Perfluorocyclobutane (PFC-318, <i>c</i>-C<sub>4</sub>F<sub>8</sub>) in the global atmosphere

We reconstruct atmospheric abundances of the potent greenhouse gas span classCombining double low line inline-formula span classCombining double low line inline-formula perfluorocyclobutane, perfluorocarbon PFC-318) from measurements of in situ, archived, firn, and aircraft air samples with precisions of span classCombining double low line inline-formula reported on the SIO-14 gravimetric calibration scale. Combined with inverse methods, we found near-zero atmospheric abundances from the early 1900s to the early 1960s, after which they rose sharply, reaching 1.66ppt (parts per trillion dry-air mole fraction) in 2017. Global span classCombining double low line inline-formula span classCombining double low line inline-formula emissions rose from near zero in the 1960s to span classCombining double low line inline-formula (1span classCombining double low line inline-formula gyrspan classCombining double low line inline-formula in the late 1970s to late 1980s, then declined to span classCombining double low line inline-formula classCombining double low line inline-formula in the mid-1990s to early 2000s, followed by a rise since the early 2000s to span classCombining double low line inline-formula 2.20±0.05 Ggyrspan classCombining double low line inline-formula in 2017. These emissions are significantly larger than inventory-based emission estimates. Estimated emissions from eastern Asia rose from 0.36Ggyrspan classCombining double low line inline-formula in 2010 to 0.73Ggyrspan classCombining double low line inline-formula in 2016 and 2017, 31% of global emissions, mostly from eastern China. We estimate emissions of 0.14Ggyrspan classCombining double low line inline-formula from northern and central India in 2016 and find evidence for significant emissions from Russia. In contrast, recent emissions from northwestern Europe and Australia are estimated to be small (span classCombining double low line inline-formula % each). We suggest that emissions from China, India, andspan idCombining double low line page10336 Russia are likely related to production of polytetrafluoroethylene (PTFE, Teflon ) and other fluoropolymers and fluorochemicals that are based on the pyrolysis of hydrochlorofluorocarbon HCFC-22 (span classCombining double low line inline-formula) in which span classCombining double low line inline-formula classCombining double low line inline-formula is a known by-product. The semiconductor sector, where span classCombining double low line inline-formula span classCombining double low line inline-formula is used, is estimated to be a small source, at least in South Korea, Japan, Taiwan, and Europe. Without an obvious correlation with population density, incineration of waste-containing fluoropolymers is probably a minor source, and we find no evidence of emissions from electrolytic production of aluminum in Australia. While many possible emissive uses of span classCombining double low line inline-formula span classCombining double low line inline-formula are known and though we cannot categorically exclude unknown sources, the start of significant emissions may well be related to the advent of commercial PTFE production in 1947. Process controls or abatement to reduce the span classCombining double low line inline-formula span classCombining double low line inline-formula by-product were probably not in place in the early decades, explaining the increase in emissions in the 1960s and 1970s. With the advent of by-product reporting requirements 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 span classCombining double low line inline-formula span classCombining double low line inline-formula by-product for use in the semiconductor industry where it can be easily abated, it is conceivable that emissions in developed countries were stabilized and then reduced, explaining the observed emission reduction in the 1980s and 1990s. Concurrently, production of PTFE in China began to increase rapidly. Without emission reduction requirements, it is plausible that global emissions today are dominated by China and other developing countries. We predict that span classCombining double low line inline-formula span classCombining double low line inline-formula emissions will continue to rise and that span classCombining double low line inline-formula span classCombining double low line inline-formula will become the second most important emitted PFC in terms of span classCombining double low line inline-formula equivalent emissions within a year or two. The 2017 radiative forcing of span classCombining double low line inline-formula span classCombining double low line inline-formula 0.52mWmspan classCombining double low line inline-formula) is small but emissions of span classCombining double low line inline-formula span classCombining double low line inline-formula and other PFCs, due to their very long atmospheric lifetimes, essentially permanently alter Earth's radiative budget and should be reduced. Significant emissions inferred outside of the investigated regions clearly show that observational capabilities and reporting requirements need to be improved to understand global and country-scale emissions of PFCs and other synthetic greenhouse gases and ozone-depleting substances.United States. National Aeronautics and Space Administration (Grant NNX07AE89G)United States. National Aeronautics and Space Administration (Grant NNX07AF09G)United States. National Aeronautics and Space Administration (Grant NNX07AE87G)Great Britain. Department for Business, Energy & Industrial Strategy (Grant 1028/06/2015)United States. National Oceanic and Atmospheric Administration (Grant RA-133-R15-CN-0008)National Natural Science Foundation of China (Grant 41575114)National Science Foundation (U.S.) (Grant ARC-1203779)National Science Foundation (U.S.) (Grant ARC-1204084)Natural Environment Research Council (Great Britain) (Grant NE/I027282/1

Spitzer observations of two TW Hydrae association brown dwarfs

We present Spitzer Space Telescope observations of two TW Hydrae association brown dwarfs, 2MASSW J1207334-393254 and 2MASSW J1139511-315921, in the IRAC and MIPS 24 mm bands. On the basis of their IRAC colors, we have classified them as classical and weak-line T Tauri stars, respectively. For 2MASSW J1207334-393254, we have found that a flat-disk model fits the data very well. This brown dwarf shows the presence of warm (T >= 100 K) circumstellar dust close (R <= 0.2 AU) to it and does not display any signs of cleansing of dust within several AU of the star. In comparison with other TWA members that show excess in IR, we suggest that there exists a different disk evolution/dust processing mechanism for stellar and substellar objects. The star 2MASSW J1139511-315921 does not show any significant excess in any of the IRAC bands but a small one at 24 mm, which is not significant enough to suggest the presence of warm dust around this star. It shows signs of dust cleansing in the inner several AU, similar to most of the other TWA members.Peer reviewe

The potential of 14CO in glacial ice as a tracer for past cosmic ray flux and atmospheric hydroxyl radical abundance

The amount of 14C-containing carbon monoxide (14CO) in glacial ice is determined by trapping of atmospheric 14CO into air bubbles in the ice and in situ cosmogenic production of 14CO in relatively shallow ice and firn. Earlier studies of 14CO in ice cores showed large disagreements with regard to rates of in situ cosmogenic production as well as with regard to whether 14CO produced in the firn layer is well retained or largely escapes to the atmosphere via the interconnected pore space. We have reviewed previously published work that included 14CO measurements in ice or firn air, and compared with our more recent high-precision measurements on very large ice and firn samples. The available evidence suggests that very little in situ cosmogenic 14CO is retained in the diffusive part of the firn (the upper ≈ 40 – 100m). In situ cosmogenic 14CO production rates below the firn diffusive zone are non-negligible, with production due to deeper-penetrating muons. At sites with low snow accumulation rates, the in situ cosmogenic 14CO component is expected to be larger than the trapped atmospheric component. This potentially allows to use ice core 14CO measurements from such sites to improve our understanding of past cosmic ray flux variations. In contrast, at sites with very high accumulation rates, trapped atmospheric 14CO is expected to be dominant over the in situ cosmogenic component. This potentially allows 14CO records from such sites to be used for reconstructions of past atmospheric hydroxyl radical (OH) variations

Anthropogenic Impacts on Atmospheric Carbonyl Sulfide Since the 19th Century Inferred From Polar Firn Air and Ice Core Measurements

Carbonyl sulfide (COS) was measured in firn air collected during seven different field campaigns carried out at four different sites in Greenland and Antarctica between 2001 and 2015. A Bayesian probabilistic statistical model is used to conduct multisite inversions and to reconstruct separate atmospheric histories for Greenland and Antarctica. The firn air inversions cover most of the 20th century over Greenland and extend back to the 19th century over Antarctica. The derived atmospheric histories are consistent with independent surface air time series data from the corresponding sites and the Antarctic ice core COS records during periods of overlap. Atmospheric COS levels began to increase over preindustrial levels starting in the 19th century, and the increase continued for much of the 20th century. Atmospheric COS peaked at higher than present-day levels around 1975 CE over Greenland and around 1987 CE over Antarctica. An atmosphere/surface ocean box model is used to investigate the possible causes of observed variability. The results suggest that changes in the magnitude and location of anthropogenic sources have had a strong influence on the observed atmospheric COS variability

Understanding the production and retention of in situ cosmogenic 14C in polar firn

Radiocarbon in CO 2 , CO and CH4 trapped in polar ice is of interest for dating of ice cores, studies of past solar activity and cosmic ray flux, as well as studies of the paleoatmospheric CH4 budget. The major difficulty with interpreting 14C measurements in ice cores stems from the fact that the measured 14C represents a combination of trapped paleoatmospheric 14C and 14C that is produced within the firn and ice lattice by secondary cosmic ray particles. This in situ cosmogenic 14C component in ice is at present poorly understood. Prior ice core 14C studies show conflicting results with regard to the retention of cosmogenic 14C in polar firn and partitioning of this 14C among CO 2 , CO and CH4. Our new study aims to comprehensively characterize the 14C of CO 2 , CO, and CH4 in both the air and the ice matrix throughout the firn column at Summit, Greenland. We will present measurements of 14C in Summit firn air (the first phase of this study) and discuss the implications for in situ cosmogenic 14C production and retention from initial modeling studies. Preliminary results from firn air indicate a 14CO increase with depth in the lock-in zone resulting from in situ production by muons, as well as a lock-in zone 14CO 2 bomb peak originating from nuclear testing in the late 1950s and early 1960s. A decrease in 14CH4 with depth is observed in the lock-in zone that is in agreement with observations of increasing atmospheric 14CH4 over the past several decades

Constraining the sources of the CH4 increase during the Oldest Dryas-Bølling abrupt warming event using 14CH4 measurements from Taylor Glacier, Antarctica

Methane (CH4) is an important greenhouse gas with both natural and anthropogenic sources. Understanding how the natural CH4 budget has changed in response to changing climate in the past can provide insights on the sensitivity of the natural CH4 emissions to the current anthropogenic warming. Low latitude wetlands are the largest natural source of CH¬4 to the atmosphere. It has been proposed, however, that in the future warming world emissions from marine CH4 clathrates and Arctic permafrost might increase significantly. CH4 isotopes from ice cores in Greenland and Antarctica have been used to constrain the past CH¬4 budget. 14CH4 is unique in its ability to unambiguously distinguish between “old” CH4 sources (e.g. marine clathrate, geologic sources, old permafrost) and “modern” CH4 sources (e.g. tropical and boreal wetlands). We have successfully collected six large volume (~1000 kg) samples of ancient ice from Taylor Glacier, Antarctica that span the Oldest Dryas – Bølling (OD-BO) CH4 transition (~14.5ka). The OD-BO is the first large abrupt CH4 increase following the Last Glacial Maximum, with atmospheric CH4 increasing by ≈30% in the span of ≈ 200 years. All samples have recently been successfully measured for 14CH4, δ13C-CH4, and δD-CH4. 14CH4 measurements of accompanying procedural blanks show that effects from extraneous carbon addition during processing are small. Results are currently undergoing corrections for in-situ cosmogenic 14C based on 14CO measurements in the same samples. We will present the corrected 14CH4 results and preliminary interpretation with regard to causes of the OD-BO CH4 increase

Radioactive and stable paleoatmospheric methane isotopes across the last deglaciation and early holocene from Taylor Glacier, Antarctica

Methane (CH4) is an important greenhouse gas with both natural and anthropogenic sources. Understanding how the natural CH4 budget has changed in response to changing climate in the past can provide insights on the sensitivity of the natural CH4 emissions to the current anthropogenic warming. Both radioactive and stable CH4 isotopes (Delta14C-CH4, delta13C-CH4, and deltaD-CH4) from ice cores in Greenland and Antarctica have been used to constrain the past CH­4 budget. Among the CH4 isotopes, 14CH4 is unique in its ability to unambiguously distinguish between "old" CH4 sources (e.g. marine clathrate, geologic sources, old permafrost) and "modern" CH4 sources (e.g. tropical and boreal wetlands). During the 2013-2014 and 2014-2015 field seasons at Taylor Glacier, Antarctica, we have successfully extracted 12 large volume ice samples across the Last Deglaciation to early Holocene (20ka-8ka BP). All samples have been successfully measured for CH4 mole fraction ([CH4]), Delta14C-14CH4, delta13C-CH4, and deltaD-CH4. The [CH4], delta13C-CH4, and deltaD-CH4 measurements in our samples are consistent with existing delta13C-CH4, and deltaD-CH4 datasets from other deep cores, confirming the integrity of CH4 in Taylor Glacier ice. Preliminary 14CH4 results across the Oldest Dryas - Bølling (OD-BO) CH4 transition suggest that the 150 ppb [CH4] increase during the transition was caused by increased wetland emissions. Early Holocene and Last Glacial Maximum (LGM) 14C results are still undergoing corrections for in-situ cosmogenic 14C based on 14CO measurements in the same samples. We will present the corrected 14CH4 results from these samples and our preliminary interpretations with regard to the strength of old CH4 sources during the LGM and early Holocene. © 2016 American Geophysical UnionTuesday, 13 December 2016 08:00 - 12:20 Moscone South - Poster Hall PP21A Abrupt Climate Change: Causes, Mechanisms, and Consequences IV Poster