scholarly journals Abundances, emissions, and loss processes of the long-lived and potent greenhouse gas octafluorooxolane (octafluorotetrahydrofuran, <i>c</i>-C<sub>4</sub>F<sub>8</sub>O) in the atmosphere

2019 ◽  
Vol 19 (6) ◽  
pp. 3481-3492 ◽  
Author(s):  
Martin K. Vollmer ◽  
François Bernard ◽  
Blagoj Mitrevski ◽  
L. Paul Steele ◽  
Cathy M. Trudinger ◽  
...  
Keyword(s):  
Greenhouse Gas ◽  
Transport Model ◽  
Atmospheric Transport ◽  
Semiconductor Industry ◽  
Infrared Absorption Spectrum ◽  
Full Range ◽  
Ambient Air ◽  
Atmospheric Measurements ◽  
Air Samples ◽  
Atmospheric Observations

Abstract. The first atmospheric observations of octafluorooxolane (octafluorotetrahydrofuran, c-C4F8O), a persistent greenhouse gas, are reported. In addition, a complementary laboratory study of its most likely atmospheric loss processes, its infrared absorption spectrum, and global warming potential (GWP) are reported. First atmospheric measurements of c-C4F8O are provided from the Cape Grim Air Archive (41∘ S, Tasmania, Australia, 1978–present), supplemented by two firn air samples from Antarctica, in situ measurements of ambient air at Aspendale, Victoria (38∘ S), and a few archived air samples from the Northern Hemisphere. The atmospheric abundance in the Southern Hemisphere has monotonically grown over the past decades and leveled at 74 ppq (parts per quadrillion, femtomole per mole in dry air) by 2015–2018. The growth rate of c-C4F8O has decreased from a maximum in 2004 of 4.0 to <0.25 ppq yr−1 in 2017 and 2018. Using a 12-box atmospheric transport model, globally averaged yearly emissions and abundances of c-C4F8O are calculated for 1951–2018. Emissions, which we speculate to derive predominantly from usage of c-C4F8O as a solvent in the semiconductor industry, peaked at 0.15 (±0.04, 2σ) kt yr−1 in 2004 and have since declined to <0.015 kt yr−1 in 2017 and 2018. Cumulative emissions over the full range of our record amount to 2.8 (2.4–3.3) kt, which correspond to 34 Mt of CO2-equivalent emissions. Infrared and ultraviolet absorption spectra for c-C4F8O as well as the reactive channel rate coefficient for the O(1D) + c-C4F8O reaction were determined from laboratory studies. On the basis of these experiments, a radiative efficiency of 0.430 W m−2 ppb−1 (parts per billion, nanomol mol−1) was determined, which is one of the largest found for synthetic greenhouse gases. The global annually averaged atmospheric lifetime, including mesospheric loss, is estimated to be >3000 years. GWPs of 8975, 12 000, and 16 000 are estimated for the 20-, 100-, and 500-year time horizons, respectively.

scholarly journals Abundances, emissions, and loss processes of the long-lived and potent greenhouse gas octafluorooxolane (octafluorotetrahydrofuran, <i>c</i>-C<sub>4</sub>F<sub>8</sub>O) in the atmosphere

2018 ◽  
Author(s):  
Martin K. Vollmer ◽  
François Bernard ◽  
Blagoj Mitrevski ◽  
L. Paul Steele ◽  
Cathy M. Trudinger ◽  
...  
Keyword(s):  
Growth Rate ◽  
Greenhouse Gas ◽  
Infrared Absorption Spectrum ◽  
Ambient Air ◽  
Atmospheric Measurements ◽  
Air Samples ◽  
Dry Air ◽  
Atmospheric Loss ◽  
Cape Grim

Abstract. The first observations of octafluorooxolane (octafluorotetrahydrofuran, c-C4F8O), a persistent greenhouse gas, in the atmosphere are reported. In addition, a complimentary laboratory study of its most likely atmospheric loss processes and infrared absorption spectrum and global warming potential (GWP) are reported. First atmospheric measurements of c-C4F8O are provided from the Cape Grim Air Archive (41° S, Tasmania, Australia, 1978–present), supplemented by two firn air samples from Antarctica, in situ measurements of ambient air at Aspendale, Victoria (38° S), and a few archived air samples from the Northern Hemisphere. Atmospheric abundances in the Southern Hemisphere have reached 74 ppq (parts per quadrillion, femtomol mol-1 in dry air) by 2017. However its growth rate has decreased from a maximum in 2004 of 4.3 ppq yr-1 to

scholarly journals Atmospheric histories and emissions of chlorofluorocarbons CFC-13 (CClF<sub>3</sub>), ΣCFC-114 (C<sub>2</sub>Cl<sub>2</sub>F<sub>4</sub>), and CFC-115 (C<sub>2</sub>ClF<sub>5</sub>)

2018 ◽  
Vol 18 (2) ◽  
pp. 979-1002 ◽  
Author(s):  
Martin K. Vollmer ◽  
Dickon Young ◽  
Cathy M. Trudinger ◽  
Jens Mühle ◽  
Stephan Henne ◽  
...  
Keyword(s):  
Mole Fraction ◽  
Transport Model ◽  
Atmospheric Transport ◽  
Global Analysis ◽  
Large Fraction ◽  
Ambient Air ◽  
Atmospheric Observations ◽  
Transport Patterns ◽  
The 1960S ◽  
Global Emissions

Abstract. Based on observations of the chlorofluorocarbons CFC-13 (chlorotrifluoromethane), ΣCFC-114 (combined measurement of both isomers of dichlorotetrafluoroethane), and CFC-115 (chloropentafluoroethane) in atmospheric and firn samples, we reconstruct records of their tropospheric histories spanning nearly 8 decades. These compounds were measured in polar firn air samples, in ambient air archived in canisters, and in situ at the AGAGE (Advanced Global Atmospheric Gases Experiment) network and affiliated sites. Global emissions to the atmosphere are derived from these observations using an inversion based on a 12-box atmospheric transport model. For CFC-13, we provide the first comprehensive global analysis. This compound increased monotonically from its first appearance in the atmosphere in the late 1950s to a mean global abundance of 3.18 ppt (dry-air mole fraction in parts per trillion, pmol mol−1) in 2016. Its growth rate has decreased since the mid-1980s but has remained at a surprisingly high mean level of 0.02 ppt yr−1 since 2000, resulting in a continuing growth of CFC-13 in the atmosphere. ΣCFC-114 increased from its appearance in the 1950s to a maximum of 16.6 ppt in the early 2000s and has since slightly declined to 16.3 ppt in 2016. CFC-115 increased monotonically from its first appearance in the 1960s and reached a global mean mole fraction of 8.49 ppt in 2016. Growth rates of all three compounds over the past years are significantly larger than would be expected from zero emissions. Under the assumption of unchanging lifetimes and atmospheric transport patterns, we derive global emissions from our measurements, which have remained unexpectedly high in recent years: mean yearly emissions for the last decade (2007–2016) of CFC-13 are at 0.48 ± 0.15 kt yr−1 (> 15 % of past peak emissions), of ΣCFC-114 at 1.90 ± 0.84 kt yr−1 (∼ 10 % of peak emissions), and of CFC-115 at 0.80 ± 0.50 kt yr−1 (> 5 % of peak emissions). Mean yearly emissions of CFC-115 for 2015–2016 are 1.14 ± 0.50 kt yr−1 and have doubled compared to the 2007–2010 minimum. We find CFC-13 emissions from aluminum smelters but if extrapolated to global emissions, they cannot account for the lingering global emissions determined from the atmospheric observations. We find impurities of CFC-115 in the refrigerant HFC-125 (CHF2CF3) but if extrapolated to global emissions, they can neither account for the lingering global CFC-115 emissions determined from the atmospheric observations nor for their recent increases. We also conduct regional inversions for the years 2012–2016 for the northeastern Asian area using observations from the Korean AGAGE site at Gosan and find significant emissions for ΣCFC-114 and CFC-115, suggesting that a large fraction of their global emissions currently occur in northeastern Asia and more specifically on the Chinese mainland.

scholarly journals Verification of greenhouse gas emission reductions: the prospect of atmospheric monitoring in polluted areas

2011 ◽  
Vol 369 (1943) ◽  
pp. 1906-1924 ◽  
Author(s):  
Ingeborg Levin ◽  
Samuel Hammer ◽  
Elke Eichelmann ◽  
Felix R. Vogel
Keyword(s):  
Greenhouse Gas Emissions ◽  
Greenhouse Gas ◽  
Catchment Area ◽  
Greenhouse Gas Emission ◽  
Atmospheric Transport ◽  
Atmospheric Measurements ◽  
Transport Modelling ◽  
Gas Emissions ◽  
Atmospheric Transport Modelling

Independent verification of greenhouse gas emissions reporting is a legal requirement of the Kyoto Protocol, which has not yet been fully accomplished. Here, we show that dedicated long-term atmospheric measurements of greenhouse gases, such as carbon dioxide (CO 2 ) and methane (CH 4 ), continuously conducted at polluted sites can provide the necessary tool for this undertaking. From our measurements at the semi-polluted Heidelberg site in the upper Rhine Valley, we find that in the catchment area CH 4 emissions decreased on average by 32±6% from the second half of the 1990s until the first half of the 2000s, but the observed long-term trend of emissions is considerably smaller than that previously reported for southwest Germany. In contrast, regional fossil fuel CO 2 levels, estimated from high-precision 14 CO 2 observations, do not show any significant decreasing trend since 1986, in agreement with the reported emissions for this region. In order to provide accurate verification, these regional measurements would best be accompanied by adequate atmospheric transport modelling as required to precisely determine the relevant catchment area of the measurements. Furthermore, reliable reconciliation of reported emissions will only be possible if these are known at high spatial resolution in the catchment area of the observations. This information should principally be available in all countries that regularly report their greenhouse gas emissions to the United Nations Framework Convention on Climate Change.

scholarly journals Inverse modelling of CF<sub>4</sub> and NF<sub>3</sub> emissions in East Asia

2018 ◽  
Vol 18 (18) ◽  
pp. 13305-13320 ◽  
Author(s):  
Tim Arnold ◽  
Alistair J. Manning ◽  
Jooil Kim ◽  
Shanlan Li ◽  
Helen Webster ◽  
...  
Keyword(s):  
South Korea ◽  
East Asia ◽  
Transport Model ◽  
Atmospheric Transport ◽  
Atmospheric Gases ◽  
Atmospheric Measurements ◽  
Small Uncertainty ◽  
Measurement Location ◽  
Atmospheric Transport Model ◽  
Good Agreement

Abstract. Decadal trends in the atmospheric abundances of carbon tetrafluoride (CF4) and nitrogen trifluoride (NF3) have been well characterised and have provided a time series of global total emissions. Information on locations of emissions contributing to the global total, however, is currently poor. We use a unique set of measurements between 2008 and 2015 from the Gosan station, Jeju Island, South Korea (part of the Advanced Global Atmospheric Gases Experiment network), together with an atmospheric transport model, to make spatially disaggregated emission estimates of these gases in East Asia. Due to the poor availability of good prior information for this study, our emission estimates are largely influenced by the atmospheric measurements. Notably, we are able to highlight emission hotspots of NF3 and CF4 in South Korea due to the measurement location. We calculate emissions of CF4 to be quite constant between the years 2008 and 2015 for both China and South Korea, with 2015 emissions calculated at 4.3±2.7 and 0.36±0.11 Gg yr−1, respectively. Emission estimates of NF3 from South Korea could be made with relatively small uncertainty at 0.6±0.07 Gg yr−1 in 2015, which equates to ∼1.6 % of the country's CO2 emissions. We also apply our method to calculate emissions of CHF3 (HFC-23) between 2008 and 2012, for which our results find good agreement with other studies and which helps support our choice in methodology for CF4 and NF3.

scholarly journals Rapid hydrolysis of tertiary isoprene nitrate efficiently removes NOx from the atmosphere

2020 ◽  
Vol 117 (52) ◽  
pp. 33011-33016
Author(s):  
Krystal T. Vasquez ◽  
John D. Crounse ◽  
Benjamin C. Schulze ◽  
Kelvin H. Bates ◽  
Alexander P. Teng ◽  
...  
Keyword(s):  
Transport Model ◽  
Deuterium Oxide ◽  
Ambient Air ◽  
Water Volume ◽  
Isomer Ratio ◽  
Atmospheric Measurements ◽  
Laboratory Findings ◽  
Loss Process ◽  
Isomer Distribution ◽  
Hydrolysis Of

The formation of a suite of isoprene-derived hydroxy nitrate (IHN) isomers during the OH-initiated oxidation of isoprene affects both the concentration and distribution of nitrogen oxide free radicals (NOx). Experiments performed in an atmospheric simulation chamber suggest that the lifetime of the most abundant isomer, 1,2-IHN, is shortened significantly by a water-mediated process (leading to nitric acid formation), while the lifetime of a similar isomer, 4,3-IHN, is not. Consistent with these chamber studies, NMR kinetic experiments constrain the 1,2-IHN hydrolysis lifetime to less than 10 s in deuterium oxide (D2O) at 298 K, whereas the 4,3-IHN isomer has been observed to hydrolyze much less efficiently. These laboratory findings are used to interpret observations of the IHN isomer distribution in ambient air. The IHN isomer ratio (1,2-IHN to 4,3-IHN) in a high NOx environment decreases rapidly in the afternoon, which is not explained using known gas-phase chemistry. When simulated with an observationally constrained model, we find that an additional loss process for the 1,2-IHN isomer with a time constant of about 6 h best explains our atmospheric measurements. Using estimates for 1,2-IHN Henry’s law constant and atmospheric liquid water volume, we show that condensed-phase hydrolysis of 1,2-IHN can account for this loss process. Simulations from a global chemistry transport model show that the hydrolysis of 1,2-IHN accounts for a substantial fraction of NOx lost (and HNO3 produced), resulting in large impacts on oxidant formation, especially over forested regions.

scholarly journals The Canadian atmospheric transport model for simulating greenhouse gas evolution on regional scales: GEM-MACH-GHG v.137-reg

2019 ◽  
Author(s):  
Jinwoong Kim ◽  
Saroja Polavarapu ◽  
Douglas Chan ◽  
Michael Neish
Keyword(s):  
Greenhouse Gas ◽  
Transport Model ◽  
Atmospheric Transport ◽  
Forecast Error ◽  
Regional Scale ◽  
The United States ◽  
Regional Model ◽  
Boreal Summer ◽  
Chemical Transport Model ◽  
Atmospheric Transport Model

Abstract. In this study, we present the development of a regional atmospheric transport model for greenhouse gas (GHG) simulation based on an operational weather forecast model and a chemical transport model at Environment and Climate Change Canada (ECCC), with the goal of improving our understanding of the high spatio-temporal resolution interaction between the atmosphere and surface GHG fluxes over Canada and the United States. The regional model uses 10 km × 10 km horizontal grid spacing and 80 vertical levels spanning the ground to 0.1 hPa. The lateral boundary conditions of meteorology and tracers are provided by the global transport model used for GHG simulation at ECCC. The performance of the regional model and added benefit of the regional model over our lower resolution global models is investigated in terms of modelled CO2 concentration and meteorological forecast quality for multiple seasons in 2015. We find that our regional model has the capability to simulate high spatial (horizontal and vertical) and temporal scales of atmospheric CO2 concentrations, based on comparisons to surface and aircraft observations. In addition, reduced bias and standard deviation of forecast error in boreal summer are obtained by the regional model. Better representation of model topography in the regional model reduces transport and representation errors significantly compared to the global model, especially in regions of complex topography, as revealed by the more precise and detailed structure of the CO2 diurnal cycle produced at observation sites and in model space. The new regional model will form the basis of a flux inversion system that estimates regional scale fluxes of GHGs over Canada.

scholarly journals The Canadian atmospheric transport model for simulating greenhouse gas evolution on regional scales: GEM–MACH–GHG v.137-reg

2020 ◽  
Vol 13 (1) ◽  
pp. 269-295
Author(s):  
Jinwoong Kim ◽  
Saroja M. Polavarapu ◽  
Douglas Chan ◽  
Michael Neish
Keyword(s):  
Greenhouse Gas ◽  
Transport Model ◽  
Atmospheric Transport ◽  
Forecast Error ◽  
Regional Scale ◽  
The United States ◽  
Regional Model ◽  
Boreal Summer ◽  
Spatiotemporal Resolution ◽  
Atmospheric Transport Model

Abstract. In this study, we present the development of a regional atmospheric transport model for greenhouse gas (GHG) simulation based on an operational weather forecast model and a chemical transport model at Environment and Climate Change Canada (ECCC), with the goal of improving our understanding of the high-spatiotemporal-resolution interaction between the atmosphere and surface GHG fluxes over Canada and the United States. The regional model uses 10 km×10 km horizontal grid spacing and 80 vertical levels spanning the ground to 0.1 hPa. The lateral boundary conditions of meteorology and tracers are provided by the global transport model used for GHG simulation at ECCC. The performance of the regional model and added benefit of the regional model over our lower-resolution global models is investigated in terms of modelled CO2 concentration and meteorological forecast quality for multiple seasons in 2015. We find that our regional model has the capability to simulate the high spatial (horizontal and vertical) and temporal scales of atmospheric CO2 concentrations based on comparisons to surface and aircraft observations. In addition, the bias and standard deviation of forecast error in boreal summer are reduced by the regional model. Better representation of model topography in the regional model results in improved simulation of the CO2 diurnal cycle compared to the global model at Walnut Grove, California. The new regional model will form the basis of a flux inversion system that estimates regional-scale fluxes of GHGs over Canada.

scholarly journals Global emissions of HFC-143a (CH<sub>3</sub>CF<sub>3</sub>) and HFC-32 (CH<sub>2</sub>F<sub>2</sub>) from in situ and air archive atmospheric observations

2014 ◽  
Vol 14 (17) ◽  
pp. 9249-9258 ◽  
Author(s):  
S. O'Doherty ◽  
M. Rigby ◽  
J. Mühle ◽  
D. J. Ivy ◽  
B. R. Miller ◽  
...  
Keyword(s):  
Growth Rate ◽  
Mole Fraction ◽  
Radiative Forcing ◽  
Transport Model ◽  
Atmospheric Transport ◽  
Lower Troposphere ◽  
Emission Rates ◽  
Global Emission ◽  
Atmospheric Observations

Abstract. High-frequency, in situ observations from the Advanced Global Atmospheric Gases Experiment (AGAGE), for the period 2003 to 2012, combined with archive flask measurements dating back to 1977, have been used to capture the rapid growth of HFC-143a (CH3CF3) and HFC-32 (CH2F2) mole fractions and emissions into the atmosphere. Here we report the first in situ global measurements of these two gases. HFC-143a and HFC-32 are the third and sixth most abundant hydrofluorocarbons (HFCs) respectively and they currently make an appreciable contribution to the HFCs in terms of atmospheric radiative forcing (1.7 ± 0.04 and 0.7 ± 0.02 mW m−2 in 2012 respectively). In 2012 the global average mole fraction of HFC-143a was 13.4 ± 0.3 ppt (1σ) in the lower troposphere and its growth rate was 1.4 ± 0.04 ppt yr−1; HFC-32 had a global mean mole fraction of 6.2 ± 0.2 ppt and a growth rate of 1.1 ± 0.04 ppt yr−1 in 2012. The extensive observations presented in this work have been combined with an atmospheric transport model to simulate global atmospheric abundances and derive global emission estimates. It is estimated that 23 ± 3 Gg yr−1 of HFC-143a and 21 ± 11 Gg yr−1 of HFC-32 were emitted globally in 2012, and the emission rates are estimated to be increasing by 7 ± 5% yr−1 for HFC-143a and 14 ± 11% yr−1 for HFC-32.

scholarly journals Assessment of an atmospheric transport model for annual inverse estimates of California greenhouse gas emissions

2017 ◽  
Vol 122 (3) ◽  
pp. 1901-1918 ◽  
Author(s):  
Justin E. Bagley ◽  
Seongeun Jeong ◽  
Xinguang Cui ◽  
Sally Newman ◽  
Jingsong Zhang ◽  
...  
Keyword(s):  
Greenhouse Gas Emissions ◽  
Greenhouse Gas ◽  
Transport Model ◽  
Atmospheric Transport ◽  
Gas Emissions ◽  
Atmospheric Transport Model

scholarly journals Global emissions of HFC-143a (CH<sub>3</sub>CF<sub>3</sub>) and HFC-32 (CH<sub>2</sub>F<sub>2</sub>) from in situ and air archive atmospheric observations

2014 ◽  
Vol 14 (5) ◽  
pp. 6471-6500 ◽  
Author(s):  
S. O'Doherty ◽  
M. Rigby ◽  
J. Mühle ◽  
D. J. Ivy ◽  
B. R. Miller ◽  
...  
Keyword(s):  
Growth Rate ◽  
Mole Fraction ◽  
Radiative Forcing ◽  
Transport Model ◽  
Atmospheric Transport ◽  
Lower Troposphere ◽  
Emission Rates ◽  
Global Emission ◽  
Atmospheric Observations

Abstract. High frequency, in situ observations from the Advanced Global Atmospheric Gases Experiment (AGAGE), for the period 2003 to 2012, combined with archive flask measurements dating back to 1977, have been used to capture the rapid growth of HFC-143a (CH3CF3) and HFC-32 (CH2F2) mole fractions and emissions into the atmosphere. Here we report the first in situ global measurements of these two gases. HFC-143a and HFC-32 are the third and sixth most abundant HFCs respectively and they currently make an appreciable contribution to the HFCs in terms of atmospheric radiative forcing (1.7 and 0.7 mW m2 in 2012, respectively). In 2012 the global average mole fraction of HFC-143a was 13.4 ± 0.3 ppt (1-sigma) in the lower troposphere and its growth rate was 1.4 ± 0.04 ppt yr−1; HFC-32 had a global mean mole fraction of 6.2 ± 0.2 ppt and a growth rate of 1.1 ± 0.04 ppt yr−1 in 2012. The extensive observations presented in this work have been combined with an atmospheric transport model to simulate global atmospheric abundances and derive global emission estimates. It is estimated that 23 ± 3 Gg yr−1 of HFC-143a and 21 ± 11 Gg yr−1 of HFC-32 were emitted globally in 2012, and the emission rates are estimated to be increasing 7 ± 5% yr−1 for HFC-143a and 14 ± 11% yr−1 for HFC-32.

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