Atmospheric histories and growth trends of C4F10, C5F12, C6F14, C7F16 and C8F18

Abstract

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 10(12)) 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 10(15)) 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.