Abstract. Air samples collected at Cape

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

Abstract. Perfluorocarbons (PFCs) are very potent and long-lived greenhouse gases in the atmosphere, released predominantly during aluminium production and semiconductor manufacture. They have been targeted for emission controls under the United Nations Framework Convention on Climate Change. Here we present the first continuous records of the atmospheric abundance of CF4 (PFC-14), C2F6 (PFC-116) and C3F8 (PFC-218) from 1800 to 2014. The records are derived from high-precision measurements of PFCs in air extracted from polar firn or ice at six sites (DE08, DE08-2, DSSW20K, EDML, NEEM and South Pole) and air archive tanks and atmospheric air sampled from both hemispheres. We take account of the age characteristics of the firn and ice core air samples and demonstrate excellent consistency between the ice core, firn and atmospheric measurements. We present an inversion for global emissions from 1900 to 2014. We also formulate the inversion to directly infer emission factors for PFC emissions due to aluminium production prior to the 1980s. We show that 19th century atmospheric levels, before significant anthropogenic influence, were stable at 34.1 ± 0.3 ppt for CF4 and below detection limits of 0.002 and 0.01 ppt for C2F6 and C3F8, respectively. We find a significant peak in CF4 and C2F6 emissions around 1940, most likely due to the high demand for aluminium during World War II, for example for construction of aircraft, but these emissions were nevertheless much lower than in recent years. The PFC emission factors for aluminium production in the early 20th century were significantly higher than today but have decreased since then due to improvements and better control of the smelting process. Mitigation efforts have led to decreases in emissions from peaks in 1980 (CF4) or early-to-mid-2000s (C2F6 and C3F8) despite the continued increase in global aluminium production; however, these decreases in emissions appear to have recently halted. We see a temporary reduction of around 15 % in CF4 emissions in 2009, presumably associated with the impact of the global financial crisis on aluminium and semiconductor production.

The Southern Hemisphere ADditional OZonesonde (SHADOZ) network was assembled to validate a new generation of ozone‐monitoring satellites and to better characterize the vertical structure of tropical ozone in the troposphere and stratosphere. Beginning with nine stations in 1998, more than 7,000 ozone and P‐T‐U profiles are available from 14 SHADOZ sites that have operated continuously for at least a decade. We analyze ozone profiles from the recently reprocessed SHADOZ data set that is based on adjustments for inconsistencies caused by varying ozonesonde instruments and operating techniques. First, sonde‐derived total ozone column amounts are compared to the overpasses from the Earth Probe/Total Ozone Mapping Spectrometer, Ozone Monitoring Instrument, and Ozone Mapping and Profiler Suite satellites that cover 1998–2016. Second, characteristics of the stratospheric and tropospheric columns are examined along with ozone structure in the tropical tropopause layer (TTL). We find that (1) relative to our earlier evaluations of SHADOZ data, in 2003, 2007, and 2012, sonde‐satellite total ozone column offsets at 12 stations are 2% or less, a significant improvement; (2) as in prior studies, the 10 tropical SHADOZ stations, defined as within ±19° latitude, display statistically uniform stratospheric column ozone, 229 ± 3.9 DU (Dobson units), and a tropospheric zonal wave‐one pattern with a 14 DU mean amplitude; (3) the TTL ozone column, which is also zonally uniform, masks complex vertical structure, and this argues against using satellites for lower stratospheric ozone trends; and (4) reprocessing has led to more uniform stratospheric column amounts across sites and reduced bias in stratospheric profiles. As a consequence, the uncertainty in total column ozone now averages 5%.