Atmospheric histories and global emissions of the anthropogenic hydrofluorocarbons HFC-365mfc, HFC-245fa, HFC-227ea, and HFC-236fa

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.