 5 Tg CH4 yr−1 in our estimations. During the twentieth century, the consumption rates increased at 0.03–0.20 Tg CH4 yr−2 with seasonal amplitudes increasing from 1.44 to 3.13 Tg CH4 month−1. Deserts, shrublands, and xeric woodlands were the largest sinks. Atmospheric CH4 concentrations and soil moisture exerted significant effects on the soil consumption while nitrogen deposition had a moderate effect. During the 21st century, the consumption is predicted to increase at 0.05-1.0 Tg CH4 yr−2, and total consumption will reach 45–140 Tg CH4 yr−1 at the end of the 2090s, varying under different future climate scenarios. Dry areas will persist as sinks, boreal ecosystems will become stronger sinks, mainly due to increasing soil temperatures. Nitrogen deposition will modestly reduce the future sink strength at the global scale. When we incorporated the estimated global soil consumption into our chemical transport model simulations, we found that nitrogen deposition suppressed the total methane sink by 26 Tg during the period 1998–2004, resulting in 6.6 ppb higher atmospheric CH4 mixing ratios compared to without considering nitrogen deposition effects. On average, a cumulative increase of every 1 Tg soil CH4 consumption decreased atmospheric CH4 mixing ratios by 0.26 ppb during the period 1998–2004.

#### Extreme 13C depletion of CCl2F2 in firn air samples from NEEM, Greenland (2013) [link]

Authors: Zuiderweg, Holzinger, Martinerie, Schneider, Kaiser, Witrant, Etheridge, Petrenko, Blunier, Röckmann

A series of 12 high volume air samples collected from the S2 firn core during the North Greenland Eemian Ice Drilling (NEEM) 2009 campaign have been measured for mixing ratio and stable carbon isotope composition of the chlorofluorocarbon CFC-12 (CCl2F2). While the mixing ratio measurements compare favorably to other firn air studies, the isotope results show extreme 13C depletion at the deepest measurable depth (65 m), to values lower than δ13C = −80‰ vs. VPDB (the international stable carbon isotope scale), compared to present day surface tropospheric measurements near −40‰. Firn air modeling was used to interpret these measurements. Reconstructed atmospheric time series indicate even larger depletions (to −120‰) near 1950 AD, with subsequent rapid enrichment of the atmospheric reservoir of the compound to the present day value. Mass-balance calculations show that this change is likely to have been caused by a large change in the isotopic composition of anthropogenic CFC-12 emissions, probably due to technological advances in the CFC production process over the last 80 yr, though direct evidence is lacking.

### 2014

#### Source Identification and Apportionment of Halogenated Compounds Observed at a Remote Site in East Asia (2014) [link]

Authors: Kim, Park, Kim, Park, Mühle, Lee, Lee, Jo, Kim

The sources of halogenated compounds in East Asia associated with stratospheric ozone depletion and climate change are relatively poorly understood. High-precision in situ measurements of 18 halogenated compounds and carbonyl sulfide (COS) made at Gosan, Jeju Island, Korea, from November 2007 to December 2011 were analyzed by a positive matrix factorization (PMF). Seven major industrial sources were identified from the enhanced concentrations of halogenated compounds observed at Gosan and corresponding concentration-based source contributions were also suggested: primary aluminum production explaining 37% of total concentration enhancements, solvent usage of which source apportionment is 25%, fugitive emissions from HCFC/HFC production with 11%, refrigerant replacements (9%), semiconductor/electronics industry (9%), foam blowing agents (6%), and fumigation (3%). Statistical trajectory analysis was applied to specify the potential emission regions for seven sources using back trajectories. Primary aluminum production, solvent usage and fugitive emission sources were mainly contributed by China. Semiconductor/electronics sources were dominantly located in Korea. Refrigerant replacement, fumigation and foam blowing agent sources were spread throughout East Asian countries. The specified potential source regions are consistent with country-based consumptions and emission patterns, verifying the PMF analysis results. The industry-based emission sources of halogenated compounds identified in this study help improve our understanding of the East Asian countries’ industrial contributions to halogenated compound emissions.

#### HFC-43-10mee atmospheric abundances and global emission estimates (2014) [link]

Authors: Arnold, Ivy, Harth, Vollmer, Mühle, Salameh, Steele, Krummel, Wang, Young, Lunder, Hermansen, Rhee, Kim, Reimann, O’Doherty, Fraser, Simmonds, Prinn, Weiss

We report in situ atmospheric measurements of hydrofluorocarbon HFC-43-10mee (C5H2F10; 1,1,1,2,2,3,4,5,5,5-decafluoropentane) from seven observatories at various latitudes, together with measurements of archived air samples and recent Antarctic flask air samples. The global mean tropospheric abundance was 0.21 ± 0.05 ppt (parts per trillion, dry air mole fraction) in 2012, rising from 0.04 ± 0.03 ppt in 2000. We combine the measurements with a model and an inverse method to estimate rising global emissions—from 0.43 ± 0.34 Gg yr−1 in 2000 to 1.13 ± 0.31 Gg yr−1 in 2012 (~1.9 Tg CO2-eq yr−1 based on a 100 year global warming potential of 1660). HFC-43-10mee—a cleaning solvent used in the electronics industry—is currently a minor contributor to global radiative forcing relative to total HFCs; however, our calculated emissions highlight a significant difference from the available reported figures and projected estimates.

#### Update on Ozone-Depleting Substances (ODSs) and Other Gases of Interest to the Montreal Protocol [Chapter 1] (2014) [link]

Authors: Carpenter, Reimann

The Scientific Assessment of Ozone Depletion: 2014 made extensive use of AGAGE ODS data and contributions from AGAGE scientists and collaborators (Fraser, Krummel, Mühle, O’Doherty, Reimann, Rigby).

#### On the consistency between global and regional methane emissions inferred from SCIAMACHY, TANSO-FTS, IASI and surface measurements (2014) [link]

Authors: Cressot, Chevallier, Bousquet, Crevoisier, Dlugokencky, Fortems-Cheiney, Frankenberg, Parker, Pison, Scheepmaker, Montzka, Krummel, Steele, Langenfelds

Satellite retrievals of methane weighted atmospheric columns are assimilated within a Bayesian inversion system to infer the global and regional methane emissions and sinks for the period August 2009 to July 2010. Inversions are independently computed from three different space-borne observing systems and one surface observing system under several hypotheses for prior-flux and observation errors. Posterior methane emissions are compared and evaluated against surface mole fraction observations via a chemistry-transport model. Apart from SCIAMACHY (SCanning Imaging Absorption spectroMeter for Atmospheric CartograpHY), the simulations agree fairly well with the surface mole fractions. The most consistent configurations of this study using TANSO-FTS (Thermal And Near infrared Sensor for carbon Observation – Fourier Transform Spectrometer), IASI (Infrared Atmospheric Sounding Interferometer) or surface measurements induce posterior methane global emissions of, respectively, 565 ± 21 Tg yr−1, 549 ± 36 Tg yr−1 and 538 ± 15 Tg yr−1 over the one-year period August 2009–July 2010. This consistency between the satellite retrievals (apart from SCIAMACHY) and independent surface measurements is promising for future improvement of CH4 emission estimates by atmospheric inversions.

#### Atmospheric Monitoring [Chapter 15] (2014) [link]

Authors: Etheridge, Leuning, Luhar, Loh, Spender, Allison, Steele, Zegelin, Jenkins, Krummel, Fraser

Carbon capture and geological storage (CCS) is presently the only way that we can make deep cuts in emissions from fossil fuel-based, large-scale sources of CO2 such as power stations and industrial plants. But if this technology is to be acceptable to the community, it is essential that it is credibly demonstrated by world-class scientists and engineers in an open and transparent manner at a commercially significant scale. The aim of the Otway Project was to do just this.Geologically Storing Carbon provides a detailed account of the CO2CRC Otway Project, one of the most comprehensive demonstrations of the deep geological storage or geosequestration of carbon dioxide undertaken anywhere. This book of 18 comprehensive chapters written by leading experts in the field is concerned with outstanding science, but it is not just a collection of scientific papers – it is about 'learning by doing'. For example, it explains how the project was organised, managed, funded and constructed, as well as the approach taken to community issues, regulations and approvals. It also describes how to understand the site: Are the rocks mechanically suitable? Will the CO2 leak? Is there enough storage capacity? Is monitoring effective? This is the book for geologists, engineers, regulators, project developers, industry, communities or anyone who wants to better understand how a carbon storage project really 'works'. It is also for people concerned with obtaining an in-depth appreciation of one of the key technology options for decreasing greenhouse emissions to the atmosphere. The CO2CRC Otway Project was one of the first geological storage projects to include comprehensive atmospheric monitoring as part of the assurance monitoring programme. This programme was designed to detect if any change had occurred in nearby soil, aquifers or atmosphere as a result of leakage of stored carbon dioxide. The development of methodologies able to attribute and quantify emissions was a major additional goal of the atmospheric monitoring research at the Otway site. AGAGE Cape Grim CH4, HFC-134a and SF6 data compared to data collected at Otway CO2 geosequestration site.

#### Sulfur hexafluoride (SF6) emissions in East Asia determined by inverse modeling (2014) [link]

Authors: Fang, Thompson, Saito, Yokouchi, Kim, Li, Kim, Park, Graziosi, Stohl

Sulfur hexafluoride (SF6) has a global warming potential of around 22 800 over a 100-year time horizon and is one of the greenhouse gases regulated under the Kyoto Protocol. Around the year 2000 there was a reversal in the global SF6 emission trend, from a decreasing to an increasing trend, which was likely caused by increasing emissions in countries that are not obligated to report their annual emissions to the United Nations Framework Convention on Climate Change. In this study, SF6 emissions during the period 2006-2012 for all East Asian countries - including Mongolia, China, Taiwan, North Korea, South Korea and Japan - were determined by using inverse modeling and in situ atmospheric measurements. We found that the most important sources of uncertainty associated with these inversions are related to the choice of a priori emissions and their assumed uncertainty, the station network as well as the meteorological input data. Much lower uncertainties are due to seasonal variability in the emissions, inversion geometry and resolution, and the measurement calibration scale. Based on the results of these sensitivity tests, we estimate that the total SF6 emission in East Asia increased rapidly from 2404 +/- 325 Mg yr(-1) in 2006 to 3787 +/- 512 Mg yr(-1) in 2009 and stabilized thereafter. China contributed 60-72% to the total East Asian emission for the different years, followed by South Korea (8-16 %), Japan (5-16 %) and Taiwan (4-7 %), while the contributions from North Korea and Mongolia together were less than 3% of the total. The per capita SF6 emissions are highest in South Korea and Taiwan, while the per capita emissions for China, North Korea and Japan are close to global average. During the period 2006-2012, emissions from China and from South Korea increased, while emissions from Taiwan and Japan decreased overall.

#### Australian carbon tetrachloride emissions in a global context (2014) [link]

Authors: Fraser, Dunse, Manning, Walsh, Wang, Krummel, Steele, Porter, Allison, O’Doherty, Simmonds, Mühle, Weiss, Prinn

Global (1978–2012) and Australian (1996–2011) carbon tetrachloride emissions are estimated from atmospheric observations of CCl4 using data from the Advanced Global Atmospheric Gases Experiment (AGAGE) global network, in particular from Cape Grim, Tasmania. Global and Australian emissions are in decline in response to Montreal Protocol restrictions on CCl4 production and consumption for dispersive uses in the developed and developing world. However, atmospheric data-derived emissions are significantly larger than ‘bottom-up’ estimates from direct and indirect CCl4 production, CCl4 transportation and use. Australian CCl4 emissions are not a result of these sources, and the identification of the origin of Australian emissions may provide a clue to the origin of some of these ‘missing’ global sources.

#### Equivalent effective stratospheric chlorine from Cape Grim Air Archive, Antarctic firn and AGAGE global measurements of ozone depleting substances (2014) [link]

Authors: Fraser, Krummel, Steele, Trudinger, Etheridge, Derek, O’Doherty, Simmonds, Miller, Mühle, Weiss, Oram, Prinn, Wang

Equivalent Effective Stratospheric Chlorine (EESC) is a parameter designed to estimate that component of ozone variability in the stratosphere that is driven by changes in the long-term abundances of Ozone Depleting Substances (ODSs) in the atmosphere. Currently available estimates of EESC from the past to the present are based on a combination of direct ODS measurements, ODS measurements on Antarctic firn/ice air and estimates of ODS abundances based on ODS emissions. The latter are also used to estimate future EESC values. In this paper we derive past (from about 1930) and present EESC values based entirely on atmospheric and Antarctic firn air measurements, avoiding the need to invoke ODS emissions estimates to ‘fill-in’ observational ‘gaps’. The EESC values we calculate based entirely on observations agree very well with the EESC values from a combination of observations and emission estimates published in the most recent (2011) international assessment of stratospheric ozone depletion, and also agree well with the observed variability of Antarctic ozone hole metrics over the past 35 years.

#### Estimating regional fluxes of CO2 and CH4 using space-borne observations of XCH4: XCO2 (2014) [link]

Authors: Fraser, Palmer, Feng, Bösch, Parker, Dlugokencky, Krummel, Langenfelds

We use the GEOS-Chem global 3-D atmospheric chemistry transport model to interpret XCH4:XCO2 column ratios retrieved from the Japanese Greenhouse Gases Observing Satellite (GOSAT). The advantage of these data over CO2 and CH4 columns retrieved independently using a full physics optimal estimation algorithm is that they are less prone to scattering-related regional biases. We show that the model is able to reproduce observed global and regional spatial (mean bias =0.7%) and temporal variations (global r2=0.92) of this ratio with a model bias

#### Characterization of uncertainties in atmospheric trace gas inversions using hierarchical Bayesian methods (2014) [link]

Authors: Ganesan, Rigby, Zammit-Mangion, Manning, Prinn, Fraser, Harth, Kim, Krummel, Li, Mühle, O’Doherty, Park, Salameh, Steele, Weiss

We present a hierarchical Bayesian method for atmospheric trace gas inversions. This method is used to estimate emissions of trace gases as well as "hyper-parameters" that characterize the probability density functions (PDFs) of the a priori emissions and model-measurement covariances. By exploring the space of "uncertainties in uncertainties", we show that the hierarchical method results in a more complete estimation of emissions and their uncertainties than traditional Bayesian inversions, which rely heavily on expert judgment. We present an analysis that shows the effect of including hyper-parameters, which are themselves informed by the data, and show that this method can serve to reduce the effect of errors in assumptions made about the a priori emissions and model-measurement uncertainties. We then apply this method to the estimation of sulfur hexafluoride (SF6) emissions over 2012 for the regions surrounding four Advanced Global Atmospheric Gases Experiment (AGAGE) stations. We find that improper accounting of model representation uncertainties, in particular, can lead to the derivation of emissions and associated uncertainties that are unrealistic and show that those derived using the hierarchical method are likely to be more representative of the true uncertainties in the system. We demonstrate through this SF6 case study that this method is less sensitive to outliers in the data and to subjective assumptions about a priori emissions and model-measurement uncertainties than traditional methods.

#### Results from the International Halocarbons in Air Comparison Experiment (IHALACE) (2014) [link]

Authors: Hall, Engel, Mühle, Elkins, Artuso, Atlas, Aydin, Blake, Brunke, Chiavarini, Fraser, Happell, Krummel, Levin, Loewenstein, Maione, Montzka, O’Doherty, Reimann, Rhoderick, Saltzman, Scheel, Steele, Vollmer, Weiss, Worthy, Yokouchi

The International Halocarbons in Air Comparison Experiment (IHALACE) was conducted to document relationships between calibration scales among various laboratories that measure atmospheric greenhouse and ozone depleting gases. This study included trace gases such as chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs), and hydrofluorocarbons (HFCs), as well as nitrous oxide, methane, sulfur hexafluoride, very short-lived halocompounds, and carbonyl sulfide. Many of these gases are present in the unpolluted atmosphere at pmol mol−1 (parts per trillion) or nmol mol−1 (parts per billion) levels. Six stainless steel cylinders containing natural and modified natural air samples were circulated among 19 laboratories. Results from this experiment reveal relatively good agreement (within a few percent) among commonly used calibration scales. Scale relationships for some gases, such as CFC-12 and CCl4, were found to be consistent with those derived from estimates of global mean mole fractions, while others, such as halon-1211 and CH3Br, revealed discrepancies. The transfer of calibration scales among laboratories was problematic in many cases, meaning that measurements tied to a particular scale may not, in fact, be compatible. Large scale transfer errors were observed for CH3CCl3 (10–100%) and CCl4 (2–30%), while much smaller scale transfer errors (< 1%) were observed for halon-1211, HCFC-22, and HCFC-142b. These results reveal substantial improvements in calibration over previous comparisons. However, there is room for improvement in communication and coordination of calibration activities with respect to the measurement of halogenated and related trace gases.

#### Development of a Spectroscopic Technique for Continuous Online Monitoring of Oxygen and Site-Specific Nitrogen Isotopic Composition of Atmospheric Nitrous Oxide (2014) [link]

Authors: Harris, Nelson, Olszewski, Zahniser, Potter, McManus, Whitehill, Prinn, Ono

Nitrous oxide is an important greenhouse gas and ozone-depleting-substance. Its sources are diffuse and poorly characterized, complicating efforts to understand anthropogenic impacts and develop mitigation policies. Online, spectroscopic analysis of N2O isotopic composition can provide continuous measurements at high time resolution, giving new insight into N2O sources, sinks, and chemistry. We present a new preconcentration unit, ?Stheno II?, coupled to a tunable infrared laser direct absorption spectroscopy (TILDAS) instrument, to measure ambient-level variations in 18O and site-specific 15N N2O isotopic composition at remote sites with a temporal resolution of

#### Quantifying aluminum and semiconductor industry perfluorocarbon emissions from atmospheric measurements (2014) [link]

Authors: Kim, Fraser, Mühle, Ganesan, Krummel, Steele, Park, Kim, Park, Arnold, Harth, Salameh, Prinn, Weiss, Kim

The potent anthropogenic perfluorocarbon greenhouse gases tetrafluoromethane (CF4) and hexafluoroethane (C2F6) are emitted to the atmosphere mainly by the aluminum and semiconductor industries. Global emissions of these perfluorocarbons (PFCs) calculated from atmospheric measurements are significantly greater than expected from reported national and industry-based emission inventories. In this study, in situ measurements of the two PFCs in the Advanced Global Atmospheric Gases Experiment network are used to show that their emission ratio varies according to the relative regional presence of these two industries, providing an industry-specific emission “signature” to apportion the observed emissions. Our results suggest that underestimated emissions from the global semiconductor industry during 1990–2010, as well as from China's aluminum industry after 2002, account for the observed differences between emissions based on atmospheric measurements and on inventories. These differences are significant despite the large uncertainties in emissions based on the methodologies used by these industries.

#### The Antarctic ozone hole during 2011 (2014) [link]

Authors: Klekociuk, Tully, Krummel, Gies, Petelina, Alexander, Deschamps, Fraser, Henderson, Javorniczky, Shanklin, Siddaway, Stone

The Antarctic ozone hole of 2011 is reviewed from a variety of perspectives, making use of various data and analyses. The ozone hole of 2011 was relatively large in terms of maximum area, minimum ozone level and total ozone deficit, being ranked amongst the top ten in terms of severity of the 32 ozone holes adequately characterised since 1979. In particular, the estimated integrated ozone mass effectively removed within the ozone hole of 2011 was 2119 Mt, which is the 7th largest deficit on record and 82 per cent of the peak value observed in 2006. The key factors in promoting the extent of Antarctic ozone loss in 2011 were the relatively low temperatures that occurred in the lower stratosphere of the polar cap region over most of the year, and the fact that the stratospheric vortex was relatively strong and stable, at least up to mid-spring. Dynamical disturbance of the polar vortex from mid-spring increased Antarctic ozone levels in the latter part of the ozone hole’s evolution and helped to limit the overall severity of depletion. Through examination of regression of various ozone metrics against expected levels of equivalent effective stratospheric chlorine, we suggest that recent changes in averaged ozone levels over Antarctica show some evidence of the recovery expected due to international controls on the manufacture of ozone depleting chemicals, albeit at a statistically low level of confidence due to the influence of meteorological factors that largely dictate year-to-year variability of Antarctic ozone loss.

#### The Antarctic ozone hole during 2012 (2014) [link]

Authors: Klekociuk, Tully, Krummel, Gies, Alexander, Fraser, Henderson, Javorniczky, Petelina, Shanklin, Schofield, Stone

We review the 2012 Antarctic ozone hole, making use of various meteorological reanalyses, remotely sensed ozone measurements and ground-based measurements of ultra-violet radiation. Based on analysis of 33 years of satellite records, we find that the ozone hole of 2012 was one of the least severe since the late 1980s in terms of maximum area, minimum ozone level and total ozone deficit. In particular, the estimated integrated ozone mass effectively depleted within the ozone hole of 2012 was approximately 720 Mt, which is the 12th smallest deficit on record and 28 per cent of the peak deficit observed in 2006. The key factor in limiting the extent of Antarctic ozone loss in 2012 was the relatively warm temperatures that occurred in the Antarctic stratosphere from early July. These warm temperatures, which were driven by dynamical activity, limited the activation of ozone depletion chemistry within the polar vortex during the latter part of the polar winter. Additionally, dynamical disturbances to the polar cap region during spring were aided by the prevailing phase of the Quasi-Biennial Oscillation (QBO) which was strongly negative (westward) and favouring the poleward propagation of heat flux anomalies; these disturbances resulted in the steady erosion of the vortex and caused it to breakdown relatively early compared to recent years. The metrics for the Antarctic ozone hole of 2012 showed some similarity with those of 1988 and 2002 (which were years of anomalously small ozone holes) despite all three years having distinctly different QBO indices indicating variant strengths of the polar vortex (and severity of ozone loss).

#### Atmospheric Abundances, Trends and Emissions of CFC-216ba, CFC-216ca and HCFC-225ca (2014) [link]

Authors: Kloss, Newland, Oram, Fraser, Brenninkmeijer, Röckmann, Laube

The first observations of the feedstocks, CFC-216ba (1,2-dichlorohexafluoropropane) and CFC-216ca (1,3-dichlorohexafluoropropane), as well as the CFC substitute HCFC-225ca (3,3-dichloro-1,1,1,2,2-pentafluoropropane), are reported in air samples collected between 1978 and 2012 at Cape Grim, Tasmania. Present day (2012) mixing ratios are 37.8 ± 0.08 ppq (parts per quadrillion; 1015) and 20.2 ± 0.3 ppq for CFC-216ba and CFC-216ca, respectively. The abundance of CFC-216ba has been approximately constant for the past 20 years, whilst that of CFC-216ca is increasing, at a current rate of 0.2 ppq/year. Upper tropospheric air samples collected in 2013 suggest a further continuation of this trend. Inferred annual emissions peaked 421 at 0.18 Gg/year (CFC-216ba) and 0.05 Gg/year (CFC-216ca) in the mid-1980s and then decreased sharply as expected from the Montreal Protocol phase-out schedule for CFCs. The atmospheric trend of CFC-216ca and CFC-216ba translates into continuing emissions of around 0.01 Gg/year in 2011, indicating that significant banks still exist or that they are still being used. HCFC-225ca was not detected in air samples collected before 1992. The highest mixing ratio of 52 ± 1 ppq was observed in 2001. Increasing annual emissions were found in the 1990s (i.e., when HCFC-225ca was being introduced as a replacement for CFCs). Emissions peaked around 1999 at about 1.51 Gg/year. In accordance with the Montreal Protocol, restrictions on HCFC consumption and the short lifetime of HCFC-225ca, mixing ratios declined after 2001 to 23.3 ± 0.7 ppq by 2012.

#### Newly detected ozone-depleting substances in the atmosphere (2014) [link]

Authors: Laube, Newland, Hogan, Brenninkmeijer, Fraser, Martinerie, Oram, Reeves, Röckmann, Schwander, Witrant, Sturges

Ozone-depleting substances emitted through human activities cause large-scale damage to the stratospheric ozone layer, and influence global climate. Consequently, the production of many of these substances has been phased out; prominent examples are the chlorofluorocarbons (CFCs), and their intermediate replacements, the hydrochlorofluorocarbons (HCFCs). So far, seven types of CFC and six types of HCFC have been shown to contribute to stratospheric ozone destruction. Here, we report the detection and quantification of a further three CFCs and one HCFC. We analysed the composition of unpolluted air samples collected in Tasmania between 1978 and 2012, and extracted from deep firn snow in Greenland in 2008, using gas chromatography with mass spectrometric detection. Using the firn data, we show that all four compounds started to emerge in the atmosphere in the 1960s. Two of the compounds continue to accumulate in the atmosphere. We estimate that, before 2012, emissions of all four compounds combined amounted to more than 74,000 tonnes. This is small compared with peak emissions of other CFCs in the 1980s of more than one million tonnes each year. However, the reported emissions are clearly contrary to the intentions behind the Montreal Protocol, and raise questions about the sources of these gases.

#### Spectrometric monitoring of atmospheric carbon tetrafluoride (CF4) above the Jungfraujoch station since 1989: evidence of continued increase but at a slowing rate (2014) [link]

Authors: Mahieu, Zander, Toon, Vollmer, Reimann, Mühle, Bader, Bovy, Lejeune, Servais, Demoulin, Roland, Bernath, Boone, Walker, Duchatelet

The long-term evolution of the vertical column abundance of carbon tetrafluoride (CF4) above the high-altitude Jungfraujoch station (Swiss Alps, 46.5° N, 8.0° E, 3580 m a.s.l.) has been derived from the spectrometric analysis of Fourier transform infrared solar spectra recorded at that site between 1989 and 2012. The investigation is based on a multi-microwindow approach, two encompassing pairs of absorption lines belonging to the R-branch of the strong ν3 band of CF4 centered at 1283 cm−1, and two additional ones to optimally account for weak but overlapping HNO3 interferences. The analysis reveals a steady accumulation of the very long-lived CF4 above the Jungfraujoch at mean rates of (1.38 ± 0.11) × 1013 molec cm−2 yr−1 from 1989 to 1997, and (0.98 ± 0.02) × 1013 molec cm−2 yr−1 from 1998 to 2012, which correspond to linear growth rates of 1.71 ± 0.14 and 1.04 ± 0.02% yr−1 respectively referenced to 1989 and 1998. Related global CF4 anthropogenic emissions required to sustain these mean increases correspond to 15.8 ± 1.3 and 11.1 ± 0.2 Gg yr−1 over the above specified time intervals. Findings reported here are compared and discussed with respect to relevant northern mid-latitude results obtained remotely from space and balloons as well as in situ at the ground, including new gas chromatography mass spectrometry measurements performed at the Jungfraujoch since 2010.

#### Estimates of European emissions of methyl chloroform using a Bayesian inversion method (2014) [link]

Authors: Maione, Graziosi, Arduini, Furlani, Giostra, Blake, Bonasoni, Fang, Montzka, O’Doherty, Reimann, Stohl, Vollmer

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.

#### Ecosystem fluxes of hydrogen: a comparison of flux-gradient methods (2014) [link]

Authors: Meredith, Commane, Munger, Dunn, Tang, Wofsy, Prinn

Our understanding of biosphere–atmosphere exchange has been considerably enhanced by eddy covariance measurements. However, there remain many trace gases, such as molecular hydrogen (H2), that lack suitable analytical methods to measure their fluxes by eddy covariance. In such cases, flux-gradient methods can be used to calculate ecosystem-scale fluxes from vertical concentration gradients. The budget of atmospheric H2 is poorly constrained by the limited available observations, and thus the ability to quantify and characterize the sources and sinks of H2 by flux-gradient methods in various ecosystems is important. We developed an approach to make nonintrusive, automated measurements of ecosystem-scale H2 fluxes both above and below the forest canopy at the Harvard Forest in Petersham, Massachusetts, for over a year. We used three flux-gradient methods to calculate the fluxes: two similarity methods that do not rely on a micrometeorological determination of the eddy diffusivity, K, based on (1) trace gases or (2) sensible heat, and one flux-gradient method that (3) parameterizes K. We quantitatively assessed the flux-gradient methods using CO2 and H2O by comparison to their simultaneous independent flux measurements via eddy covariance and soil chambers. All three flux-gradient methods performed well in certain locations, seasons, and times of day, and the best methods were trace gas similarity for above the canopy and K parameterization below it. Sensible heat similarity required several independent measurements, and the results were more variable, in part because those data were only available in the winter, when heat fluxes and temperature gradients were small and difficult to measure. Biases were often observed between flux-gradient methods and the independent flux measurements, and there was at least a 26% difference in nocturnal eddy-derived net ecosystem exchange (NEE) and chamber measurements. H2 fluxes calculated in a summer period agreed within their uncertainty and pointed to soil uptake as the main driver of H2 exchange at Harvard Forest, with H2 deposition velocities ranging from 0.04 to 0.10 cm s−1.

#### Global emissions of HFC-143a (CH3CF3) and HFC-32 (CH2F2) from in situ and air archive atmospheric observations (2014) [link]

Authors: O’Doherty, Rigby, Mühle, Ivy, Miller, Young, Simmonds, Reimann, Vollmer, Krummel, Fraser, Steele, Dunse, Salameh, Harth, Arnold, Weiss, Kim, Park, Li, Lunder, Hermansen, Schmidbauer, Zhou, Yao, Wang, Manning, Prinn

High-frequency, in situ observations from the Advanced Global Atmospheric Gases Experiment (AGAGE), for the period 2003 to 2012, combined with archive flask measurements dating back to 1977, have been used to capture the rapid growth of HFC-143a (CH3CF3) and HFC-32 (CH2F2) mole fractions and emissions into the atmosphere. Here we report the first in situ global measurements of these two gases. HFC-143a and HFC-32 are the third and sixth most abundant hydrofluorocarbons (HFCs) respectively and they currently make an appreciable contribution to the HFCs in terms of atmospheric radiative forcing (1.7 ± 0.04 and 0.7 ± 0.02 mW m−2 in 2012 respectively). In 2012 the global average mole fraction of HFC-143a was 13.4 ± 0.3 ppt (1σ) in the lower troposphere and its growth rate was 1.4 ± 0.04 ppt yr−1; HFC-32 had a global mean mole fraction of 6.2 ± 0.2 ppt and a growth rate of 1.1 ± 0.04 ppt yr−1 in 2012. The extensive observations presented in this work have been combined with an atmospheric transport model to simulate global atmospheric abundances and derive global emission estimates. It is estimated that 23 ± 3 Gg yr−1 of HFC-143a and 21 ± 11 Gg yr−1 of HFC-32 were emitted globally in 2012, and the emission rates are estimated to be increasing by 7 ± 5% yr−1 for HFC-143a and 14 ± 11% yr−1 for HFC-32.

Authors: Patra, Krol, Montzka, Arnold, Atlas, Lintner, Stephens, Xiang, Elkins, Fraser, Ghosh, Hintsa, Hurst, Ishijima, Krummel, Miller, Miyazaki, Moore, Mühle, O’Doherty, Prinn, Steele, Takigawa, Wang, Weiss, Wofsy, Young

The hydroxyl radical (OH) is a key oxidant involved in the removal of air pollutants and greenhouse gases from the atmosphere. The ratio of Northern Hemispheric to Southern Hemispheric (NH/SH) OH concentration is important for our understanding of emission estimates of atmospheric species such as nitrogen oxides and methane. It remains poorly constrained, however, with a range of estimates from 0.85 to 1.4 (refs 4, 7,8,9,10). Here we determine the NH/SH ratio of OH with the help of methyl chloroform data (a proxy for OH concentrations) and an atmospheric transport model that accurately describes interhemispheric transport and modelled emissions. We find that for the years 2004–2011 the model predicts an annual mean NH–SH gradient of methyl chloroform that is a tight linear function of the modelled NH/SH ratio in annual mean OH. We estimate a NH/SH OH ratio of 0.97 ± 0.12 during this time period by optimizing global total emissions and mean OH abundance to fit methyl chloroform data from two surface-measurement networks and aircraft campaigns. Our findings suggest that top-down emission estimates of reactive species such as nitrogen oxides in key emitting countries in the NH that are based on a NH/SH OH ratio larger than 1 may be overestimated.

#### Recent and future trends in synthetic greenhouse gas radiative forcing (2014) [link]

Authors: Rigby, Prinn, O’Doherty, Miller, Ivy, Mühle, Harth, Salameh, Arnold, Weiss, Krummel, Steele, Fraser, Young, Simmonds

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 355 mW m−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 240 mW m−2 by 2050 or a cumulative emissions saving equivalent to 0.5 to 2.8 years 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.

#### Global and regional emissions estimates for N2O (2014) [link]

Authors: Saikawa, Prinn, Dlugokencky, Ishijima, Dutton, Hall, Langenfelds, Tohjima, Machida, Manizza, Rigby, O’Doherty, Patra, Harth, Weiss, Krummel, van der Schoot, Fraser, Steele, Aoki, Nakazawa, Elkins

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.

#### Corrigendum to "Global and regional emission estimates for HCFC-22", Atmos. Chem. Phys., 12, 10033–10050, 2012 (2014) [link]

Authors: Saikawa, Rigby, Prinn, Montzka, Miller, Kuijpers, Fraser, Vollmer, Saito, Yokouchi, Harth, Mühle, Weiss, Salameh, Kim, Li, Park, Kim, Young, O’Doherty, Simmonds, McCulloch, Krummel, Steele, Lunder, Hermansen, Maione, Arduini, Yao, Zhou, Wang, Elkins, Hall

No abstract available.

#### Nitrous oxide emissions 1999–2009 from a global atmospheric inversion (2014) [link]

Authors: Thompson, Chevallier, Crotwell, Dutton, Langenfelds, Prinn, Weiss, Tohjima, Nakazawa, Krummel, Steele, Fraser, O’Doherty, Ishijima, Aoki

N2O 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 N2O source varied from 17.5 to 20.1 Tg a−1 N. Tropical and subtropical land regions were found to consistently have the highest N2O 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 N2O emissions (0.045 Tg a−2 N) from South Asia was found and confirms inventory estimates of this trend. Considerable interannual variability in the global N2O source was observed (0.8 Tg a−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−1 N, 1 SD) and Africa (0.3 Tg a−1 N, 1 SD). Notable variability was also found for N2O fluxes in the tropical and southern oceans (0.15 and 0.2 Tg a−1 N, 1 SD, respectively). Interannual variability in the N2O source shows some correlation with the El Niño–Southern Oscillation (ENSO), where El Niño conditions are associated with lower N2O fluxes from soils and from the ocean and vice versa for La Niña conditions.

#### TransCom N2O model inter-comparison – Part 1: Assessing the influence of transport and surface fluxes on tropospheric N2O variability (2014) [link]

Authors: Thompson, Patra, Ishijima, Saikawa, Corazza, Karstens, Wilson, Bergamaschi, Dlugokencky, Sweeney, Prinn, Weiss, O’Doherty, Fraser, Steele, Krummel, Saunois, Chipperfield, Bousquet

We present a comparison of chemistry-transport models (TransCom-N2O) to examine the importance of atmospheric transport and surface fluxes on the variability of N2O mixing ratios in the troposphere. Six different models and two model variants participated in the inter-comparison and simulations were made for the period 2006 to 2009. In addition to N2O, simulations of CFC-12 and SF6 were made by a subset of four of the models to provide information on the models' proficiency in stratosphere–troposphere exchange (STE) and meridional transport, respectively. The same prior emissions were used by all models to restrict differences among models to transport and chemistry alone. Four different N2O flux scenarios totalling between 14 and 17 TgN yr−1 (for 2005) globally were also compared. The modelled N2O mixing ratios were assessed against observations from in situ stations, discrete air sampling networks and aircraft. All models adequately captured the large-scale patterns of N2O and the vertical gradient from the troposphere to the stratosphere and most models also adequately captured the N2O tropospheric growth rate. However, all models underestimated the inter-hemispheric N2O gradient by at least 0.33 parts per billion (ppb), equivalent to 1.5 TgN, which, even after accounting for an overestimate of emissions in the Southern Ocean of circa 1.0 TgN, points to a likely underestimate of the Northern Hemisphere source by up to 0.5 TgN and/or an overestimate of STE in the Northern Hemisphere. Comparison with aircraft data reveal that the models overestimate the amplitude of the N2O seasonal cycle at Hawaii (21° N, 158° W) below circa 6000 m, suggesting an overestimate of the importance of stratosphere to troposphere transport in the lower troposphere at this latitude. In the Northern Hemisphere, most of the models that provided CFC-12 simulations captured the phase of the CFC-12, seasonal cycle, indicating a reasonable representation of the timing of STE. However, for N2O all models simulated a too early minimum by 2 to 3 months owing to errors in the seasonal cycle in the prior soil emissions, which was not adequately represented by the terrestrial biosphere model. In the Southern Hemisphere, most models failed to capture the N2O and CFC-12 seasonality at Cape Grim, Tasmania, and all failed at the South Pole, whereas for SF6, all models could capture the seasonality at all sites, suggesting that there are large errors in modelled vertical transport in high southern latitudes.

#### TransCom N2O model inter-comparison – Part 2: Atmospheric inversion estimates of N2O emissions (2014) [link]

Authors: Thompson, Ishijima, Saikawa, Corazza, Karstens, Patra, Bergamaschi, Chevallier, Dlugokencky, Prinn, Weiss, O’Doherty, Fraser, Steele, Krummel, Vermeulen, Tohjima, Jordan, Haszpra, Steinbacher, Van der Laan, Aalto, Meinhardt, Popa, Moncrieff, Bousquet

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 yr−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.

#### Comparisons of continuous atmospheric CH₄, CO₂ and N₂O measurements – results from a travelling instrument campaign at Mace Head (2014) [link]

Authors: Vardag, Hammer, O’Doherty, Spain, Wastine, Jordan, Levin

A 2-month measurement campaign with a Fourier transform infrared analyser as a travelling comparison instrument (TCI) was performed at the Advanced Global Atmospheric Gases Experiment (AGAGE) and World Meteorological Organization (WMO) Global Atmosphere Watch (GAW) station at Mace Head, Ireland. The aim was to evaluate the compatibility of atmospheric methane (CH4), carbon dioxide (CO2) and nitrous oxide (N2O) measurements of the routine station instrumentation, consisting of a gas chromatograph (GC) for CH4 and N2O as well as a cavity ring-down spectroscopy (CRDS) system for CH4 and CO2. The advantage of a TCI approach for quality control is that the comparison covers the entire ambient air measurement system, including the sample intake system and the data evaluation process. For initial quality and performance control, the TCI was run in parallel with the Heidelberg GC before and after the measurement campaign at Mace Head. Median differences between the Heidelberg GC and the TCI were well within the WMO inter-laboratory compatibility target for all three greenhouse gases. At Mace Head, the median difference between the station GC and the TCI were −0.04 nmol mol−1 for CH4 and −0.37 nmol mol−1 for N2O (GC-TCI). For N2O, a similar difference (−0.40 nmol mol−1) was found when measuring surveillance or working gas cylinders with both instruments. This suggests that the difference observed in ambient air originates from a calibration offset that could partly be due to a difference between the WMO N2O X2006a reference scale used for the TCI and the Scripps Institution of Oceanography (SIO-1998) scale used at Mace Head and in the whole AGAGE network. Median differences between the CRDS G1301 and the TCI at Mace Head were 0.12 nmol mol−1 for CH4 and 0.14 μmol mol−1 for CO2 (CRDS G1301 – TCI). The difference between both instruments for CO2 could not be explained, as direct measurements of calibration gases show no such difference. The CH4 differences between the TCI, the GC and the CRDS G1301 at Mace Head are much smaller than the WMO inter-laboratory compatibility target, while this is not the case for CO2 and N2O.

#### Global emissions of refrigerants HCFC-22 and HFC-134a: Unforeseen seasonal contributions (2014) [link]

Authors: Xiang, Patra, Montzka, Miller, Elkins, Moore, Atlas, Miller, Weiss, Prinn, Wofsy

HCFC-22 (CHClF2) and HFC-134a (CH2FCF3) are two major gases currently used worldwide in domestic and commercial refrigeration and air conditioning. HCFC-22 contributes to stratospheric ozone depletion, and both species are potent greenhouse gases. In this work, we study in situ observations of HCFC-22 and HFC-134a taken from research aircraft over the Pacific Ocean in a 3-y span [HIaper-Pole-to-Pole Observations (HIPPO) 2009–2011] and combine these data with long-term ground observations from global surface sites [National Oceanic and Atmospheric Administration (NOAA) and Advanced Global Atmospheric Gases Experiment (AGAGE) networks]. We find the global annual emissions of HCFC-22 and HFC-134a have increased substantially over the past two decades. Emissions of HFC-134a are consistently higher compared with the United Nations Framework Convention on Climate Change (UNFCCC) inventory since 2000, by 60% more in recent years (2009–2012). Apart from these decadal emission constraints, we also quantify recent seasonal emission patterns showing that summertime emissions of HCFC-22 and HFC-134a are two to three times higher than wintertime emissions. This unforeseen large seasonal variation indicates that unaccounted mechanisms controlling refrigerant gas emissions are missing in the existing inventory estimates. Possible mechanisms enhancing refrigerant losses in summer are (i) higher vapor pressure in the sealed compartment of the system at summer high temperatures and (ii) more frequent use and service of refrigerators and air conditioners in summer months. Our results suggest that engineering (e.g., better temperature/vibration-resistant system sealing and new system design of more compact/efficient components) and regulatory (e.g., reinforcing system service regulations) steps to improve containment of these gases from working devices could effectively reduce their release to the atmosphere.

#### Atmospheric sulfur hexafluoride in-situ measurements at the Shangdianzi regional background station in China (2014) [link]

Authors: Yao, Zhou, Xia, Zhang, Guo, Liu, Fang

We present in-situ measurements of atmospheric sulfur hexafluoride (SF6) conducted by an automated gas chromatograph–electron capture detector system and a gas chromatography/mass spectrometry system at a regional background site, Shangdianzi, in China, from June 2009 to May 2011, using the System for Observation of Greenhouse gases in Europe and Asia and Advanced Global Atmospheric Gases Experiment (AGAGE) techniques. The mean background and polluted mixing ratios for SF6 during the study period were 7.22×10−12 (mol/mol, hereinafter) and 8.66×10−12, respectively. The averaged SF6 background mixing ratios at Shangdianzi were consistent with those obtained at other AGAGE stations located at similar latitudes (Trinidad Head and Mace Head), but larger than AGAGE stations in the Southern Hemisphere (Cape Grim and Cape Matatula). SF6 background mixing ratios increased rapidly during our study period, with a positive growth rate at 0.30×10−12year−1. The peak to peak amplitude of the seasonal cycle for SF6 background conditions was 0.07×10−12, while the seasonal fluctuation of polluted conditions was 2.16×10−12. During the study period, peak values of SF6 mixing ratios occurred in autumn when local surface horizontal winds originated from W/WSW/SW/SWS/S sectors, while lower levels of SF6 mixing ratios appeared as winds originated from N/NNE/NE/ENE/E sectors.

#### Greenhouse gas network design using backward Lagrangian particle dispersion modelling − Part 1: Methodology and Australian test case (2014) [link]

Authors: Ziehn, Nickless, Rayner, Law, Roff, Fraser

This paper describes the generation of optimal atmospheric measurement networks for determining carbon dioxide fluxes over Australia using inverse methods. A Lagrangian particle dispersion model is used in reverse mode together with a Bayesian inverse modelling framework to calculate the relationship between weekly surface fluxes, comprising contributions from the biosphere and fossil fuel combustion, and hourly concentration observations for the Australian continent. Meteorological driving fields are provided by the regional version of the Australian Community Climate and Earth System Simulator (ACCESS) at 12 km resolution at an hourly timescale. Prior uncertainties are derived on a weekly timescale for biosphere fluxes and fossil fuel emissions from high-resolution model runs using the Community Atmosphere Biosphere Land Exchange (CABLE) model and the Fossil Fuel Data Assimilation System (FFDAS) respectively. The influence from outside the modelled domain is investigated, but proves to be negligible for the network design. Existing ground-based measurement stations in Australia are assessed in terms of their ability to constrain local flux estimates from the land. We find that the six stations that are currently operational are already able to reduce the uncertainties on surface flux estimates by about 30%. A candidate list of 59 stations is generated based on logistic constraints and an incremental optimisation scheme is used to extend the network of existing stations. In order to achieve an uncertainty reduction of about 50%, we need to double the number of measurement stations in Australia. Assuming equal data uncertainties for all sites, new stations would be mainly located in the northern and eastern part of the continent.

### 2015

#### Chlorine isotope composition in chlorofluorocarbons CFC-11, CFC-12 and CFC-113 in firn, stratospheric and tropospheric air (2015) [link]

Authors: Allin, Laube, Witrant, Kaiser, McKenna, Dennis, Mulvaney, Capron, Martinerie, Röckmann, Blunier, Schwander, Fraser, Langenfelds, Sturges

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

#### Top-down estimates of European CH4 and N2O emissions based on four different inverse models (2015) [link]

Authors: Bergamaschi, Corazza, Karstens, Athanassiadou, Thompson, Pison, Manning, Bousquet, Segers, Vermeulen, Janssens-Maenhout, Schmidt, Ramonet, Meinhardt, Aalto, Haszpra, Moncrieff, Popa, Lowry, Steinbacher, Jordan, O’Doherty, Piacentino, Dlugokencky

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.

#### Global HCFC-22 measurements with MIPAS: retrieval, validation, climatologies and trends (2015) [link]

Authors: Chirkov, Stiller, Laeng, Kellmann, von Clarmann, Boone, Elkins, Engel, Glatthor, Grabowski, Harth, Kiefer, Kolonjari, Krummel, Linden, Lunder, Miller, Montzka, Mühle, O’Doherty, Orphal, Prinn, Toon, Vollmer, Walker, Weiss, Wiegele, Young

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 ν4-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.

#### Tectonic activity as a significant source of crustal tetrafluoromethane emissions to the atmosphere: Observations in groundwaters along the San Andreas Fault (2015) [link]

Authors: Deeds, Kulongoski, Mühle, Weiss

Tetrafluoromethane (CF4) concentrations were measured in 14 groundwater samples from the Cuyama Valley, Mil Potrero and Cuddy Valley aquifers along the Big Bend section of the San Andreas Fault System (SAFS) in California to assess whether tectonic activity in this region is a significant source of crustal CF4 to the atmosphere. Dissolved CF4 concentrations in all groundwater samples but one were elevated with respect to estimated recharge concentrations including entrainment of excess air during recharge (Cre; ∼30 fmol kg−1 H2O), indicating subsurface addition of CF4 to these groundwaters. Groundwaters in the Cuyama Valley contain small CF4 excesses (0.1–9 times Cre), which may be attributed to an in situ release from weathering and a minor addition of deep crustal CF4 introduced to the shallow groundwater through nearby faults. CF4 excesses in groundwaters within 200 m of the SAFS are larger (10–980 times Cre) and indicate the presence of a deep crustal flux of CF4 that is likely associated with the physical alteration of silicate minerals in the shear zone of the SAFS. Extrapolating CF4 flux rates observed in this study to the full extent of the SAFS (1300 km × 20–100 km) suggests that the SAFS potentially emits (0.3–1)×10−1 kg CF4 yr−1 to the Earth's surface. For comparison, the chemical weathering of ∼7.5×104 km2 of granitic rock in California is estimated to release (0.019–3.2)×10−1 kg CF4 yr−1. Tectonic activity is likely an important, and potentially the dominant, driver of natural emissions of CF4 to the atmosphere. Variations in preindustrial atmospheric CF4 as observed in paleo-archives such as ice cores may therefore represent changes in both continental weathering and tectonic activity, including changes driven by variations in continental ice cover during glacial–interglacial transitions.

#### State of the Climate in 2014: [Global Climate, Atmospheric chemical composition] Long-lived greenhouse gases (2015) [link]

Authors: Dlugokencky, Hall

No abstract available.

#### Multiannual Top-Down Estimate of HFC-23 Emissions in East Asia (2015) [link]

Authors: Fang, Stohl, Yokouchi, Kim, Li, Saito, Park, Hu

Trifluoromethane (CHF3, HFC-23), with a 100-year global warming potential (GWP) of 12400, is regulated under the Kyoto Protocol. HFC-23 emissions in East Asia, especially in China, are currently thought to represent the majority of global HFC-23 emissions. This study provides both a bottom-up emission inventory and the multiannual top-down estimate of HFC-23 emissions in East Asia during 2007–2012. The new bottom-up inventory yields improved simulated HFC-23 mixing ratios compared to previous bottom-up inventories. The top-down estimate uses inverse modeling to further improve the model-measurement agreement. Results show that China contributed 94–98% of all HFC-23 emissions in East Asia. Annual a posteriori emissions from China were around 6.3 Gg/yr during the period 2007–2010 after which they increased to 7.1 ± 0.7 Gg/yr in 2011 and 8.8 ± 0.8 Gg/yr in 2012. For the first time, this study also provides a top-down estimate of HFC-23/HCFC-22 (chlorodifluoromethane, CHClF2) coproduction ratios in non-CDM (Clean Development Mechanism) HCFC-22 production plants as well as in all HCFC-22 production plants in China.

#### Quantifying methane and nitrous oxide emissions from the UK and Ireland using a national-scale monitoring network (2015) [link]

Authors: Ganesan, Manning, Grant, Young, Oram, Sturges, Moncrieff, O’Doherty

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.

#### Variations in global methane sources and sinks during 1910–2010 (2015) [link]

Authors: Ghosh, Patra, Ishijima, Umezawa, Ito, Etheridge, Sugawara, Kawamura, Miller, Dlugokencky, Krummel, Fraser, Steele, Langenfelds, Trudinger, White, Vaughn, Saeki, Aoki, Nakazawa

Atmospheric methane (CH4) increased from ~900 ppb (parts per billion, or nanomoles per mole of dry air) in 1900 to ~1800 ppb in 2010 at a rate unprecedented in any observational records. However, the contributions of the various methane sources and sinks to the CH4 increase are poorly understood. Here we use initial emissions from bottom-up inventories for anthropogenic sources, emissions from wetlands and rice paddies simulated by a~terrestrial biogeochemical model, and an atmospheric general circulation model (AGCM)-based chemistry-transport model (i.e. ACTM) to simulate atmospheric CH4 concentrations for 1910–2010. The ACTM simulations are compared with the CH4 concentration records reconstructed from Antarctic and Arctic ice cores and firn air samples, and from direct measurements since the 1980s at multiple sites around the globe. The differences between ACTM simulations and observed CH4 concentrations are minimized to optimize the global total emissions using a mass balance calculation. During 1910–2010, the global total CH4 emission doubled from ~290 to ~580 Tg yr−1. Compared to optimized emission, the bottom-up emission data set underestimates the rate of change of global total CH4 emissions by ~30% during the high growth period of 1940–1990, while it overestimates by ~380% during the low growth period of 1990–2010. Further, using the CH4 stable carbon isotopic data (δ13C), we attribute the emission increase during 1940–1990 primarily to enhancement of biomass burning. The total lifetime of CH4 shortened from 9.4 yr during 1910–1919 to 9 yr during 2000–2009 by the combined effect of the increasing abundance of atomic chlorine radicals (Cl) and increases in average air temperature. We show that changes of CH4 loss rate due to increased tropospheric air temperature and CH4 loss due to Cl in the stratosphere are important sources of uncertainty to more accurately estimate the global CH4 budget from δ13C observations.

#### European emissions of HCFC-22 based on eleven years of high frequency atmospheric measurements and a Bayesian inversion method (2015) [link]

Authors: Graziosi, Arduini, Furlani, Giostra, Kuijpers, Montzka, Miller, O’Doherty, Stohl, Bonasoni, Maione

HCFC-22 (CHClF2), a stratospheric ozone depleting substance and a powerful greenhouse gas, is the third most abundant anthropogenic halocarbon in the atmosphere. Primarily used in refrigeration and air conditioning systems, its global production and consumption have increased during the last 60 years, with the global increases in the last decade mainly attributable to developing countries. In 2007, an adjustment to the Montreal Protocol for Substances that Deplete the Ozone Layer called for an accelerated phase out of HCFCs, implying a 75% reduction (base year 1989) of HCFC production and consumption by 2010 in developed countries against the previous 65% reduction. In Europe HCFC-22 is continuously monitored at the two sites Mace Head (Ireland) and Monte Cimone (Italy). Combining atmospheric observations with a Bayesian inversion technique, we estimated fluxes of HCFC-22 from Europe and from eight macro-areas within it, over an 11-year period from January 2002 to December 2012, during which the accelerated restrictions on HCFCs production and consumption have entered into force. According to our study, the maximum emissions over the entire domain was in 2003 (38.2 ± 4.7 Gg yr−1), and the minimum in 2012 (12.1 ± 2.0 Gg yr−1); emissions continuously decreased between these years, except for secondary maxima in the 2008 and 2010. Despite such a decrease in regional emissions, background values of HCFC-22 measured at the two European stations over 2002–2012 are still increasing as a consequence of global emissions, in part from developing countries, with an average trend of ca 7.0 ppt yr−1. However, the observations at the two European stations show also that since 2008 a decrease in the global growth rate has occurred. In general, our European emission estimates are in good agreement with those reported by previous studies that used different techniques. Since the currently dominant emission source of HCFC-22 is from banks, we assess the banks' size and their contribution to the total European emissions up to 2030, and we project a fast decrease approaching negligible emissions in the last five years of the considered period. Finally, inversions conducted over three month periods showed evidence for a seasonal cycle in emissions in regions in the Mediterranean basin but not outside it. Emissions derived from regions in the Mediterranean basin were ca. 25% higher in warmer months than in colder months.

#### Growth in stratospheric chlorine from short-lived chemicals not controlled by the Montreal Protocol (2015) [link]

Authors: Hossaini, Chipperfield, Saiz-Lopez, Harrison, von Glasow, Sommariva, Atlas, Navarro, Montzka, Feng, Dhomse, Harth, Mühle, Lunder, O’Doherty, Young, Reimann, Vollmer, Krummel, Bernath

We have developed a chemical mechanism describing the tropospheric degradation of chlorine containing very short-lived substances (VSLS). The scheme was included in a global atmospheric model and used to quantify the stratospheric injection of chlorine from anthropogenic VSLS (ClyVSLS) between 2005 and 2013. By constraining the model with surface measurements of chloroform (CHCl3), dichloromethane (CH2Cl2), tetrachloroethene (C2Cl4), trichloroethene (C2HCl3), and 1,2-dichloroethane (CH2ClCH2Cl), we infer a 2013 ClyVSLS mixing ratio of 123 parts per trillion (ppt). Stratospheric injection of source gases dominates this supply, accounting for ∼83% of the total. The remainder comes from VSLS-derived organic products, phosgene (COCl2, 7%) and formyl chloride (CHClO, 2%), and also hydrogen chloride (HCl, 8%). Stratospheric ClyVSLS increased by ∼52% between 2005 and 2013, with a mean growth rate of 3.7 ppt Cl/yr. This increase is due to recent and ongoing growth in anthropogenic CH2Cl2—the most abundant chlorinated VSLS not controlled by the Montreal Protocol.

#### Halomethane production by vanadium-dependent bromoperoxidase in marine <i>Synechococcus</i>: Halomethane production by Synechococcus (2015) [link]

Authors: Johnson, Brahamsha, Palenik, Mühle

No abstract available.

#### A study of global atmospheric budget and distribution of acetone using global atmospheric model STOCHEM-CRI (2015) [link]

Authors: Khan, Cooke, Utembe, Archibald, Maxwell, Morris, Xiao, Derwent, Jenkin, Percival, Walsh, Young, Simmonds, Nickless, O’Doherty, Shallcross

The impact of including a more detailed VOC oxidation scheme (CRI v2-R5) with a multi-generational approach for simulating tropospheric acetone is investigated using a 3-D global model, STOCHEM-CRI. The CRI v2-R5 mechanism contains photochemical production of acetone from monoterpenes which account for 64% (46.8 Tg/yr) of the global acetone sources in STOCHEM-CRI. Both photolysis and oxidation by OH in the troposphere contributes equally (42%, each) and dry deposition contributes 16% of the atmospheric sinks of acetone. The tropospheric life-time and the global burden of acetone are found to be 18 days and 3.5 Tg, respectively, these values being close to those reported in the study of Jacob et al. (2002). A dataset of aircraft campaign measurements are used to evaluate the inclusion of acetone formation from monoterpenes in the CRI v2-R5 mechanism used in STOCHEM-CRI. The overall comparison between measurements and models show that the parameterised approach in STOCHEM-NAM (no acetone formation from monoterpenes) underpredicts the mixing ratios of acetone in the atmosphere. However, using a detailed monoterpene oxidation mechanism forming acetone has brought the STOCHEM-CRI into closer agreement with measurements with an improvement in the vertical simulation of acetone. The annual mean surface distribution of acetone simulated by the STOCHEM-CRI shows a peak over forested regions where there are large biogenic emissions and high levels of photochemical activity. Year-long observations of acetone and methanol at the Mace Head research station in Ireland are compared with the simulated acetone and methanol produced by the STOCHEM-CRI and found to produce good overall agreement between model and measurements. The seasonal variation of model and measured acetone levels at Mace Head, California, New Hampshire and Minnesota show peaks in summer and dips in winter, suggesting that photochemical production may have the strongest effect on its seasonal trend.

#### The Antarctic Ozone Hole during 2013 (2015) [link]

Authors: Klekociuk, Krummel, Tully, Gies, Alexander, Fraser, Henderson, Javorniczky, Shanklin, Schofield, Stone

We review the 2013 Antarctic ozone hole , making use of various ground-based, in-situ and remotely-sensed ozone measurements, ground-based measurements of ultraviolet radiation and meteorological reanalyses. Based on analysis of 34 years of satellite records spanning 1979-2013 (which excludes 1995), we find that in terms of maximum area, minimum ozone level and total ozone deficit, the ozone hole in 2013 was typical of other years of moderate ozone loss. The estimated integrated ozone mass effectively depleted within the ozone hole of 2013 was approximately 1037 Mt, which was the 17th largest deficit on record and 41% of the peak deficit observed in 2006. Anomalously cold winter temperatures in the lower stratosphere over Antarctica and concurrent strong and stable vortex conditions favoured the potential for strong ozone depletion in 2013. However, anomalous warming of the polar vortex that occurred from late August limited the overall severity of ozone depletion during spring, and resulted in the relatively early breakup of the ozone hole in mid-November.

#### Biomass burning emissions of trace gases and particles in marine air at Cape Grim, Tasmania (2015) [link]

Authors: Lawson, Keywood, Galbally, Gras, Cainey, Cope, Krummel, Fraser, Steele, Bentley, Meyer, Ristovski, Goldstein

No abstract available.

#### Simulations of atmospheric methane for Cape Grim, Tasmania, to constrain southeastern Australian methane emissions (2015) [link]

Authors: Loh, Law, Haynes, Krummel, Steele, Fraser, Chambers, Williams

This study uses two climate models and six scenarios of prescribed methane emissions to compare modelled and observed atmospheric methane between 1994 and 2007, for Cape Grim, Australia (40.7° S, 144.7° E). The model simulations follow the TransCom-CH4 protocol and use the Australian Community Climate and Earth System Simulator (ACCESS) and the CSIRO Conformal-Cubic Atmospheric Model (CCAM). Radon is also simulated and used to reduce the impact of transport differences between the models and observations. Comparisons are made for air samples that have traversed the Australian continent. All six emission scenarios give modelled concentrations that are broadly consistent with those observed. There are three notable mismatches, however. Firstly, scenarios that incorporate interannually varying biomass burning emissions produce anomalously high methane concentrations at Cape Grim at times of large fire events in southeastern Australia, most likely due to the fire methane emissions being unrealistically input into the lowest model level. Secondly, scenarios with wetland methane emissions in the austral winter overestimate methane concentrations at Cape Grim during wintertime while scenarios without winter wetland emissions perform better. Finally, all scenarios fail to represent a~methane source in austral spring implied by the observations. It is possible that the timing of wetland emissions in the scenarios is incorrect with recent satellite measurements suggesting an austral spring (September–October–November), rather than winter, maximum for wetland emissions.

#### Reconciling reported and unreported HFC emissions with atmospheric observations (2015) [link]

Authors: Lunt, Rigby, Ganesan, Manning, Prinn, O’Doherty, Mühle, Harth, Salameh, Arnold, Weiss, Saito, Yokouchi, Krummel, Steele, Fraser, Park, Reimann, Vollmer, Lunder, Hermansen, Schmidbauer, Maione, Arduini, Young, Simmonds

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.

#### Comparison of halocarbon measurements in an atmospheric dry whole air sample (2015) [link]

Authors: Rhoderick, Hall, Harth, Kim, Lee, Montzka, Mühle, Reimann, Vollmer, Weiss

No abstract available.

#### First observations, trends, and emissions of HCFC-31 (CH2ClF) in the global atmosphere (2015) [link]

Authors: Schoenenberger, Vollmer, Rigby, Hill, Fraser, Krummel, Langenfelds, Rhee, Peter, Reimann

We report the first multiyear atmospheric record of HCFC-31 (CH2ClF), based on flask samples and in situ analyses of air from both hemispheres. Although HCFC-31 has never been produced in large amounts, observed mole fractions in the Northern Hemisphere increased from 2000 onward, reaching 170 ppq (parts per quadrillion, 10−15) in 2011–2012 before decreasing rapidly. By combining our observations with a two-dimensional atmospheric chemistry-transport model, we infer an increase in global emissions from 240 t yr−1 in 2000 to 840 t yr−1 in 2011–2012, followed by a relatively fast decline to 570 t yr−1 in 2014. Emissions of HCFC-31 originate most probably from intermediate product release during the manufacturing process of HFC-32 (CH2F2). The rapid decline in recent years could be due to changes in production methods rather than declines in diffusive sources such as landfills or HCFC-31 contaminations in merchandised HFC-32.

#### USA emissions estimates of CH3CHF2, CH2FCF3, CH3CF3 and CH2F2 based on in situ observations at Mace Head (2015) [link]

Authors: Simmonds, Derwent, Manning, McCulloch, O’Doherty

We investigate the low level, surface-to-surface transport of five hydrofluorocarbons (HFC-152a, -134a, -143a, -125 and -32) from North America to the Advanced Global Atmospheric Gases Experiment (AGAGE) observing station at Mace Head, Ireland during 2005–2012. Using the UK Meteorological Office Numerical Atmospheric dispersion Modelling Environment (NAME) we select air masses, which are dominated by direct transport from the North American continent to Mace Head, thereby eliminating any significant influence from local or other regional sources. To estimate emissions of individual HFCs we use the interspecies correlation method with HFC-125 as the reference compound. We then compare these derived North American emissions with those reported to UNFCCC. Our results indicate an under-reporting of HFC-152a emissions by the USA to the UNFCCC, with an annual average difference of 24 Gg (9–36 Gg). For HFC-134a our estimated emissions indicate an over-reporting of USA reported emissions by 24 Gg (21–28 Gg). For HFC-143a USA reported emissions are lower than our estimates by 1.8 Gg (1–3.5 Gg); whereas for HFC-32 there is close agreement, within the uncertainties, between the USA emissions reported to UNFCCC and our emissions estimates. Combining our USA emissions estimates for HFC-152a, HFC-134a, HFC-143a and HFC-32 with the UNFCCC estimate for HFC-125 could contribute potentially 201 ± 36 Tg-CO2 eq yr−1 to atmospheric radiative forcing in 2011–2012. This compares with UNFCCC of 146 Tg-CO2 eq yr−1 for the same five HFCs.

#### Methane emissions in East Asia for 2000–2011 estimated using an atmospheric Bayesian inversion (2015) [link]

Authors: Thompson, Stohl, Zhou, Dlugokencky, Fukuyama, Tohjima, Kim, Lee, Nisbet, Fisher, Lowry, Weiss, Prinn, O’Doherty, Young, White

We present methane (CH4) emissions for East Asia from a Bayesian inversion of CH4 mole fraction and stable isotope (δ13C-CH4) measurements. Emissions were estimated at monthly resolution from 2000 to 2011. A posteriori, the total emission for East Asia increased from 43 ± 4 to 59 ± 4 Tg yr−1 between 2000 and 2011, owing largely to the increase in emissions from China, from 39 ± 4 to 54 ± 4 Tg yr−1, while emissions in other East Asian countries remained relatively stable. For China, South Korea, and Japan, the total emissions were smaller than the prior estimates (i.e., Emission Database for Global Atmospheric Research 4.2 FT2010 for anthropogenic emissions) by an average of 29%, 20%, and 23%, respectively. For Mongolia, Taiwan, and North Korea, the total emission was less than 2 Tg yr−1 and was not significantly different from the prior. The largest reductions in emissions, compared to the prior, occurred in summer in regions important for rice agriculture suggesting that this source is overestimated in the prior. Furthermore, an analysis of the isotope data suggests that the prior underestimates emissions from landfills and ruminant animals for winter 2010 to spring 2011 (no data available for other times). The inversion also found a lower average emission trend for China, 1.2 Tg yr−1 compared to 2.8 Tg yr−1 in the prior. This trend was not constant, however, and increased significantly after 2005, up to 2.0 Tg yr−1. Overall, the changes in emissions from China explain up to 40% of the increase in global emissions in the 2000s.

#### First Observations of the Fourth Generation Synthetic Halocarbons HFC-1234yf, HFC-1234ze(E), and HCFC-1233zd(E) in the Atmosphere (2015) [link]

Authors: Vollmer, Reimann, Hill, Brunner

Halogenated alkenes are a class of anthropogenic substances, which replace ozone-depleting substances and long-lived greenhouse gases in the foam-blowing, refrigeration, and solvent sectors. We report the first multiyear atmospheric measurements of the hydrofluorocarbons HFC-1234yf (2,3,3,3-tetrafluoroprop-1-ene, CF3CF═CH2), and HFC-1234ze(E) (E-1,3,3,3-tetrafluoroprop-1-ene trans-CF3CH═CHF), and the hydrochlorofluorocarbon HCFC-1233zd(E) (E-1-chloro-3,3,3-trifluoroprop-1-ene trans-CF3CH═CHCl) from the high altitude observatory at Jungfraujoch and from urban Dubendorf (Switzerland). When observations started in 2011 HFC-1234yf was undetectable at Jungfraujoch (mole fractions <0.003 ppt, parts-per-trillion, 10–12) but since then the percentage of measurements with detectable mole fractions has steadily increased to 4.5% in 2014. By contrast, in 2014 HFC-1234ze(E) was detectable in half of our samples at Jungfraujoch and in all samples at Dubendorf demonstrating the wide use of this compound within the air mass footprints of the stations. Our back trajectory analysis for the Jungfraujoch observations suggests high emission strength of HFC-1234ze(E) in the Belgium/Netherlands region. HCFC-1233zd(E) is present at very low mole fractions (typically <0.03 ppt) at both stations, and features pronounced seasonality and a general absence of pollution events during our 2013–2014 measurements. This is indicative of the presence of significant emissions from source locations outside the footprints of the two stations. Based on a simple one-box model calculation we estimate globally increasing HCFC-1233zd(E) emissions from 0.2 Gg yr–1 in 2013 to 0.5 Gg yr–1 for 2014.

#### Modern inhalation anesthetics: Potent greenhouse gases in the global atmosphere (2015) [link]

Authors: Vollmer, Rhee, Rigby, Hofstetter, Hill, Schoenenberger, Reimann

Modern halogenated inhalation anesthetics undergo little metabolization during clinical application and evaporate almost completely to the atmosphere. Based on their first measurements in a range of environments, from urban areas to the pristine Antarctic environment, we detect a rapid accumulation and ubiquitous presence of isoflurane, desflurane, and sevoflurane in the global atmosphere. Over the past decade, their abundances in the atmosphere have increased to global mean mole fractions in 2014 of 0.097ppt, 0.30ppt, and 0.13ppt (parts per trillion, 10−12, in dry air), respectively. Emissions of these long-lived greenhouse gases inferred from the observations suggest a global combined release to the atmosphere of 3.1 ± 0.6 million t CO2 equivalent in 2014 of which ≈80% stems from desflurane. We also report on halothane, a previously widely used anesthetic. Its global mean mole fraction has declined to 9.2ppq (parts per quadrillion, 10−15) by 2014. However, the inferred present usage is still 280 ±120t yr−1.

#### Abrupt reversal in emissions and atmospheric abundance of HCFC-133a (CF3CH2Cl) (2015) [link]

Authors: Vollmer, Rigby, Laube, Henne, Rhee, Gooch, Wenger, Young, Steele, Langenfelds, Brenninkmeijer, Wang, Ou-Yang, Wyss, Hill, Oram, Krummel, Schoenenberger, Zellweger, Fraser, Sturges, O’Doherty, Reimann

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

#### Simulation of atmospheric N₂O with GEOS-Chem and its adjoint: evaluation of observational constraints (2015) [link]

Authors: Wells, Millet, Bousserez, Henze, Chaliyakunnel, Griffis, Luan, Dlugokencky, Prinn, O’Doherty, Weiss, Dutton, Elkins, Krummel, Langenfelds, Steele, Kort, Wofsy, Umezawa

No abstract available.

#### PFC Emissions from Detected Versus Nondetected Anode Effects in the Aluminum Industry (2015) [link]

Authors: Wong, Fraser, Lavoie, Kim

Perfluorinated carbon compounds (PFCs) CF4 and C2F6 are potent greenhouse gases that are generated in aluminum reduction cells during events known as anode effects (AEs). Since the 1990s, the aluminum industry has made considerable progress in reducing PFCs from conventionally defined and detected AEs. However in recent years, the industry has noted the presence of unaccounted PFCs that are generated outside the conventional AE definition. Two additional AE categories have been proposed, namely low-voltage, propagating AEs (LVP-AEs) and nonpropagating AEs (NP-AEs) that relate to continuous, background levels of PFC emissions. These unaccounted PFC phenomena may help explain the recent discrepancy between industry accounting and atmospheric measurements of global PFC emissions. Estimates from AGAGE, a global network of atmospheric observatories, suggest as much as 50% underaccounting of PFCs by the aluminum industry in the 2006–2010 period. The following work reviews this discrepancy and the potential role played by LVP-AEs and NP-AEs.