1. Perfluorocyclobutane (PFC-318, c-C4F8) in the global atmosphere
- Author
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Muhle, Jens, Trudinger, Cathy M, Western, Luke M, Rigby, Matthew, Vollmer, Martin K, Park, Sunyoung, Manning, Alistair J, Say, Daniel, Ganesan, Anita, Steele, L Paul, Ivy, Diane J, Arnold, Tim, Li, Shanlan, Stohl, Andreas, Harth, Christina M, Salameh, Peter K, McCulloch, Archie, O'Doherty, Simon, Park, Mi-Kyung, Jo, Chun Ok, Young, Dickon, Stanley, Kieran M, Krummel, Paul B, Mitrevski, Blagoj, Hermansen, Ove, Lunder, Chris, Evangeliou, Nikolaos, Yao, Bo, Kim, Jooil, Hmiel, Benjamin, Buizert, Christo, Petrenko, Vasilii V, Arduini, Jgor, Maione, Michela, Etheridge, David M, Michalopoulou, Eleni, Czerniak, Mike, Severinghaus, Jeffrey P, Reimann, Stefan, Simmonds, Peter G, Fraser, Paul J, Prinn, Ronald G, and Weiss, Ray F
- Subjects
Astronomical and Space Sciences ,Atmospheric Sciences ,Meteorology & Atmospheric Sciences - Abstract
Abstract. We reconstruct atmospheric abundances of the potentgreenhouse gas c-C4F8 (perfluorocyclobutane, perfluorocarbonPFC-318) from measurements of in situ, archived, firn, and aircraft airsamples with precisions of ∼1 %–2 % reported on the SIO-14gravimetric calibration scale. Combined with inverse methods, we found near-zero atmospheric abundances from the early 1900s to the early 1960s, afterwhich they rose sharply, reaching 1.66 ppt (parts per trillion dry-air molefraction) in 2017. Global c-C4F8 emissions rose from near zero inthe 1960s to 1.2±0.1 (1σ) Gg yr−1 in the late 1970s tolate 1980s, then declined to 0.77±0.03 Gg yr−1 in the mid-1990sto early 2000s, followed by a rise since the early 2000s to 2.20±0.05 Gg yr−1 in 2017. These emissions are significantly larger thaninventory-based emission estimates. Estimated emissions from eastern Asiarose from 0.36 Gg yr−1 in 2010 to 0.73 Gg yr−1 in 2016 and 2017,31 % of global emissions, mostly from eastern China. We estimateemissions of 0.14 Gg yr−1 from northern and central India in 2016 andfind evidence for significant emissions from Russia. In contrast, recentemissions from northwestern Europe and Australia are estimated to be small(≤1 % each). We suggest that emissions from China, India, and Russiaare likely related to production of polytetrafluoroethylene (PTFE,“Teflon”) and other fluoropolymers and fluorochemicals that are based onthe pyrolysis of hydrochlorofluorocarbon HCFC-22 (CHClF2) in whichc-C4F8 is a known by-product. The semiconductor sector, wherec-C4F8 is used, is estimated to be a small source, at least inSouth Korea, Japan, Taiwan, and Europe. Without an obvious correlation withpopulation density, incineration of waste-containing fluoropolymers isprobably a minor source, and we find no evidence of emissions fromelectrolytic production of aluminum in Australia. While many possibleemissive uses of c-C4F8 are known and though we cannotcategorically exclude unknown sources, the start of significant emissionsmay well be related to the advent of commercial PTFE production in 1947.Process controls or abatement to reduce the c-C4F8 by-product wereprobably not in place in the early decades, explaining the increase inemissions in the 1960s and 1970s. With the advent of by-product reportingrequirements to the United Nations Framework Convention on Climate Change(UNFCCC) in the 1990s, concern about climate change and product stewardship,abatement, and perhaps the collection of c-C4F8 by-product for usein the semiconductor industry where it can be easily abated, it isconceivable that emissions in developed countries were stabilized and thenreduced, explaining the observed emission reduction in the 1980s and 1990s.Concurrently, production of PTFE in China began to increase rapidly. Withoutemission reduction requirements, it is plausible that global emissions todayare dominated by China and other developing countries. We predict thatc-C4F8 emissions will continue to rise and that c-C4F8will become the second most important emitted PFC in terms ofCO2-equivalent emissions within a year or two. The 2017 radiativeforcing of c-C4F8 (0.52 mW m−2) is small but emissions ofc-C4F8 and other PFCs, due to their very long atmosphericlifetimes, essentially permanently alter Earth's radiative budget and shouldbe reduced. Significant emissions inferred outside of the investigatedregions clearly show that observational capabilities and reportingrequirements need to be improved to understand global and country-scaleemissions of PFCs and other synthetic greenhouse gases and ozone-depletingsubstances.
- Published
- 2019