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

O&,apos,Doherty, S.,Rigby, M.,Mü,hle, J.,Ivy, D. J.,Miller, B. R.,Young, D.,Simmonds, P. G.,Reimann, S.,Vollmer, M. K.,Krummel, P. B.,Fraser, P. J.,Steele, L. P.,Dunse, B.,Salameh, P. K.,Harth, Copernicus GmbH 2014 Atmospheric chemistry and physics Vol.14 No.17

<P>Abstract. 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. </P>

Hydrochlorofluorocarbon and hydrofluorocarbon emissions in East Asia determined by inverse modeling

Stohl, A.,Kim, J.,Li, S.,O&,apos,Doherty, S.,Mü,hle, J.,Salameh, P. K.,Saito, T.,Vollmer, M. K.,Wan, D.,Weiss, R. F.,Yao, B.,Yokouchi, Y.,Zhou, L. X. Copernicus GmbH 2010 Atmospheric Chemistry and Physics Vol.10 No.8

<P>Abstract. 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%). </P>

Toward resolving the budget discrepancy of ozone-depleting carbon tetrachloride (CCl4): an analysis of top-down emissions from China

Park, Sunyoung,Li, Shanlan,Mü,hle, Jens,O&,apos,Doherty, Simon,Weiss, Ray F.,Fang, Xuekun,Reimann, Stefan,Prinn, Ronald G. Copernicus GmbH 2018 Atmospheric chemistry and physics Vol.18 No.16

<P>Abstract. Carbon tetrachloride (CCl4) is a first-generation ozone-depleting substance, and its emissive use and production were globally banned by the Montreal Protocol with a 2010 phase-out; however, production and consumption for non-dispersive use as a chemical feedstock and as a process agent are still allowed. This study uses the high frequency and magnitude of CCl4 pollution events from an 8-year real-time atmospheric measurement record obtained at Gosan station (a regional background monitoring site in East Asia) to present evidence of significant unreported emissions of CCl4. Top-down emissions of CCl4 amounting to 23.6±7.1 Gg yr−1 from 2011 to 2015 are estimated for China, in contrast to the most recently reported, post-2010, Chinese bottom-up emissions of 4.3-5.2 Gg yr−1. The missing emissions (∼19 Gg yr−1) for China contribute to approximately 54 % of global CCl4 emissions. It is also shown that 89 %±6 % of CCl4 enhancements observed at Gosan are related to CCl4 emissions from the production of CH3Cl, CH2Cl2, CHCl3 and C2Cl4 and its usage as a feedstock and process agent in chemical manufacturing industries. Specific sources and processes are identified using statistical methods, and it is considered highly unlikely that CCl4 is emitted by dispersive uses such as old landfills, contaminated soils and solvent usage. It is thus crucial to implement technical improvements and better regulation strategies to reduce evaporative losses of CCl4 occurring at the factory and/or process levels. </P>

Global and regional emissions estimates of 1,1-difluoroethane (HFC-152a, CH3CHF2) from in situ and air archive observations

Simmonds, P. G.,Rigby, M.,Manning, A. J.,Lunt, M. F.,O&,apos,Doherty, S.,McCulloch, A.,Fraser, P. J.,Henne, S.,Vollmer, M. K.,Mü,hle, J.,Weiss, R. F.,Salameh, P. K.,Young, D.,Reimann, S.,Wenger Copernicus GmbH 2016 Atmospheric Chemistry and Physics Vol.16 No.1

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

The HadGEM2-ES implementation of CMIP5 centennial simulations

Jones, C. D.,Hughes, J. K.,Bellouin, N.,Hardiman, S. C.,Jones, G. S.,Knight, J.,Liddicoat, S.,O&,apos,Connor, F. M.,Andres, R. J.,Bell, C.,Boo, K.-O.,Bozzo, A.,Butchart, N.,Cadule, P.,Corbin, K. D. Copernicus GmbH 2011 Geoscientific model development Vol.4 No.3

<P><p><strong>Abstract.</strong> The scientific understanding of the Earth's climate system, including the central question of how the climate system is likely to respond to human-induced perturbations, is comprehensively captured in GCMs and Earth System Models (ESM). Diagnosing the simulated climate response, and comparing responses across different models, is crucially dependent on transparent assumptions of how the GCM/ESM has been driven - especially because the implementation can involve subjective decisions and may differ between modelling groups performing the same experiment. This paper outlines the climate forcings and setup of the Met Office Hadley Centre ESM, HadGEM2-ES for the CMIP5 set of centennial experiments. We document the prescribed greenhouse gas concentrations, aerosol precursors, stratospheric and tropospheric ozone assumptions, as well as implementation of land-use change and natural forcings for the HadGEM2-ES historical and future experiments following the Representative Concentration Pathways. In addition, we provide details of how HadGEM2-ES ensemble members were initialised from the control run and how the palaeoclimate and AMIP experiments, as well as the 'emission-driven' RCP experiments were performed.</p> </P>

Inverse modelling of CF4 and NF3 emissions in East Asia

Arnold, Tim,Manning, Alistair J.,Kim, Jooil,Li, Shanlan,Webster, Helen,Thomson, David,Mü,hle, Jens,Weiss, Ray F.,Park, Sunyoung,O&,apos,Doherty, Simon Copernicus GmbH 2018 Atmospheric Chemistry and Physics Vol.18 No.18

<P>Abstract. Decadal trends in the atmospheric abundances of carbon tetrafluoride (CF4) and nitrogen trifluoride (NF3) have been well characterised and have provided a time series of global total emissions. Information on locations of emissions contributing to the global total, however, is currently poor. We use a unique set of measurements between 2008 and 2015 from the Gosan station, Jeju Island, South Korea (part of the Advanced Global Atmospheric Gases Experiment network), together with an atmospheric transport model, to make spatially disaggregated emission estimates of these gases in East Asia. Due to the poor availability of good prior information for this study, our emission estimates are largely influenced by the atmospheric measurements. Notably, we are able to highlight emission hotspots of NF3 and CF4 in South Korea due to the measurement location. We calculate emissions of CF4 to be quite constant between the years 2008 and 2015 for both China and South Korea, with 2015 emissions calculated at 4.3±2.7 and 0.36±0.11 Gg yr−1, respectively. Emission estimates of NF3 from South Korea could be made with relatively small uncertainty at 0.6±0.07 Gg yr−1 in 2015, which equates to ∼1.6 % of the country's CO2 emissions. We also apply our method to calculate emissions of CHF3 (HFC-23) between 2008 and 2012, for which our results find good agreement with other studies and which helps support our choice in methodology for CF4 and NF3. </P>

Characterization of uncertainties in atmospheric trace gas inversions using hierarchical Bayesian methods

Ganesan, A. L.,Rigby, M.,Zammit-Mangion, A.,Manning, A. J.,Prinn, R. G.,Fraser, P. J.,Harth, C. M.,Kim, K.-R.,Krummel, P. B.,Li, S.,Mü,hle, J.,O&,apos,Doherty, S. J.,Park, S.,Salameh, P. K.,Ste Copernicus GmbH 2014 Atmospheric chemistry and physics Vol.14 No.8

<P>Abstract. 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. </P>

History of atmospheric SF6 from 1973 to 2008

Rigby, M.,Mü,hle, J.,Miller, B. R.,Prinn, R. G.,Krummel, P. B.,Steele, L. P.,Fraser, P. J.,Salameh, P. K.,Harth, C. M.,Weiss, R. F.,Greally, B. R.,O&,apos,Doherty, S.,Simmonds, P. G.,Vollmer, M Copernicus GmbH 2010 Atmospheric Chemistry and Physics Vol.10 No.21

<P>Abstract. 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. </P>